JP2016069501A - Resin composition comprising 4-methyl-1-pentene polymer and having excellent deodorant property, and molding prepared therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that has excellent persistence of deodorant property, and also has high deodorizing performance.SOLUTION: A resin composition comprises a 4-methyl-1-pentene polymer, and a deodorant comprising at least one compound selected from (A) a tetravalent metal phosphate compound and (B) a metal oxide or a composite metal oxide.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition containing a 4-methyl-1-pentene polymer and a specific deodorant, and a molded body comprising the same.

  Various resin materials that are lightweight, have excellent strength, and can be molded into various forms are widely used in various applications. These resin materials are required to be provided with various and advanced functions. In particular, the provision of deodorant performance tends to increase due to factors such as the recent trend toward cleanliness, and various materials are being studied.

  For example, Patent Documents 1 and 2 propose a method of imparting deodorizing properties to a molded article by applying a dispersion containing a deodorant and a binder component to the surface of a base material and then immobilizing the dispersion. However, in these methods, the surface is rubbed when the molded body is used, and the deodorant is dropped, or when the molded body is a fiber, the deodorant flows out by repeatedly washing, and the durability is poor. It was not practical.

  Therefore, as a method for preventing the deodorant from falling off from the base material, Patent Document 3 discloses a technique of kneading the deodorant into a resin material as a base material, but the surface of the deodorant is covered with the material. Therefore, there has been a problem that the deodorizing performance is lowered. Further, in Patent Document 4, in order to prevent the deodorization performance from deteriorating, the base material is made porous and the surface area of the base material is increased, so that the deodorant target gas and the deodorant in the base resin are easily brought into contact with each other. However, there is a room for improvement due to the problem that the mechanical strength of the base material is lowered due to the porous structure.

JP 2001-238777 A JP 2002-235280 A Japanese Patent Publication No. 7-12431 JP 2012-57004 A

  This invention is made | formed in view of the above background arts, Comprising: It aims at providing the resin composition which is excellent in deodorant sustainability and is high in deodorizing performance.

The present inventors have intensively studied, paying attention to the high gas permeability of 4-methyl-1-pentene polymer, and a resin containing 4-methyl-1-pentene polymer and a specific deodorant. The present inventors have found that the above problems can be solved by using a composition, and have completed the present invention.
That is, the present invention relates to the following [1] to [8].
[1] A resin composition comprising a 4-methyl-1-pentene polymer and a deodorant comprising at least one compound selected from the following (A) and (B).
(A) Tetravalent metal phosphate compound (B) Metal oxide or composite metal oxide [2] The content of the deodorant is 0.1 to 4-methyl-1-pentene polymer. The resin composition according to [1], which is 10% by weight.
[3] The resin composition according to [1] or [2], wherein the (A) tetravalent metal phosphate compound is zirconium phosphate.
[4] The resin composition according to any one of [1] to [3], wherein the (B) metal oxide or composite metal oxide is zinc oxide or a mixture of zinc oxide and silicon dioxide.
[5] A molded article comprising the resin composition according to any one of [1] to [4].
[6] A film comprising the resin composition according to any one of [1] to [4].
[7] An injection molded article comprising the resin composition according to any one of [1] to [4].
[8] A fiber comprising the resin composition according to any one of [1] to [4].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition and molded object which are excellent in deodorant sustainability and have high deodorizing performance can be provided.

Hereinafter, the present invention will be specifically described.
[Resin composition]
The resin composition of the present invention comprises a 4-methyl-1-pentene polymer,
(A) a tetravalent metal phosphate compound (B) and at least one deodorant selected from a metal oxide or a composite metal oxide.
The content of the deodorant is preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight with respect to the 4-methyl-1-pentene polymer.

[4-Methyl-1-pentene polymer]
The 4-methyl-1-pentene polymer used in the present invention polymerizes a monomer containing 4-methyl-1-pentene in the presence of a known olefin polymerization catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. It is manufactured by.
Examples of the 4-methyl-1-pentene polymer include a homopolymer of 4-methyl-1-pentene, or a copolymer of 4-methyl-1-pentene and other monomers. Any meaning is included as long as the effect is achieved.

  Examples of the other monomer copolymerized with 4-methyl-1-pentene include α-olefins having 3 to 20 carbon atoms excluding ethylene and 4-methyl-1-pentene. Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-octene, Examples include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene. Of these, α-olefins having 6 to 20 carbon atoms excluding 4-methyl-1-pentene are preferable, and α-olefins having 8 to 20 carbon atoms are more preferable. These α-olefins can be used singly or in combination of two or more.

When the 4-methyl-1-pentene polymer is a copolymer, the amount of the structural unit derived from 4-methyl-1-pentene constituting the copolymer is usually 80 mol% or more, preferably 90 mol. % Or more, more preferably 95 mol% or more.
The 4-methyl-1-pentene polymer used in the present invention preferably satisfies the following requirements (Ai) and (A-ii).

  (Ai) The melt flow rate (MFR; ASTM D1238, 260 ° C., 5 kgf) is usually 1 to 500 g / 10 min, preferably 2 to 300 g / 10 min, more preferably 3 to 200 g / 10 min. When the MFR is in the above range, it is preferable in terms of fluidity during molding.

(A-ii) Melting | fusing point (Tm) is 210-250 degreeC normally, Preferably it is 215-245 degreeC, More preferably, it is 220-240 degreeC, More preferably, it is 224-240 degreeC. When the melting point is 210 ° C. or higher, the obtained resin composition and the molded article have excellent heat resistance strength, and the resin composition obtained by having the melting point of 250 ° C. or less and the impact strength of the molded article are preferred.
In addition, melting | fusing point is measured as follows using a differential scanning calorimeter (DSC), for example. 3-7 mg of sample is sealed in an aluminum pan, heated from room temperature to 280 ° C. at 10 ° C./min, and the sample is held at 280 ° C. for 5 minutes to completely melt. It is then cooled to −50 ° C. at 10 ° C./min and placed at −50 ° C. for 5 minutes, after which the sample is heated again to 280 ° C. at 10 ° C./min. The peak temperature in the second heating test is adopted as the melting point (Tm).

  The 4-methyl-1-pentene polymer may be used alone or as a mixture of a plurality of 4-methyl-1-pentene polymers.

[Method for producing 4-methyl-1-pentene polymer]
The production of the 4-methyl-1-pentene polymer according to the present invention is performed by polymerizing a polymerization catalyst containing a transition metal catalyst component and a cocatalyst component in addition to the monomer constituting the 4-methyl-1-pentene polymer. It is carried out by a method of supplying to the reactor.

  Polymerization of the monomer constituting the 4-methyl-1-pentene polymer can be carried out by a liquid phase polymerization method such as solution polymerization, suspension polymerization, bulk polymerization method, gas phase polymerization method, and other known polymerization methods. . When the polymerization is carried out by a liquid phase polymerization method, an inert hydrocarbon can be used as a solvent, or a liquid olefin that is subjected to the reaction under the reaction conditions can be used. Furthermore, in the present invention, the polymerization can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

  Examples of the transition metal catalyst component constituting the polymerization catalyst used in the method for producing a 4-methyl-1-pentene polymer include a solid titanium catalyst composed of magnesium, titanium, halogen and an electron donor, a metallocene catalyst, and the like. It is done. Among these, a solid titanium catalyst is preferable, and a magnesium compound suspended in an inert hydrocarbon solvent described in Japanese Patent Application Laid-Open No. 2003-105022 and an electron donor are particularly preferable. Examples thereof include a titanium catalyst composed of titanium, magnesium, halogen, and a compound having a plurality of ether bonds obtained by contacting a compound having two or more ether bonds with a plurality of atoms in between and a titanium compound in a liquid state.

Examples of the inert hydrocarbon solvent include hexane, decane and dodecane.
As electron donors, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane and 2-isopentyl-2-isopropyl-1,3-compounds having two or more ether bonds with a plurality of atoms in between. Examples include dimethoxypropane.
Examples of magnesium compounds include anhydrous magnesium chloride and methoxy magnesium chloride.

  In the present invention, for example, in the case of a liquid phase polymerization method, the solid titanium catalyst is usually 0.0001 to 0.5 mmol, preferably 0.0005 to 0.1 in terms of titanium atoms per liter of the total liquid volume. It is preferably used in an amount of millimolar.

  In the solid titanium catalyst, the ratio of halogen and titanium (halogen / titanium) is usually 2 to 100, preferably 4 to 90, in atomic ratio, and the ratio of the compound containing two or more ether bonds and titanium. (Compound containing two or more ether bonds / titanium) is usually in a molar ratio of 0.01 to 100, preferably 0.2 to 10, and the ratio of magnesium and titanium (magnesium / titanium) is in atomic ratio. Usually 2 to 100, preferably 4 to 50.

The cocatalyst component (organometallic compound catalyst component) to be used together with the above-mentioned solid titanium catalyst, an organoaluminum compound may be mentioned, for example, an organoaluminum compound represented by R ^a _n AlX _3-n and the like.

During ^{_{R a n AlX 3-n,}} n is 1-3. R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, and an aryl group, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. A pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group, and when n is 2 or 3, they may be the same or different. X is halogen or hydrogen, and when n is 2 or 3, they may be the same or different.

Examples of the organoaluminum compounds represented by R ^a _n AlX _3-n, for example, trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trialkyl aluminum, such as trioctyl aluminum and tri-2-ethylhexyl aluminum; isoprenylaluminum Alkenyl aluminum such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride Yo Alkyl aluminum sesquihalides such as ethylaluminum sesquibromide; alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride .
Of these, trialkylaluminums such as triethylaluminum and triisobutylaluminum are preferred.

  For example, when the transition metal catalyst component is a solid titanium catalyst, the amount of the cocatalyst component (organometallic compound catalyst component) is usually 0.1 to 1000000 g, preferably 100 to 1000000 g, per 1 g of the solid titanium catalyst. The amount of such a polymer may be such that it is usually 0.1 to 1000 mol, preferably about 0.5 to 500 mol, more preferably 1 to 200, per mol of titanium atom in the solid titanium catalyst. The amount in moles.

  The transition metal catalyst component is preferably suspended in an inert organic solvent (preferably a saturated aliphatic hydrocarbon) and supplied to the polymerization reactor.

  The transition metal catalyst component is preferably used as a solid catalyst component prepolymerized with an α-olefin such as 3-methyl-1-pentene or 4-methyl-1-pentene. The prepolymerization is carried out by polymerizing the above α-olefin in an amount of usually 0.1 to 1000 g, preferably 0.3 to 500 g, more preferably 1 to 200 g per 1 g of the transition metal catalyst component. The prepolymerization can be performed at a catalyst concentration higher than the catalyst concentration in the reaction system in the polymerization of 4-methyl-1-pentene.

  In the present invention, liquid phase polymerization methods such as solution polymerization and suspension polymerization (slurry polymerization) are preferably used in producing a 4-methyl-1-pentene polymer, and more preferably suspension polymerization (slurry polymerization). ) Method is used.

  If hydrogen is used during the main polymerization, the molecular weight of the polymer obtained can be adjusted, and a polymer having a high melt flow rate can be obtained.

  Furthermore, by selecting the type of electron donor contained in the solid titanium catalyst used in the main polymerization, it becomes possible to adjust the stereoregularity of the obtained polymer, thereby adjusting the melting point of the polymer. It becomes possible.

  In the present invention, the polymerization temperature and polymerization pressure of olefin vary depending on the polymerization method and the type of monomer to be polymerized, but the polymerization temperature is usually 10 to 200 ° C., preferably 30 to 150 ° C., and the polymerization pressure is usually normal pressure. It is set to ˜5 MPa-G, preferably 0.05 to 4 MPa-G.

[Other resins]
You may add another resin to the composition of this invention in the range which does not impair the outstanding characteristic of 4-methyl- 1-pentene polymer. The amount added is generally 30% by weight or less, preferably 20% by weight or less. Examples of other resins include olefin polymers, polyesters, polyamides, modified olefin polymers, and the like.

  As said olefin polymer, what is obtained by superposing | polymerizing 1 or more types of olefins chosen from ethylene and a C3-C20 linear or branched alpha olefin is mentioned. Specific examples of the linear or branched α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, and 3-methyl-1. -Pentene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like. As these α-olefins, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.

  In addition to the above-mentioned α-olefin, the olefin polymer is a cyclic olefin, a functionalized vinyl compound, a polar group (for example, a carbonyl group, a hydroxyl group, an ether bond group, etc.) and a polymerizable polymer as long as the object of the present invention is not impaired. A monomer having a carbon-carbon double bond in the molecule (hereinafter also referred to as a polar group-containing monomer), a conjugated diene, a non-conjugated polyene, or the like may be included as a comonomer.

  Cyclic olefins include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5. , 8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like.

  Examples of functionalized vinyl compounds include aromatic vinyl compounds and alicyclic vinyl compounds. Examples of the aromatic vinyl compound include mono- or poly-styrene such as styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, o, p-dimethyl styrene, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene. Functional group-containing styrene derivatives such as alkyl styrene; methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene; and 3-phenylpropylene, 4 -Phenylpropylene, α-methylstyrene and the like are mentioned, and examples of the alicyclic vinyl compound include vinylcyclohexane and vinylcycloheptane.

  The functionalized vinyl compound may be a homopolymer of the functionalized vinyl compound or a copolymer with a copolymer component. Specific examples of copolymer components include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid, unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride, sodium methacrylate, acrylic Unsaturated carboxylic acid salts such as sodium acetate, unsaturated carboxylic acid esters such as vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, methyl methacrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, etc. Examples include, but are not limited to, saturated carboxylic acid amides. These copolymerization components may use only 1 type and may use 2 or more types together.

  Examples of the polyester include aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, hexamethylene glycol, alicyclic glycols such as cyclohexanedimethanol, and aromatic dihydroxy compounds such as bisphenol. And aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, undecadicarboxylic acid, hexahydroterephthalic acid, etc. A crystalline thermoplastic resin formed from the alicyclic dicarboxylic acid or two or more dicarboxylic acids selected from these alicyclic dicarboxylic acids. The polyester may be modified with a small amount of trihydroxy or higher polyhydroxy compound such as triol or tricarboxylic acid, polycarboxylic acid or the like as long as it exhibits thermoplasticity. Specific examples of this polyester include polylactic acid, polyethylene terephthalate, polybutylene terephthalate, polyethylene isophthalate / terephthalate copolymer, and the like.

  Examples of the polyamide include hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, 1,3- or 1,4-bis (aminomethyl). ) Diamines such as cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine, alicyclic diamine or aromatic diamine, and adipic acid, suberic acid, sebacic acid, cyclohexane Polyamides obtained by polycondensation with dicarboxylic acids such as aliphatic dicarboxylic acids such as dicarboxylic acid, terephthalic acid and isophthalic acid, alicyclic dicarboxylic acids and aromatic dicarboxylic acids, ε-aminocaproic acid, 11-aminoundecanoic acid, etc. Obtained by condensation of aminocarboxylic acid Polyamides, .epsilon.-caprolactam, .omega. polyamides obtained from lactams laurolactam such or copolymerized polyamide composed of these ingredients, more like a mixture of these polyamides. Specific examples of the polyamide include nylon 6, nylon 66, nylon 6110, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon 6/11, and aromatic nylon.

[Deodorants]
The deodorant used in the present invention is composed of at least one compound selected from the following (A) and (B).
(A) Tetravalent metal phosphate compound (B) Metal oxide or composite metal oxide

(A) Tetravalent metal phosphate compound Examples of the tetravalent metal phosphate compound include zirconium phosphate, titanium phosphate, and tin phosphate, with zirconium phosphate being preferred. Either amorphous or crystalline compounds can be used. The tetravalent metal phosphate compound has a high adsorption and deodorizing ability for basic gases such as ammonia and trimethylamine, and has been confirmed to have a deodorizing effect such as body odor.
Examples of the deodorant composed of a tetravalent metal phosphate compound include Kesmon (registered trademark) NS-10 (manufactured by Toagosei Co., Ltd.).

(B) Metal oxide or composite metal oxide The metal oxide is preferably a metal oxide containing a metal element selected from zinc, silicon, copper, nickel, iron, aluminum and magnesium. The composite metal oxide may be an oxide containing two or more of the above metal elements, or an oxide containing the above metal elements and other metal elements. More preferred as the metal oxide or composite metal oxide is zinc oxide and a mixture of zinc oxide and silicon dioxide. These have a high deodorizing effect on acid gases such as acetic acid and isovaleric acid, and a deodorizing effect such as body odor is recognized.

  Examples of the deodorant composed of zinc oxide include Kesmon (registered trademark) NS-10K (manufactured by Toagosei Co., Ltd.), and examples of the deodorant composed of a mixture of silicon dioxide and zinc oxide include Shukurenzu (registered trademark) KD- 211G (manufactured by Rasa Industrial Co., Ltd.).

  As the deodorant comprising at least one compound selected from the above (A) and (B), a commercially available deodorant product may be used alone, or a plurality of deodorant products may be combined. It may be used.

[Other additives]
Other additives for resin can be arbitrarily added to the resin composition of the present invention within a range that does not impair the effects of the present invention, depending on the application. Examples of such additives for resins include pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, and weathering stability. Agent, heat stabilizer, anti-slip agent, anti-blocking agent, foaming agent, crystallization aid, anti-fogging agent, (transparent) nucleating agent, anti-aging agent, hydrochloric acid absorbent, impact modifier, crosslinking agent, co-crosslinking agent , Crosslinking aids, adhesives, softeners, processing aids, and the like. These additives can be used singly or in appropriate combination of two or more.

  Examples of the pigment include inorganic contents (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of the dye include azo series, anthraquinone series, and triphenylmethane series. The addition amount of these pigments and dyes is not particularly limited, but is generally 5% by weight or less, preferably 0.1 to 3% by weight, based on the total weight of the 4-methyl-1-pentene polymer. It is.

  Fillers include glass fiber, carbon fiber, silica fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, carbon black, silica, glass beads, silicate (calcium silicate, talc, clay, etc.), metal oxide ( Iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate, etc.) and various metals (magnesium, silicon, aluminum, titanium, copper, etc.) powder, mica, glass flakes and the like. These fillers may be used alone or in combination of two or more.

  Examples of the lubricant include wax (such as carnauba wax), higher fatty acid (such as stearic acid), higher alcohol (such as stearyl alcohol), and higher fatty acid amide (such as stearic acid amide).

  Examples of plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetylricinoleate), aliphatic dialcolic acid esters (such as adipic acid-propylene glycol polyester), and aliphatic tricarboxylic acids. Examples include esters (such as triethyl citrate), phosphoric acid triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

  Examples of mold release agents include lower (C1-4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters (such as hardened castor oil) of fatty acids (C4-30), glycol esters of fatty acids, liquid paraffin, etc. Is mentioned.

Antioxidants include phenolic (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenolic (2,2′-methylenebis (4-methyl-6-t-butylphenol), etc.) Phosphorus-based (tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylenediphosphonate etc.), amine-based (N, N-diisopropyl-p-phenylenediamine etc.) antioxidants Can be mentioned.
Examples of flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.). Can be mentioned.

  Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylic acid, and acrylate.

  Antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, organic iodine, and the like.

  Surfactants can include nonionic, anionic, cationic or amphoteric surfactants. Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, fatty acid esters of polyethylene oxide and glycerin. Polyanhydric alcohol type nonionic surfactants such as fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, etc. For example, sulfate salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates, Include a phosphoric acid ester salts such as grade alcohol phosphate ester salt, the cationic surfactants, such as quaternary ammonium salts such as alkyl trimethyl ammonium salts. Examples of amphoteric surfactants include amino acid-type double-sided surfactants such as higher alkylaminopropionates, betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyl hydroxyethylbetaine.

  Examples of the antistatic agent include the above surfactants, fatty acid esters, and polymer antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymer antistatic agents include polyether ester amides.

  The addition amount of various additives such as the above fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, antistatic agents, and the like impairs the purpose of the present invention. Although it does not specifically limit according to a use within the range which is not, It is preferable that it is 0.01-30 weight% with respect to the said 4-methyl- 1-pentene type polymer, respectively.

[Method for Producing Resin Composition]
The resin composition of the present invention comprises the above 4-methyl-1-pentene polymer, a deodorant comprising at least one compound selected from (A) and (B), and, if necessary, the above “ Various resins and additives mentioned in the section of “Other resins” and “Other additives” can be blended and mixed by various known methods.

  As a method of mixing, for example, a method of mixing with a plast mill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, a kneader ruder or the like, or a kneading with a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, etc. Can be manufactured. Further, a deodorant can be added in the form of a master batch and dry blended or melt mixed.

  The temperature for melt kneading is usually 220 to 300 ° C, preferably 250 to 290 ° C. When the temperature is 220 ° C. or higher, the 4-methyl-1-pentene polymer is sufficiently melted, and when it is 300 ° C. or lower, thermal decomposition can be suppressed, which is preferable. The kneading time is usually in the range of 0.1 to 30 minutes, preferably 0.5 to 5 minutes, so that the mixture can be sufficiently melt-kneaded and thermal decomposition can be suppressed.

[Molded body]
Since the resin composition of the present invention maintains the inherent moldability of the poly-4-methyl 1-pentene polymer, it can be molded into various molded products and used. The resulting molded product has excellent deodorizing performance, and also maintains the properties such as mechanical strength, transparency and hygienic properties inherent in poly-4-methyl 1-pentene polymers, so deodorizing performance is required. It can be widely applied to various molded products. For example, an injection molded body, a film, a sheet, a fiber, a hollow molded body, etc. are mentioned. Further, as the fiber, it is possible to manufacture an ultrafine fiber, so that it can be used in the form of a non-woven fabric, or in the form of a monofilament, a multifilament, or a flat yarn.

  These molded products may be molded by the resin composition of the present invention alone, or may have a multilayer structure or a composite structure with other various resins or non-resin materials.

Examples of uses of films and sheets include various packaging films for foods, various daily necessities such as garbage bags, filth bags, gloves, building materials such as wallpaper and flooring, and automobile supplies.
Examples of injection-molded products include daily necessaries such as trash cans, toilet articles, bathing utensils, kitchen utensils, various food containers such as lunch boxes, cooking utensils, building materials such as flooring, members for refrigerators, members for clogs boxes, Examples include costume cases, furniture and household items such as snowboards and chests, pet breeding items, and car interior materials.

  Examples of fiber or non-woven fabric applications include masks, disposable diapers, sanitary products, hygiene products such as wigs, medical products, hollow fiber filters, water filters, bag filters, dust filters, bags, shoes, belts, Clothing such as jackets, underwear, daily necessities such as tablecloths, curtains, carpets, car mats, padding for duvets, blankets for duvets, duvet covers, blankets, blankets for blankets, blankets covers, sheets, padding for pillows, pillows Covers, stuffed batting, down jackets and other bedding and batting.

  Also in the form of monofilament, multifilament, flat yarn, rope, curing net, fishing net, fishing line, life jacket, insect net, women's clothing, men's clothing, lining, underwear, down, vest, windbreaker, socks, Shoe insole, mask, surgical gown, release cloth, oil absorbing cloth, waterproof cloth, outdoor wear, supporter, bandage, sleeping bag fabric, tent fabric, ski wear, golf wear, swimwear and other sportswear, artificial grass, It is suitable for uses such as a belt conveyor base fabric, an optical fiber, a sound absorbing material, and a heat insulating material, and the use is not limited thereto.

[Method for producing molded article]
A molded object can be manufactured, for example with the method shown below, respectively.

(1) Extruded film, extruded sheet Obtained by molding with a general T-die extruder. For example, an extruded film or sheet is formed by molding at a cylinder temperature of 250 to 300 ° C. and a cast roll temperature of 0 to 90 ° C. in a single screw extruder.

Although the thickness of the film or sheet depends on the intended use, it is usually 5 to 1000 μm, preferably 30 to 200 μm, which is excellent in film productivity, does not cause pinholes during film formation, and has sufficient strength. Is also preferable.
Moreover, as long as the effects of the present invention are not impaired, other resins and multilayer films may be used, or laminated paper may be used as laminated paper, and co-extrusion molding, extrusion lamination, thermal lamination, dry lamination, etc. are used. be able to. In addition, the film surface may be embossed or may be stretched during or after film formation. Furthermore, the film obtained by molding may be further subjected to an annealing treatment at a temperature lower than the melting point of the resin.

(2) Stretched film The film of the present invention may be stretched. The stretched film may be produced by producing a raw sheet and stretching it. There is no restriction | limiting in particular in the manufacturing method of a raw fabric sheet, For example, it can shape | mold by well-known methods, such as methods, such as press molding, extrusion molding, and inflation molding, or a solution casting method.

  From the viewpoint of improving production efficiency, an extrusion molding method, an inflation molding method, a solution casting method, or the like may be used. Furthermore, from the viewpoint of production efficiency and stabilization of the stretched molded body, it is preferable to obtain a stretched molded body by stretching and orienting the raw sheet formed by the melt extrusion molding method.

  In the case of performing melt extrusion molding, specifically, a raw sheet is formed by molding at a predetermined cylinder temperature and a predetermined cast roll temperature with a single screw extruder. When a raw sheet is obtained by melt extrusion molding, the transparency of the resulting sheet can be further increased by pressing and compressing between rolls of the extruder. The raw sheet manufactured in advance by melt extrusion molding may be supplied to a stretch molding apparatus, or melt extrusion molding and stretch molding may be performed continuously.

  The formed raw sheet is stretched and formed at a predetermined stretching speed with a stretching machine. Stretching may be performed by any of uniaxial stretching, biaxial stretching, sequential stretching, and the like.

  The stretching temperature is usually in the temperature range of the glass transition point (Tg) to 200 ° C of the resin, preferably Tg to 180 ° C, more preferably Tg to 150 ° C. Moreover, in order to improve stretchability, it is preferable to preheat the raw sheet before stretching. It is sufficient to perform preheating before stretching in a temperature range of Tg to 180 ° C, more preferably Tg to 150 ° C, usually for about 5 minutes.

  The stretching speed is usually 0.1 mm / sec to 500 mm / sec, more preferably 0.5 mm / sec to 100 mm / sec. The draw ratio is usually 1.5 to 6 times, preferably 2 to 5 times. In order not to increase the crystallinity and the crystal size, it may be preferable to reduce the stretching ratio and increase the stretching speed. The direction of stretching is preferably performed in the direction of extruding the original sheet. If it extends | stretches on such conditions, an extending | stretching molded object can be manufactured efficiently, without producing | generating an extending | stretching nonuniformity and extending | stretching interruption.

  By stretching the film, a film having mechanical strength can be obtained. The thickness of the stretched film can be adjusted by changing the thickness of the original fabric sheet, the stretch ratio, and the like. There is no particular upper limit to the thickness of the stretched film, and it includes what was conventionally called a “sheet” in this technical field. Moreover, when using a stretched film as an optical film, it is set as the thickness which can be used for an optical use. The thickness of the stretched film is usually 10 to 200 μm, preferably 20 to 200 μm. If it is such a range, productivity of a film will improve more, and sufficient mechanical strength will also be obtained, without producing a pinhole etc. at the time of film forming.

(3) Inflation film The film of the present invention may be produced by an inflation molding method. Specifically, an inflation film can be obtained by extruding from an inflation die in an upward direction opposite to the direction of gravity with a single cylinder extruder at a predetermined cylinder temperature.

  The take-up speed of the inflation film is usually 2 to 40 m / min, preferably 4 to 30 m / min. Although the thickness of a film is not specifically limited, Usually, 10-300 micrometers, Preferably it is 20-250 micrometers, More preferably, it is 30-60 micrometers.

(4) Injection-molded product An injection-molded product can be obtained at a molding temperature of usually 250 to 300 ° C. and a molding cycle of usually 20 to 120 seconds.

(5) Fiber The fiber comprising the resin composition in the present invention is produced as a monofilament, multifilament, flat yarn, cut fiber, non-woven fabric by extruding a melted resin composition through a spinneret, for example. Can be obtained.

  The melting temperature in the melt spinning process when producing monofilaments, multifilaments, and flat yarns can be appropriately selected according to the melting point of the 4-methyl-1-pentene polymer, but is in the range of 220 to 320 ° C. The more preferable range is 250 to 310 ° C. When the melting temperature is within the above range, excessive thermal decomposition of the 4-methyl-1-pentene polymer can be suppressed, and the elongational viscosity of the fibrous strand discharged from the die is sufficiently lowered. A fiber having excellent strength and good spinning processability can be obtained.

  The fiber thus obtained may be further stretched. If the extent of this stretching is performed to such an extent that, for example, at least uniaxial molecular orientation is effectively imparted to the 4-methyl-1-pentene polymer, the elastic modulus and strength can be improved. The draw ratio is usually in the range of 1.05 to 10.0 times, more preferably in the range of 1.1 times to 7.0 times, and still more preferably in the range of 1.2 to 6.0 times.

  The stretching temperature when performing the stretching operation can be appropriately selected according to the glass transition temperature and melting point of the 4-methyl-1-pentene polymer, or the strength and elongation of the fiber obtained after stretching, It is preferable that it is 35-200 degreeC, and a more preferable range is 40-180 degreeC. When the drawing temperature is in the above range, yarn breakage is suppressed and fibers can be obtained stably.

  When performing the said extending | stretching operation, any method of a 1 step extending | stretching method or a multistage extending | stretching method of 2 steps | paragraphs or more may be sufficient.

  Using the fibers obtained by the above method, a nonwoven fabric can be produced by a wet papermaking method, a sintering method, a needle punch method, a card method, a cross layer method, a random weber method, an air forming method, or the like.

  Moreover, when manufacturing the nonwoven fabric which consists of a single layer fiber, it can carry out according to methods, such as the spun bond method, the melt blown method, and the card | curd method.

  The fiber made of the resin composition of the present invention is not particularly limited with respect to the cross-sectional shape of the fiber, and may be a perfect circular cross section or a non-circular, so-called irregular cross section. The irregular cross section includes a polygonal shape, an elliptical shape, a flat shape, a multi-leaf shape having a large number of branches on the fiber surface (specifically, a multi-leaf shape having 3 to 32 leaves), a star shape Examples include a shape, a C-shape, an H-shape, an S-shape, a T-shape, a Y-shape, a W-shape, and a well shape.

  Furthermore, the fiber comprising the resin composition of the present invention may be a solid fiber that does not have a cavity portion continuous in the length direction in the fiber cross section, or one or more cavity portions that are continuous in the length direction. It may be a hollow fiber.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
The physical properties measured in the examples were carried out according to the following methods.

<Evaluation method of deodorant performance>
After putting 1 g of a sample in a 5 L PVA polymer bag (manufactured by GL Sciences Inc., Smart Bag PA), 3 L of test gas was sealed so as to have the initial gas concentration shown in Table 1, and the remaining in the bag after 24 hours. The gas concentration was measured using a detector tube. The deodorization rate was calculated according to the following formula (1) and used as an index for evaluating the deodorization performance.
Formula (1) Deodorization rate (%) = {initial gas concentration (ppm) −gas concentration (ppm) after 24 hours / initial gas concentration (ppm)} × 100

[material]
・ 4-Methyl-1-pentene polymer (A)
TPX (registered trademark) manufactured by Mitsui Chemicals, Inc., brand name: MX002 (melting point: 233 ° C., MFR (260 ° C., 5 kgf): 21 g / 10 min)
・ Polypropylene (B)
Prime Polypro (registered trademark) manufactured by Prime Polymer Co., Ltd., Brand Name: E-200GP (melting point: 160 ° C., MFR (230 ° C., 2.16 kgf): 1.8 g / 10 min)
・ Deodorant (C)
(C-1) Shoe lens (registered trademark) manufactured by Rasa Industrial Co., Ltd., Brand name: KD-211GF
(C-2) Kesmon (registered trademark) manufactured by Toagosei Co., Ltd., Brand Name: NS-10

[Example 1]
To 100 parts by weight of 4-methyl-1-pentene polymer (A), 1.0 part by weight of deodorant (C-1) dried under reduced pressure at 200 ° C. for 14 hours was added. Melt-kneading was performed with a shaft extruder (manufactured by Ikegai Co., Ltd., φ = 43 mm, L / D = 32, cylinder temperature: 280 ° C.) to obtain 4-methyl-1-pentene resin composition 1.

  Furthermore, after the resin composition 1 was dried under reduced pressure at 120 ° C. for 12 hours, the cylinder temperature was 270 ° C. and the die temperature was 270 ° C. in a single screw extruder (manufactured by Thermo Plastics Co., Ltd., φ = 30 mm). An extruded film having a thickness of 100 μm was produced under the condition of roll temperature: 80 ° C. The results of measuring the deodorizing performance of the film of the obtained resin composition 1 are summarized in Table 2. Since the film of the resin composition 1 is a 4-methyl-1-pentene polymer in which the matrix resin has a high gas permeability, the film has an excellent deodorizing performance.

[Example 2]
The same procedure as in Example 1 was conducted except that the amount of the deodorant (C-1) added to 100 parts by weight of the 4-methyl-1-pentene polymer (A) was changed to 3.0 parts by weight. A methyl-1-pentene resin composition 2 and a film were obtained. The results of measuring the deodorizing performance of the film of the resin composition 2 obtained are summarized in Table 2. Since the film of the resin composition 2 is a 4-methyl-1-pentene polymer in which the matrix resin has high gas permeability, the film has excellent deodorizing performance.

[Example 3]
A resin composition 3 and a film were obtained in the same manner as in Example 1 except that the deodorant (C-2) was used as the deodorant component. The results of measuring the deodorizing performance of the film of the obtained resin composition 3 are summarized in Table 2. Since the film of the resin composition 3 is a 4-methyl-1-pentene polymer in which the matrix resin has high gas permeability, the film has excellent deodorizing performance.

[Example 4]
The resin composition 2 obtained in Example 2 was dried under reduced pressure at 120 ° C. for 12 hours, and then subjected to a 70t injection molding machine (M70B, manufactured by Meiki Seisakusho Co., Ltd.). Cylinder temperature: 300 ° C., mold temperature: A square plate having a size of 100 mm × 100 mm × 2 mmt was produced under injection conditions of 80 ° C. Table 2 summarizes the measurement results of the deodorizing performance of the obtained injection-molded article of 4-methyl-1-pentene resin composition 2. Since the square plate of the resin composition 2 is a 4-methyl-1-pentene polymer in which the matrix resin has high gas permeability, the deodorizing performance was excellent.

[Example 5]
The resin composition 1 obtained in Example 1 was subjected to a capillary rheometer (manufactured by Toyo Seiki Co., Ltd., Capillograph 1B, barrel diameter = 10 mmφ), under the condition of a set temperature of 270 ° C., the hole diameter was 1 mm (circular), the number of holes The melted polymer was melt-extruded from the nozzle 1 at a cylinder speed of 10 mm / min, and the spun yarn was wound at a winding speed of 10 m / min while cooling at room temperature to obtain an undrawn yarn. Subsequently, using a heat drawing machine (manufactured by Imoto Seisakusho Co., Ltd.), the fiber was drawn 6 times at a feed line speed of 0.2 m / min at a temperature of 100 to 120 ° C. to obtain a fiber having a diameter of 50 μm. The results of measuring the deodorizing performance of the obtained fibers are summarized in Table 2. Since the fiber of the resin composition 1 is a 4-methyl-1-pentene polymer in which the matrix resin has high gas permeability, the deodorizing performance was excellent.

[Comparative Example 1]
Using 4-methyl-1-pentene polymer (A) alone, a film was produced in the same manner as in Example 1. The results of measuring the deodorizing performance of the obtained film are summarized in Table 2.

[Comparative Example 2]
1.0 part by weight of deodorant (C-1) dried under reduced pressure at 200 ° C. for 14 hours was added to 100 parts by weight of polypropylene (B), and a twin-screw extruder (manufactured by Ikegai Co., Ltd., φ = 43 mm, L / D = 32, cylinder temperature: 230 ° C.) to obtain a polypropylene resin composition.

  Furthermore, after the polypropylene resin composition was dried under reduced pressure at 120 ° C. for 12 hours, the cylinder temperature was 240 ° C. and the die temperature was 240 using a single screw extruder (manufactured by Thermo Plastics Co., Ltd., φ = 30 mm). An extruded film having a thickness of 100 μm was produced under the conditions of ° C and roll temperature: 40 ° C. The odor performance measurement results of the film of the obtained polypropylene resin composition are summarized in Table 2. The film of the polypropylene resin composition has insufficient deodorizing performance.

Claims (8)

A resin composition comprising a 4-methyl-1-pentene polymer and a deodorant comprising at least one compound selected from the following (A) and (B).
(A) Tetravalent metal phosphate compound (B) Metal oxide or composite metal oxide The resin composition according to claim 1, wherein the content of the deodorant is 0.1 to 10% by weight with respect to the 4-methyl-1-pentene polymer. The resin composition according to claim 1 or 2, wherein the (A) tetravalent metal phosphate compound is zirconium phosphate. The resin composition according to any one of claims 1 to 3, wherein the (B) metal oxide or composite metal oxide is zinc oxide or a mixture of zinc oxide and silicon dioxide. The molded object which consists of a resin composition as described in any one of Claims 1-4. The film which consists of a resin composition as described in any one of Claims 1-4. An injection-molded article comprising the resin composition according to any one of claims 1 to 4. The fiber which consists of a resin composition as described in any one of Claims 1-4.