Manufacturing method of recycled resin

Abstract

To provide resin with excellent heat resistance.SOLUTION: A manufacturing method of recycled resin comprises a step of cleaning resin after physically removing the surface of resin materials without adhesion of coat films.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to recycled resin.

Background Art

[0002] When recycling automobile parts with a coating film, such as a bumper (made of polypropylene) of a vehicle, the coating film adhering to the surface is peeled off and recycled. On the other hand, parts without a coating film on the surface are recycled without surface polishing.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In recent years, resins used in automobile materials, home appliance materials, container packaging materials, etc. are required to have heat resistance.

[0005] Therefore, an object of the present application is to provide a recycled resin capable of manufacturing a molded body having excellent heat resistance.

Means for Solving the Problems

[0006] The present invention relates to, but is not limited to, the following. [Invention A1] A method for producing a recycled resin, comprising a step of physically removing the surface of a resin material without coating film and then washing the resin. [Invention A2] The method according to Invention A1, wherein the resin material contains a propylene polymer. [Invention A3] The method according to Invention A1 or A2, wherein the resin material contains a heterophasic propylene polymer material. [Invention A4] The method according to any one of Inventions A1 to A3, wherein the surface of 3% by weight or more is removed by the removal process. [Invention A5] Recycled resin obtained by the method according to any one of Inventions A1 to A4. [Invention A6] Recycled resin derived from a resin material without coating film adhesion, having its surface physically removed. [Invention A7] A resin composition containing the recycled resin according to Invention A5 or A6. [Invention A8] The resin composition according to Invention A7, further comprising a virgin propylene polymer. [Invention A9] The resin composition according to Invention A7 or A8, further comprising an ethylene-α-olefin copolymer. [Invention A10] The resin composition according to Invention A9, containing a recycled ethylene-α-olefin copolymer as the ethylene-α-olefin copolymer. [Invention A11] The resin composition according to any one of Inventions A7 to A10, containing filler F. [Invention A12] The resin composition according to Invention A11, containing a recycled filler as filler F. [Invention A13] The resin composition according to Invention A11, containing an inorganic filler as filler F. [Invention A14] A molded article containing the recycled resin according to Invention A5 or A6 or the resin composition according to any one of Inventions A7 to A13.

[0007] Other aspects of the present invention are as follows, but are not limited thereto. [Invention B1] A method for producing a recycled resin, comprising a step of physically removing the surface of a resin material without coating film adhesion and then washing the resin, wherein the resin material without coating film adhesion contains a propylene polymer, and the weight ratio of the xylene-soluble component in the resin material, measured by the following method, is 2.0% by weight to 40% by weight. Method <Method for Measuring Weight Ratio of Xylene-Soluble Component> About 4 g of the resin material is refluxed with boiling xylene for 5 hours using a cylindrical filter paper and a Soxhlet extraction tube. Next, the extract is concentrated under reduced pressure using a rotary evaporator to obtain a polymer component. About 2 g of the obtained polymer component is precisely weighed (this "weight of the polymer component" is referred to as "a"), and heated and dissolved with boiling xylene for 2 hours. Then, after cooling to 20 °C, it is filtered using a filter paper. The filtered filtrate is concentrated under reduced pressure using a rotary evaporator to obtain a xylene-soluble component. The obtained xylene-soluble component is precisely weighed (hereinafter, the "weight of the xylene-soluble component" is referred to as "b"). The weight ratio of the xylene-soluble component in the resin material is calculated by the following formula using the numerical values a and b. Weight ratio of CXS component (wt%) = (b / a) × 100 [Invention B2] The method according to Invention B1, wherein the resin material contains a heterophasic propylene polymerization material. [Invention B3] The method according to Invention B1 or B2, wherein 3 wt% or more of the surface is removed by a removal step. [Invention B4] Recycled resin obtained by the method according to any one of Inventions B1 to B3. [Invention B5] A recycled resin derived from a resin material without coating film adhesion and with its surface physically removed, wherein the resin material without coating film adhesion contains a propylene polymer, and the weight ratio of the xylene-soluble component in the resin material, measured by the following method, is 2.0 wt% to 40 wt%. Recycled resin. <Method for Measuring Weight Ratio of Xylene-Soluble Component> Weigh approximately 4 g of the resin material and reflux it with boiling xylene for 5 hours using a cylindrical filter paper and a Soxhlet extraction tube. Then, concentrate the extract under reduced pressure using a rotary evaporator to obtain the polymer component. Precisely weigh approximately 2 g of the obtained polymer component (let this "weight of the polymer component" be "a"), and heat and dissolve it with boiling xylene for 2 hours. Then, after cooling to 20°C, filter it using filter paper. Concentrate the filtered filtrate under reduced pressure using a rotary evaporator to obtain the xylene-soluble component. Precisely weigh the obtained xylene-soluble component (hereinafter, let the "weight of the xylene-soluble component" be "b"). The weight ratio of the xylene-soluble component in the resin material is calculated by the following formula using the numerical values a and b. Weight ratio of CXS component (wt%) = (b / a) × 100 [Invention B6] A resin composition comprising the recycled resin according to Invention B4 or B5. [Invention B7] The resin composition according to Invention B6, further comprising a virgin propylene polymer. [Invention B8] The resin composition according to Invention B6 or B7, further comprising an ethylene-α-olefin copolymer. [Invention B9] The resin composition according to Invention B8, comprising a recycled ethylene-α-olefin copolymer as the ethylene-α-olefin copolymer. [Invention B10] The resin composition according to any one of Inventions B6 to B9, comprising a filler F. [Invention B11] The resin composition according to Invention B10, comprising a recycled filler as the filler F. [Invention B12] The resin composition according to Invention B10, comprising an inorganic filler as the filler F. [Invention B13] A molded article comprising the recycled resin according to Invention B4 or B5 or the resin composition according to any one of Inventions B6 to B12. [Advantages of the Invention]

[0008] According to the present invention, a molded article excellent in heat resistance and a resin as a raw material thereof can be provided.

Mode for Carrying Out the Invention

[0009] Definition In the present specification, the term "propylene polymer" means a polymer having 50% by weight or more of monomer units derived from propylene. This will be described in detail later. In the present specification, the term "propylene resin composition" means a composition containing a propylene polymer. This will be described in detail later. In the present specification, the term "α-olefin" means an aliphatic unsaturated hydrocarbon having a carbon-carbon unsaturated double bond at the α-position. In the present specification, the term "hydrocarbon group having 4 to 10 carbon atoms" means a hydrocarbon group having 4 to 10 carbon atoms. The same applies to other similar expressions. In the present specification, the term "ethylene-α-olefin copolymer" means a copolymer containing monomer units derived from ethylene and monomer units derived from an α-olefin having 4 or more carbon atoms (meaning 4 or more carbon atoms. The same applies to other similar expressions), and substantially not containing monomer units derived from propylene. This will be described in detail later. In the present specification, the term "heterophasic propylene polymerization material" means a polymer I containing 80% by weight or more of monomer units derived from propylene (where the total weight of the polymer I is taken as 100% by weight), and a polymer II containing monomer units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms and monomer units derived from propylene. In the present specification, the term "xylene-insoluble component (also referred to as "CXIS component")" means a component insoluble in p-xylene contained in the polymer. Details will be described later. In the present specification, the term "xylene-soluble component (also referred to as "CXS component")" means a component other than the "CXIS component" in the polymer. The CXS component is mainly considered to be derived from components with low stereoregularity of the propylene polymer contained in the resin material, random copolymers of propylene and monomers other than propylene, polymer II in the heterophasic propylene polymerization material which is a kind of propylene polymer, ethylene-α-olefin copolymers (outside the category of propylene polymers), etc. The CXIS component is mainly considered to be derived from components with high stereoregularity of the propylene polymer contained in the resin material, homopolymers of propylene, polymer I in the heterophasic propylene polymerization material which is a kind of propylene polymer, etc.

[0010] The description of "lower limit ~ upper limit" representing a numerical range means "greater than or equal to the lower limit and less than or equal to the upper limit", and the description of "upper limit ~ lower limit" means "less than or equal to the upper limit and greater than or equal to the lower limit". That is, these descriptions represent a numerical range including the lower limit and the upper limit, but in one aspect, one or both of the upper limit and the lower limit may be excluded, that is, "lower limit ~ upper limit" may represent "greater than the lower limit and less than or equal to the upper limit", "greater than or equal to the lower limit and less than the upper limit", or "greater than the lower limit and less than the upper limit". Similarly, "xx or more" may represent "more than xx", and "xx or less" may represent "less than xx".

[0011] Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0012] Resin material The present invention relates to a method for manufacturing recycled resin, etc., which includes a step of physically removing the surface of the resin material without coating adhesion and then washing the resin.

[0013] In this specification, the term "recycled resin" means a resin that is reused (has been reused) after undergoing a recovery process once it has been processed such as molded or after being used for some end use. The same applies to other "recycled xxx" such as "recycled propylene polymer".

[0014] Examples of raw materials used in the recovery process include molded products or parts of products or parts recovered from the market, such as interior parts of automobiles (instrument panels, door trims, etc.), exterior parts of automobiles (bumpers, etc.), other automobile parts (battery cases, etc.), packaging containers (food retort pouches, refill pouches, detergent bottles, etc.), housings of household electrical appliances, office supplies (trays, etc.), household daily necessities (contact lens cases, etc.), etc. They may also be those recovered during a certain manufacturing process.

[0015] These recovered raw materials may contain an elastomer component that enhances impact resistance, such as an ethylene-α-olefin copolymer, and / or a filler such as an inorganic filler, a neutralizing agent, an antioxidant, an ultraviolet absorber, a nucleating agent, a lubricant, an antistatic agent, an antiblocking agent, a colorant (inorganic pigment, organic pigment, pigment dispersant, etc.), a flame retardant, and other additives, depending on the application. The recovery process is not particularly limited, and for example, known methods can be mentioned.

[0016] From a comprehensive perspective such as the market value, it is preferable to use crushed materials as the resin material that is the raw material of the method of the present invention. In one aspect, at least a part of the crushed material is derived from materials recovered from automotive parts. The crushed material can have, for example, a maximum dimension of 10 to 15 mm and be sized to pass through a punching screen with a pore diameter of 15 mm.

[0017] In one aspect, the process of preparing the resin material may include any process in addition to the recovery process - for example, a crushing process, a purification process, a melting process, a kneading process with other substances, a forming process into pellet form. Examples of the purification process include washing with water, aqueous and / or oily agents, microbial treatment, magnetic separation, and specific gravity separation. The molded body includes, for example, an injection molded body, but is not limited thereto.

[0018] The resin material and the recycled resin preferably contain a propylene polymer and / or an ethylene-α-olefin copolymer.

[0019] In one aspect, the present resin composition may contain components other than the present recycled resin (hereinafter also referred to as other components). Examples of the other components include propylene polymers, fillers, ethylene-α-olefin copolymers (hereinafter also referred to as "propylene polymers etc."). These may be recycled propylene polymers etc., or virgin propylene polymers etc.

[0020] In this specification, the term "virgin propylene polymer" is different from the above-mentioned "recycled propylene polymer". It means a propylene polymer that has not been molded into a product such as an automobile or its parts after being produced by a process including a polymerization step and has not been used for any final application. The same applies to other "virgin xxx".

[0021] The content of the xylene-insoluble component (CXIS component) in the resin material is preferably 50 to 99% by weight based on the total weight of the resin material. The lower limit may be 60% by weight, 70% by weight, or 75% by weight. The upper limit may be 95% by weight, 98% by weight, or 98.5% by weight.

[0022] The content of the xylene-soluble component (CXS component) in the resin material is preferably 1 to 50% by weight based on the total weight of the resin material. The lower limit may be 1.5% by weight, 2.0% by weight, or 5.0% by weight. The upper limit may be 40% by weight, 30% by weight, or 25% by weight.

[0023] Preferably, the isotactic pentad fraction of CXIS of the resin material is less than 0.981, and may be, for example, 0.980 or less, 0.978 or less, 0.975 or less, 0.961 or less, 0.958 or less, 0.955 or less, 0.950 or less. The lower limit is not particularly limited, and may be, for example, 0.900 or more, 0.925 or more, 0.930 or more, 0.961 or more, 0.965 or more, 0.968 or more.

[0024] In the present invention, it is considered that the CXIS component in the resin material is mainly composed of polymer I, and the CXS component in the resin material is mainly composed of polymer II.

[0025] In this specification, the weight ratio of the CXIS component and the CXS component is measured by the method described in the examples.

[0026] The melt flow rate (MFR) (temperature: 230°C, load: 2.16 kgf) of the resin material is preferably 1 to 100 g / 10 min, more preferably 12 to 70 g / 10 min, and even more preferably 5 to 40 g / 10 min, from the viewpoint of the moldability of the resin composition and the like. The MFR of the resin material is preferably 10 g / 10 min or more from the viewpoint of improving the moldability of the obtained resin composition. The MFR of the resin material is preferably 100 g / 10 min or less from the viewpoint of improving the impact resistance of the obtained resin composition and molded article.

[0027] In this specification, the melt flow rate refers to a value measured in accordance with JIS K7210. Further, the melt flow rate may be hereinafter referred to as MFR.

[0028] As one aspect, the resin material contains ash. The ash of the resin material means the components remaining as ash after heating the resin material at 600°C for 60 minutes. The weight ratio of the ash is determined by the following method. <Measurement method of weight ratio of ash> The crucible is heated at 600°C for 60 minutes using an electric furnace, taken out of the furnace, cooled in a desiccator for 1 hour, and then weighed with an analytical balance. Weigh 10 g of the resin material into the crucible (measured to the nearest 1 mg), heat it at 600°C for 60 minutes using an electric furnace until it is completely ashed. Then, after cooling the crucible in a desiccator for 1 hour, measure the weight of the ash to the nearest 0.1 mg with an analytical balance, and calculate the weight ratio (wt%) of the ash to the resin material.

[0029] In one aspect, the weight ratio of the ash content is 4% by weight or more, 5% by weight or more, or 10% by weight or more based on the total weight of the resin material. In one aspect, the weight ratio of the ash content is 40% by weight or less, 30% by weight or less, or 25% by weight or less based on the total weight of the resin material.

[0030] In one aspect, the resin material contains the aforementioned filler. When the resin material contains a filler, most of the filler is included in the ash content of the resin material. When the resin material contains a filler, the weight ratio of the filler is considered to generally correspond to the weight ratio of the ash content of the resin material. When the resin material contains a filler, in the <Method for Measuring the Weight Ratio of CXS Component and CXS Component> described below, about 4 g of the resin material is refluxed with boiling xylene for 5 hours using a cylindrical filter paper and a Soxhlet extraction tube, and then the residue other than the polymer component obtained by concentrating the extract under reduced pressure using a rotary evaporator is considered to generally correspond to the ash content of the resin material.

[0031] Propylene polymer When the resin material and the recycled resin contain a propylene polymer, and / or when the resin composition of the present invention contains a propylene polymer as a component other than the recycled resin, examples of the propylene polymer include a propylene homopolymer, a random copolymer of propylene and a monomer other than propylene, and a heterophasic propylene polymerization material. The resin material and the recycled resin, and / or the resin composition may contain only one kind of propylene polymer, or may contain two or more kinds. From the viewpoints of the rigidity and impact resistance of the molded article, the propylene polymer preferably contains at least one selected from the group consisting of a propylene homopolymer and a heterophasic propylene polymerization material.

[0032] Propylene homopolymer When the resin material and the recycled resin contain a propylene homopolymer, and / or when the resin composition of the present invention contains a propylene homopolymer as a component other than the recycled resin, preferred embodiments of the propylene homopolymer are shown below.

[0033] The intrinsic viscosity ([η]) of the propylene homopolymer is preferably 0.10 to 4.00 dL / g, more preferably 0.50 to 3.00 dL / g, and even more preferably 0.70 to 2.00 dL / g, from the viewpoints of the melt fluidity of the resin composition and the toughness of the molded article.

[0034] In this specification, the intrinsic viscosity (unit: dL / g) means a value measured at a temperature of 135 °C using tetralin as a solvent by the following method.

[0035] Using an Ubbelohde viscometer, the reduced viscosity is measured at three points of concentrations of 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL. The reduced viscosity is plotted against the concentration, and the intrinsic viscosity is determined by the extrapolation method of extrapolating the concentration to zero. The calculation method of the intrinsic viscosity by the extrapolation method is described, for example, on page 491 of "Polymer Solutions, Polymer Experimentation 11" (published by Kyoritsu Shuppan Co., Ltd. in 1982).

[0036] The molecular weight distribution (Mw / Mn) of the propylene homopolymer is preferably 3.0 or more, more preferably 4.0 or more, and may be 15.0 or less, or may be 10.0 or less. The molecular weight distribution of the propylene homopolymer is preferably 3.0 to 15.0, more preferably 4.0 to 10.0.

[0037] In this specification, the molecular weight distribution means the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), which is calculated using the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) under the following conditions. Apparatus: HLC-8121 GPC / HT manufactured by Tosoh Corporation Separation column: Three GMHHR-H(S)HT columns manufactured by Tosoh Corporation Measurement temperature: 140 °C Carrier: Orthodichlorobenzene Flow rate: 1.0 mL / min Sample concentration: approximately 1 mg / mL Sample injection volume: 400 μL Detector: differential refraction Calibration curve preparation method: using standard polystyrene

[0038] The propylene homopolymer may be produced, for example, by polymerizing propylene using a polymerization catalyst.

[0039] Examples of the polymerization catalyst include Ziegler catalysts; Ziegler-Natta catalysts; catalysts containing a compound of a Group 4 transition metal of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; catalysts containing a compound of a Group 4 transition metal of the periodic table having a cyclopentadienyl ring, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound; and modified catalysts in which catalyst components (a compound of a Group 4 transition metal of the periodic table having a cyclopentadienyl ring, a compound that forms an ionic complex, an organoaluminum compound, etc.) are supported on inorganic particles (such as silica and clay minerals).

[0040] Examples of the above polymerization catalysts include the catalysts described in JP-A-61-218606, JP-A-5-194685, JP-A-7-216017, JP-A-9-316147, JP-A-10-212319, JP-A-2004-182981, JP-A-2010-168545, JP-A-2011-246699, etc.

[0041] Also, a polymer obtained by prepolymerizing propylene in the presence of the above polymerization catalyst can be used as the polymerization catalyst.

[0042] Examples of polymerization methods include bulk polymerization, solution polymerization, and gas-phase polymerization. Here, bulk polymerization refers to a method of performing polymerization using a liquid olefin as a medium at the polymerization temperature, and solution polymerization refers to a method of performing polymerization in an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, octane, etc. Gas-phase polymerization refers to a method of polymerizing a monomer in a gaseous state using the gaseous monomer as a medium.

[0043] Examples of polymerization modes include batch, continuous, and combinations thereof. The polymerization mode may be a multi-stage type in which a plurality of polymerization reaction vessels are connected in series.

[0044] From the viewpoints of industrial and economic excellence, a continuous gas-phase polymerization method or a bulk-gas-phase polymerization method that continuously performs a bulk polymerization method and a gas-phase polymerization method is preferable.

[0045] Various conditions in the polymerization step (polymerization conditions such as polymerization temperature, polymerization pressure, monomer concentration, catalyst input amount, polymerization time, etc.) may be appropriately determined according to the molecular structure of the target polymer.

[0046] Other steps may be carried out before or after the polymerization step. For example, after the polymerization step, in order to remove residual solvents contained in the polymer, ultra-low molecular weight oligomers by-produced during production, etc., the polymer may be dried (dehydrated) at a temperature below the melting temperature of the polymer as necessary. Examples of drying methods include those described in JP-A-55-75410 and Japanese Patent No. 2565753.

[0047] Random copolymer of propylene and monomers other than propylene A random copolymer of propylene and a monomer other than propylene contains a monomer unit derived from propylene and a monomer unit derived from a monomer other than propylene. When the resin material and the recycled resin contain the random copolymer, and / or when the resin composition of the present invention contains the random copolymer as a component other than the recycled resin, preferred embodiments of the random copolymer are shown below.

[0048] It is preferable that the random copolymer contains 0.01 to 20% by weight of monomer units derived from monomers other than propylene, based on the weight of the random copolymer.

[0049] Examples of monomers other than propylene include ethylene and C4-12 α-olefins. Among them, at least one selected from the group consisting of ethylene and C4-10 α-olefins is preferable, at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, and 1-octene is more preferable, and at least one selected from the group consisting of ethylene and 1-butene is even more preferable.

[0050] Examples of the random copolymer include propylene-ethylene random copolymer, propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, propylene-ethylene-1-butene random copolymer, propylene-ethylene-1-hexene random copolymer, and propylene-ethylene-1-octene random copolymer.

[0051] From the viewpoint of the fluidity during melting of the resin composition, the intrinsic viscosity ([η]) of the random copolymer is preferably 0.10 to 4.00 dL / g, more preferably 0.50 to 3.00 dL / g, and even more preferably 0.70 to 2.00 dL / g.

[0052] The molecular weight distribution (Mw / Mn) of the random polymer is preferably 3.0 or more, more preferably 4.0 or more. The molecular weight distribution of the random polymer may be 10.0 or less, or may be 7.0 or less. The molecular weight distribution of the random polymer is preferably 3.0 to 10.0, more preferably 4.0 to 7.0.

[0053] The random copolymer may be produced, for example, by polymerizing propylene and monomers other than propylene according to the polymerization catalyst, polymerization method, polymerization mode, and polymerization conditions that can be used in the production of the propylene homopolymer.

[0054] Heterophasic propylene polymerization material As described above, a heterophasic propylene polymerization material is exemplified as the propylene polymer. That is, the heterophasic propylene polymerization material is a subordinate concept of the propylene polymer. When the resin material and the recycled resin contain a heterophasic propylene polymerization material, and / or when the resin composition of the present invention contains a heterophasic propylene polymerization material as a component other than the recycled resin, preferred embodiments of the heterophasic propylene polymerization material are shown below.

[0055] The heterophasic propylene polymerization material may be produced, for example, by performing a first polymerization step for forming polymer I and a second polymerization step for forming polymer II. These polymerization steps can be carried out according to the polymerization catalyst, polymerization method, polymerization mode, and polymerization conditions that can be used in the production of the propylene homopolymer. In the heterophasic propylene polymerization material, assuming the total weight of the heterophasic propylene polymerization material is 100% by weight, the total of polymer I and polymer II contained in the heterophasic propylene polymerization material may be 100% by weight.

[0056] As described above, polymer I contains 80% by weight or more of monomer units derived from propylene (where the total weight of polymer I is 100% by weight). Polymer I may be, for example, a propylene homopolymer, or may contain monomer units derived from monomers other than propylene. When polymer I contains monomer units derived from monomers other than propylene, the content may be, for example, 0.01% by weight or more and less than 20% by weight based on the total weight of polymer I.

[0057] Examples of monomers other than propylene include ethylene and α-olefins having 4 or more carbon atoms. Among them, at least one selected from the group consisting of ethylene and C4-10 α-olefins is preferable, at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, and 1-octene is more preferable, and at least one selected from the group consisting of ethylene and 1-butene is even more preferable.

[0058] Examples of copolymers containing monomer units derived from monomers other than propylene include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers, propylene-ethylene-1-butene copolymers, propylene-ethylene-1-hexene copolymers, and propylene-ethylene-1-octene copolymers.

[0059] From the viewpoint of the dimensional stability of the molded article, the polymer I is preferably a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-ethylene-1-butene copolymer, and more preferably a propylene homopolymer.

[0060] Preferably, the isotactic pentad fraction of the polymer I is less than 0.981, for example, it may be 0.980 or less, 0.978 or less, 0.975 or less, 0.961 or less, or 0.950 or less. The lower limit is not particularly limited, and it may be, for example, 0.900 or more, 0.925 or more, 0.930 or more, 0.961 or more, 0.965 or more, or 0.968 or more.

[0061] The content of the polymer I is preferably 50 to 99% by weight based on the total weight of the heterophasic propylene polymer material. The lower limit may be 60% by weight, 70% by weight, or 75% by weight. The upper limit may be 95% by weight, 98% by weight, or 98.5% by weight.

[0062] As described above, Polymer II contains monomer units derived from at least one α-olefin selected from the group consisting of ethylene and C4-12 α-olefins and monomer units derived from propylene. Preferably, Polymer II contains 30% by weight or more of monomer units derived from at least one α-olefin selected from the group consisting of ethylene and C4-12 α-olefins and contains monomer units derived from propylene (however, the total weight of Polymer II is taken as 100% by weight).

[0063] In Polymer II, the content of monomer units derived from at least one α-olefin selected from the group consisting of ethylene and C4-12 α-olefins may be 30-70% by weight, and may also be 35-60% by weight (however, the total weight of Polymer II is taken as 100% by weight).

[0064] In Polymer II, as the at least one α-olefin selected from the group consisting of ethylene and C4-12 α-olefins, at least one selected from the group consisting of ethylene and C4-10 α-olefins is preferred, at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, 1-octene and 1-decene is more preferred, and at least one selected from the group consisting of ethylene and 1-butene is even more preferred.

[0065] Examples of Polymer II include propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, propylene-ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer and propylene-1-decene copolymer. Among them, propylene-ethylene copolymer, propylene-1-butene copolymer and propylene-ethylene-1-butene copolymer are preferred, and propylene-ethylene copolymer is more preferred.

[0066] The content of the polymer II is preferably 1 to 50% by weight based on the total weight of the heterophasic propylene polymerization material. The lower limit may be 1.5% by weight, 2.0% by weight, or 5.0% by weight. The upper limit may be 40% by weight, 30% by weight, or 25% by weight.

[0067] In the heterophasic propylene polymerization material, the content of the monomer unit derived from at least one α-olefin selected from the group consisting of ethylene and C4-12 α-olefins may be 0.3 to 35% by weight, or may be 0.7 to 24% by weight (provided that the total weight of the heterophasic propylene polymerization material is 100% by weight).

[0068] The content of the xylene-insoluble component (CXIS component) in the heterophasic propylene polymerization material is preferably 50 to 99% by weight based on the total weight of the heterophasic propylene polymerization material. The lower limit may be 60% by weight, 70% by weight, or 75% by weight. The upper limit may be 95% by weight, 98% by weight, or 98.5% by weight.

[0069] The content of the xylene-soluble component (CXS component) in the heterophasic propylene polymerization material is preferably 1 to 50% by weight based on the total weight of the heterophasic propylene polymerization material. The lower limit may be 1.5% by weight, 2.0% by weight, or 5.0% by weight. The upper limit may be 40% by weight, 30% by weight, or 25% by weight.

[0070] Preferably, the isotactic pentad fraction of the CXIS of the heterophasic propylene polymerization material is less than 0.981, for example, it may be 0.980 or less, 0.978 or less, 0.975 or less, 0.961 or less, 0.958 or less, 0.955 or less, 0.950 or less. The lower limit is not particularly limited, for example, it may be 0.900 or more, 0.925 or more, 0.930 or more, 0.961 or more, 0.965 or more, 0.968 or more.

[0071] In the present invention, it is considered that the CXIS component in the heterophagic propylene polymerization material is mainly composed of polymer I, and the CXS component in the heterophagic propylene polymerization material is mainly composed of polymer II.

[0072] Examples of heterophasic propylene polymerization materials include (propylene)-(propylene-ethylene) polymerization materials, (propylene)-(propylene-ethylene-1-butene) polymerization materials, (propylene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene)-(propylene-ethylene-1-octene) polymerization materials, (propylene)-(propylene-1-butene) polymerization materials, (propylene)-(propylene-1-hexene) polymerization materials, (propylene)-(propylene-1-octene) polymerization materials, (propylene)-(propylene-1-decene) polymerization materials, (propylene-ethylene)-(propylene-ethylene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-octene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-decene) polymerization materials, (propylene-ethylene)-(propylene-1-butene) polymerization materials, (propylene-ethylene)-(propylene-1-hexene) polymerization materials, (propylene-ethylene)-(propylene-1-octene) polymerization materials, (propylene-ethylene)-(propylene-1-decene) polymerization materials, (propylene-1-butene)-(propylene-ethylene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-butene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-octene) polymerization materials, (propylene-1-butene)-(propylene-ethylene-1-decene) polymerization materials, (propylene-1-butene)-(propylene-1-butene) polymerization materials, (propylene-1-butene)-(propylene-1-hexene) polymerization materials, (propylene-1-butene)-(propylene-1-octene) polymerization materials, (propylene-1-butene)-(propylene-1-decene) polymerization materials, (propylene-1-hexene)-(propylene-1-hexene) polymerization materials, (propylene-1-hexene)-(propylene-1-octene) polymerization materials, (propylene-1-hexene)-(propylene-1-decene) polymerization materials, (propylene-1-octene)-(propylene-1-octene) polymerization materials,And (propylene-1-octene)-(propylene-1-decene) polymerization materials are included.

[0073] Here, the description of "(propylene)-(propylene-ethylene) polymerization material" means "a heterophasic propylene polymerization material in which polymer I is a propylene homopolymer and polymer II is a propylene-ethylene copolymer". The same applies to other similar expressions.

[0074] As the heterophasic propylene polymerization material, (propylene)-(propylene-ethylene) polymerization material, (propylene)-(propylene-ethylene-1-butene) polymerization material, (propylene-ethylene)-(propylene-ethylene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization material, or (propylene-1-butene)-(propylene-1-butene) polymerization material is preferable, and (propylene)-(propylene-ethylene) polymerization material is more preferable.

[0075] The intrinsic viscosity ([η]I) of polymer I is preferably 0.10 to 4.00 dL / g, more preferably 0.50 to 3.00 dL / g, and still more preferably 0.70 to 2.00 dL / g.

[0076] The intrinsic viscosity ([η]II) of polymer II is preferably 1.00 to 10.00 dL / g, more preferably 2.00 to 10.00 dL / g, and still more preferably 2.00 to 9.00 dL / g.

[0077] Also, the ratio ([η]II / [η]I) of the intrinsic viscosity ([η]II) of polymer II to the intrinsic viscosity ([η]I) of polymer I is preferably 1 to 20, and more preferably 1 to 10.

[0078] As an example of the method for measuring the intrinsic viscosity ([η]I) of polymer I, a method of extracting polymer I formed from the reactor forming polymer I and measuring the intrinsic viscosity of the polymer can be mentioned.

[0079] The intrinsic viscosity ([η]II) of Polymer II can be calculated, for example, by the following formula (6) using the intrinsic viscosity ([η]Total) of the heterophasic propylene polymerization material, the intrinsic viscosity ([η]I) of Polymer I, and the contents of Polymer II and Polymer I.

[0080] [η]II = ([η]Total - [η]I × XI) / XII ···(6) [η]Total: Intrinsic viscosity of the heterophasic propylene polymerization material (dL / g) [η]I: Intrinsic viscosity of Polymer I (dL / g) XI: Ratio of the weight of Polymer I to the total weight of the heterophasic propylene polymerization material (weight of Polymer I / weight of heterophasic propylene polymerization material) XII: Ratio of the weight of Polymer II to the total weight of the heterophasic propylene polymerization material (weight of Polymer II / weight of heterophasic propylene polymerization material)

[0081] Here, XI and XII can be determined from the material balance during polymerization.

[0082] Note that XII may also be calculated using the following formula by measuring the heat of fusion of Polymer I and the heat of fusion of the heterophasic propylene polymerization material. XII = 1 - (ΔHf)T / (ΔHf)P (ΔHf)T: Heat of fusion of the heterophasic propylene polymerization material (J / g) (ΔHf)P: Heat of fusion of Polymer I (J / g)

[0083] The intrinsic viscosity ([η]CXIS) of the CXIS component is preferably 0.10 to 4.00 dL / g, more preferably 0.50 to 3.00 dL / g, and even more preferably 0.70 to 2.00 dL / g.

[0084] The intrinsic viscosity ([η]CXS) of the CXS component is preferably from 1.00 to 10.00 dL / g, more preferably from 2.00 to 10.00 dL / g, and still more preferably from 2.00 to 9.00 dL / g.

[0085] The ratio ([η]CXS / [η]CXIS) of the intrinsic viscosity ([η]CXS) of the CXS component to the intrinsic viscosity ([η]CXIS) of the CXIS component is preferably from 1 to 20, more preferably from 1 to 10.

[0086] The molecular weight distribution (Mw(I) / Mn(I)) of Polymer I is preferably 3.0 or more, more preferably 4.0 or more.

[0087] The molecular weight distribution (Mw(CXIS) / Mn(CXIS)) of the CXIS component is preferably 3.0 or more, more preferably 4.0 or more.

[0088] The melt flow rate (MFR) (temperature: 230 °C, load: 2.16 kgf) of the propylene polymer is preferably from 1 to 100 g / 10 min, more preferably from 12 to 70 g / 10 min, and still more preferably from 5 to 40 g / 10 min, from the viewpoint of the moldability of the resin composition and the like. The MFR of the propylene polymer is preferably 10 g / 10 min or more from the viewpoint of improving the moldability of the resulting resin composition. The MFR of the resin material is preferably 100 g / 10 min or less from the viewpoint of improving the impact resistance of the resulting resin composition and molded article.

[0089] Filler In one aspect, the resin material, this recycled resin, and / or this resin composition contain a filler.

[0090] Examples of the filler include inorganic fillers and organic fillers. The resin composition of the present invention may contain only one type of filler or two or more types of fillers.

[0091] Examples of the inorganic filler include glass, silicate minerals, alumina, silica, silicon dioxide, titanium oxide, iron oxide, aluminum oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, carbonate minerals, calcium sulfate, magnesium sulfate, basic magnesium sulfate, calcium sulfite, carbon black, and cadmium sulfide.

[0092] Examples of the organic filler include polyester, aromatic polyamide, cellulose, and vinylon.

[0093] The shape of the filler may be plate-like, needle-like, or fibrous.

[0094] From the viewpoints of the rigidity, impact resistance, and dimensional stability of the molded article, the inorganic filler is preferable, and talc, which is a plate-like silicate mineral, is more preferable.

[0095] Ethylene-α-olefin copolymer E When the resin material and the recycled resin contain an ethylene-α-olefin polymer, and / or when the resin composition of the present invention contains an ethylene-α-olefin polymer as a component other than the recycled resin, preferable embodiments of the ethylene-α-olefin polymer are shown below.

[0096] The ethylene-α-olefin polymer may be an ethylene-α-olefin block polymer or an ethylene-α-olefin random polymer.

[0097] In the ethylene-α-olefin polymer, assuming the total weight of the ethylene-α-olefin polymer is 100% by weight, the total content of the monomer units derived from ethylene and the monomer units derived from α-olefins having 4 or more carbon atoms contained in the ethylene-α-olefin polymer may be 100% by weight.

[0098] Examples of α-olefins having 4 or more carbon atoms include α-olefins having 4 to 12 carbon atoms. Examples of α-olefins having 4 to 12 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene. Among them, 1-butene, 1-hexene, and 1-octene are preferred. The above α-olefin may be an α-olefin having a cyclic structure such as vinylcyclopropane or vinylcyclobutane.

[0099] Examples of ethylene-α-olefin polymers include ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, ethylene-1-decene copolymers, ethylene-(3-methyl-1-butene) copolymers, and copolymers of ethylene and an α-olefin having a cyclic structure.

[0100] In the ethylene-α-olefin polymer, the content of monomer units derived from α-olefins having 4 or more carbon atoms is preferably 1 to 49% by weight, more preferably 5 to 49% by weight, and still more preferably 24 to 49% by weight based on the total weight of the ethylene-α-olefin polymer.

[0101] From the viewpoint of the impact resistance of the molded article, the density of the ethylene-α-olefin polymer is preferably 0.85 to 0.89 g / cm3, more preferably 0.85 to 0.88 g / cm3, and still more preferably 0.85 to 0.87 g / cm3.

[0102] The MFR (at a temperature of 230°C and a load of 2.16 kgf) of the ethylene-α-olefin random polymer is preferably 0.1 to 80 g / 10 min.

[0103] The MFR (at a temperature of 190°C and a load of 2.16 kgf) of the ethylene-α-olefin block polymer is preferably 0.1 to 80 g / 10 min, 0.5 to 10 g / 10 min, or 1 to 8 g / 10 min.

[0104] Method for producing ethylene-α-olefin polymer The ethylene-α-olefin polymer may be produced by polymerizing ethylene and an α-olefin having 4 or more carbon atoms using a polymerization catalyst.

[0105] Examples of the polymerization catalyst include homogeneous catalysts typified by metallocene catalysts and Ziegler-Natta type catalysts.

[0106] Examples of the homogeneous catalyst include a catalyst containing a compound of a Group 4 transition metal of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; a catalyst containing a compound of a Group 4 transition metal of the periodic table having a cyclopentadienyl ring, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound; and a catalyst obtained by supporting and modifying an inorganic particle (such as silica, clay mineral, etc.) with a catalyst component (such as a compound of a Group 4 transition metal of the periodic table having a cyclopentadienyl ring, a compound that forms an ionic complex, an organoaluminum compound, etc.).

[0107] Examples of the Ziegler-Natta type catalyst include a catalyst in which a titanium-containing solid transition metal component and an organometallic component are combined.

[0108] As the virgin ethylene-α-olefin random copolymer, a commercially available product may be used. Examples of commercially available ethylene-α-olefin random copolymers include Engage (registered trademark) manufactured by The Dow Chemical Company Japan Ltd., Tafmer (registered trademark) manufactured by Mitsui Chemicals, Inc., Neozex (registered trademark), Ultrezex (registered trademark) manufactured by Prime Polymer Co., Ltd., Exxcelen FX (registered trademark), Sumika Sen (registered trademark), and Esprene SPO (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.

[0109] Content of each component In the resin material used in the method of the present invention and the recycled resin produced, the content of the contained components is not particularly limited. However, from the viewpoint of the heat resistance of the produced recycled resin, it is preferable that the resin material and the present recycled resin contain 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight, or 90% by weight or more of a propylene polymer (assuming the weight of the resin material or the present recycled resin is 100% by weight).

[0110] From the viewpoint of heat resistance, it is preferable that the present resin composition or molded article contains 0.1% by weight or more, 1% by weight or more, 5% by weight or more, 10% by weight or more, 30% by weight or more, 50% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, 98% by weight or more, or 99% by weight or more of the present recycled resin (assuming the weight of the present resin composition or molded article is 100% by weight). The upper limit of the content may be any of 99% by weight, 95% by weight, 90% by weight, 80% by weight, 70% by weight, 60% by weight, 50% by weight, 40% by weight, 30% by weight, 20% by weight, 10% by weight, 5% by weight, 4% by weight, 3% by weight, 2% by weight, 1% by weight, from the comprehensive viewpoints of heat resistance, impact resistance, hinge resistance, moldability, etc.

[0111] When the present resin composition or molded article contains an ethylene-α-olefin polymer as a contained component of the present recycled resin or as another component, the content of the ethylene-α-olefin polymer may be 0 to 50% by weight, 0.1 to 40% by weight, 1 to 30% by weight, or 5 to 25% by weight based on the total weight of the content of the present resin composition or molded article, from the comprehensive viewpoints of heat resistance, impact resistance, hinge resistance, moldability, etc.

[0112] When the present resin composition or molded article contains a filler, the content of the filler may be 0 to 80% by weight, 1 to 60% by weight, 5 to 50% by weight, 10 to 40% by weight, 10 to 35% by weight, or 15 to 25% by weight based on the total weight of the content of the present resin composition or molded article, from the comprehensive viewpoints of heat resistance, impact resistance, hinge resistance, moldability, etc.

[0113] The total amount of polymers contained in the resin composition or molded article is preferably 70% by weight or more, 80% by weight or more, or 90% by weight or more based on the total weight of the resin composition or molded article from the comprehensive viewpoints of heat resistance, impact resistance, hinge resistance, moldability, etc.

[0114] Surface removal In the step of physically removing the surface of the resin material in the present invention, the removal means is not limited as long as the surface of the material can be physically removed. Examples thereof include polishing (a process of finely shaving the surface of an object using flowing particles), grinding (a process of shaving an object with abrasive grains on the surface of a rotating grindstone), and cutting (a process of shaving a workpiece using a tool such as a blade). Grinding may be included in polishing. Examples of polishing and grinding include grinding wheel polishing, cloth paper polishing, lapping polishing, polishing (buff polishing), and barrel polishing. Conditions such as the type of grindstone, the size (roughness) of the grindstone, the polishing speed, the polishing pressure, and the polishing temperature in polishing can be set as appropriate. Examples of the instruments used for polishing include an electric naloberter (for example, NR-11E manufactured by Office Mine Co., Ltd.) and a plastic pellet surface treatment machine (PBA25A manufactured by Satake Co., Ltd.). Further, as an example of a document related to a surface treatment apparatus, JP2011-148166A can be cited. An example of cutting includes milling.

[0115] In the present invention, during the above-mentioned "physical" surface removal, "chemical" surface removal and / or surface smoothing such as melting by heat and melting by chemical reaction may be performed before, and / or after.

[0116] The amount of the surface to be removed is not limited, but from the viewpoint of heat resistance, it is preferably 1% by weight, 2% by weight, or 3% by weight or more of the surface is removed in one removal step. If desired, the surface removal treatment may be performed once or two or more times. When the surface removal is performed two or more times, washing and / or drying (dehydration) described later may be performed before the second or subsequent removal.

[0117] Washing, drying (dehydration) The method for producing the recycled resin of the present invention includes a step of washing the resin material after surface removal. Other steps may be included between surface removal and washing. The production method may also include a step of washing the resin material before surface removal, and may include a step of washing the recycled resin before and / or after surface removal. For washing, for example, gases such as air, water, organic solvents, etc. can be used. These cleaning agents may contain additives according to the desired purpose. The washing temperature, washing pressure, etc. can be set as appropriate, for example, it can be -20 to 80 °C, 0 to 60 °C, 20 to 40 °C. One or more washing treatments may be performed.

[0118] For example, after washing with a liquid, the resin material and / or the recycled resin may be dried (dehydrated). For drying, for example, natural drying, drying by heat, drying by wind, centrifugation can be used. One or more drying treatments may be performed. Examples of the devices used for washing and drying include a washing and dehydrating machine (Elgata manufactured by Nippon Seam Co., Ltd.).

[0119] Method for producing a propylene resin composition The resin composition of the present invention can be obtained by melt-kneading each raw material component. The temperature during melt-kneading may be 180 °C or higher, may be 180 to 300 °C, or may be 180 to 250 °C.

[0120] For melt-kneading, a Banbury mixer, a single-screw extruder, a twin-screw co-rotating extruder, etc. can be used.

[0121] The kneading order of each raw material component is not particularly limited. For example, all components may be kneaded together, or among all components, some components may be kneaded first, and then the obtained kneaded product and other components may be kneaded.

[0122] The shape of the propylene resin composition is not particularly limited, and the propylene resin composition may be, for example, in the form of strands, sheets, flat plates or pellets. The pellet-shaped resin composition can be produced, for example, by forming a strand-shaped resin composition and then cutting it to an appropriate length.

[0123] From the viewpoints of the moldability of the resin composition and the production stability when producing a molded article, the shape of the resin composition before being molded into a molded article is preferably in the form of pellets having a length of about 1 to 50 mm.

[0124] The resin composition of the present invention may contain components other than those described above. Although there may be overlap with the above components, examples of such components include, for example, thermoplastic resins (polystyrenes (such as polystyrene, poly(p-methylstyrene), poly(α-methylstyrene), AS (acrylonitrile / styrene copolymer) resin), ABS (acrylonitrile / butadiene / styrene copolymer) resin, AAS (special acrylic rubber / acrylonitrile / styrene copolymer) resin, ACS (acrylonitrile / chlorinated polyethylene / styrene copolymer) resin, polychloroprene, chlorinated rubber, polyvinyl chloride, polyvinylidene chloride, acrylic resins, ethylene / vinyl alcohol copolymer resin, fluororesins, polyacetal, grafted polyphenylene ether resin and polyphenylene sulfide resin, polyurethane, polyamide, polyester resins (such as polyethylene terephthalate, polybutylene terephthalate), polycarbonate, polysulfone, polyether ether ketone, polyether sulfone, aromatic polyester resin, polybutadiene, 1,2-polybutadiene, polyisoprene, styrene / butadiene copolymer, butadiene / acrylonitrile copolymer, natural rubber, etc.), epoxy resins, diallyl phthalate prepolymers, silicone resins, silicone rubbers, epichlorohydrin rubbers, acrylic rubbers, and further PLA resin (polylactic acid) produced by polymerizing plant-derived monomers extracted from bio-based raw materials, neutralizing agents, antioxidants, ultraviolet absorbers, nucleating agents, lubricants, antistatic agents, antiblocking agents, processing aids, organic peroxides, colorants (inorganic pigments, organic pigments, pigment dispersants, etc.), foaming agents, foaming nucleating agents, plasticizers, flame retardants, crosslinking agents, crosslinking aids, brightening agents, antibacterial agents, and light diffusing agents).

[0125] The above components that the resin composition may contain may be virgin materials, may be recycled materials, may be included in the raw materials during recycling, and may be included in the raw materials for manufacturing the resin composition together with the recycled propylene polymer.

[0126] Resin composition

[0127] The resin composition of the present invention can be used as a material for forming a molded article by molding. The resin composition of the present invention is preferably used as a material for injection molding. Hereinafter, an example of an injection molded article manufactured using the resin composition of the present invention as a material for injection molding will be described.

[0128] The melt flow rate (MFR) (temperature: 230 °C, load: 2.16 kgf) of the resin composition is preferably 1 to 100 g / 10 minutes, more preferably 12 to 70 g / 10 minutes, and even more preferably 5 to 40 g / 10 minutes, from the viewpoint of the moldability of the resin composition and the like. The MFR of the resin composition is preferably 10 g / 10 minutes or more from the viewpoint of improving its moldability. The MFR of the resin composition is preferably 100 g / 10 minutes or less from the viewpoint of improving the impact resistance of the resulting resin composition and molded article.

[0129] Molded article The molded article of the present invention contains (is made from) the resin composition of the present invention. The molded article of the present invention is excellent in heat resistance and / or hinge resistance.

[0130] The above injection molded article can be manufactured by an injection molding method. Examples of the injection molding method include a general injection molding method, an injection foam molding method, a supercritical injection foam molding method, a super high-speed injection molding method, an injection compression molding method, a gas assist injection molding method, a sandwich molding method, a sandwich foam molding method, and an insert / outset molding method. There is no particular limitation on the shape of the injection molded article.

[0131] The injection molded article of the present invention can be preferably used, for example, in applications for automotive materials, home appliance materials, and container applications, and among them, it is suitable for automotive interior and exterior applications. Examples of automotive interior and exterior parts include door trims, pillars, instrument panels, and bumpers.

Examples

[0132] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[0133] In the examples and comparative examples, the following raw materials were used.

[0134] First sample: Sample 1 (automobile interior material crushed to under 15 mm (resin composition containing propylene polymer (heterophasic propylene polymerization material), ethylene-1-butene-random copolymer, ethylene-1-octene-random copolymer, talc)) Melt flow rate (MFR) (230 °C, 2.16 kg load): 32.5 g / 10 min Ash content: 4.6 wt% CXIS component (xylene-insoluble component): 77.0 wt% CXS component (xylene-soluble component): 23.0 wt% Samples from the second time onwards: Samples that were processed in the previous round

[0135] Surface treatment device: Surface treatment device PBA25A (manufactured by Satake Corporation) Washing and dewatering device: Washing and dewatering machine ERGATA (manufactured by Nippon Seam Co., Ltd.)

[0136] Surface treatment conditions Main shaft motor load: Target value 60 A Blower fan (for internal cooling): ON when over 110 °C, OFF when 110 °C or below Number of treatments: 3 to 5 times Rotary valve: Frequency 60 Hz Washing and dewatering conditions Water flow rate: 900 L / hr Resin flow rate: 400 kg / hr

[0137] Measurement conditions Weight of the sample: Measured using a weighing platform scale HW-60KGL (manufactured by A&D Company, Limited) Surface temperature immediately after surface treatment (only for samples with 0 treatment times, temperature before polishing): Measured using a radiation thermometer IT-540 (manufactured by Horiba, Ltd.) Supply flow rate of the sample to the surface treatment device: 291 - 304 kg / hr Oxidation induction time (OIT): Measured by a differential scanning calorimeter (DSC250 manufactured by TA Instruments)

[0138] <Measurement method of the weight ratio of CXI component and CXS component> About 4 g of the resin material was refluxed with boiling xylene for 5 hours using a cylindrical filter paper and a Soxhlet extraction tube. Next, the extract was concentrated under reduced pressure using a rotary evaporator to obtain a polymer component. About 2 g of the obtained polymer component was precisely weighed (this "weight of the polymer component" is referred to as "a"), and heated and dissolved in boiling xylene for 2 hours. Then, after cooling to 20 °C, it was filtered using a filter paper. The filtered filtrate was concentrated under reduced pressure using a rotary evaporator to obtain a CXS component. The obtained CXS component was precisely weighed (hereinafter, the "weight of the CXS component" is referred to as "b"). The weight ratio of the CXI component and the weight ratio of the CXS component in the resin material were calculated by the following formula using the numerical values a and b. Also, the CXI component was obtained by vacuum drying the solid matter remaining on the filter paper. Weight ratio of CXS component (wt%) = (b / a) × 100 Weight ratio of CXI component (wt%) = 100 - Weight ratio of CXS component (wt%)

[0139] Experimental procedure 1. 1.130 kg of the sample was pneumatically conveyed to the supply tank above the surface treatment apparatus. 2. The sample was supplied from the supply tank to the surface treatment apparatus through the rotary valve at its lower part. 3. While adjusting the pressing force of the lid so that the motor load becomes 60 A, the entire amount of the sample was surface-removed, and the obtained recycled resin was collected. 4. The weight and surface temperature of the collected recycled resin were measured. 5. If the surface temperature exceeded 110 °C, the blower fan was turned on, and if it dropped below 110 °C, it was turned off. 6. Immediately after the completion of step 5, steps 1 to 4 were performed again using the recycled resin, and repeated a total of 5 times including the first time. 7. The extracted sample was put into a washing and dehydrating apparatus, and washing and drying treatments were carried out.

[0140] The removal yields for each cycle, the cumulative removal yield from the first cycle to each subsequent cycle, the surface temperature of the recycled resin immediately after recovery, and the supply flow rate of the sample are shown in Table 1, and the comparison of the oxidation induction times before and after polishing is shown in Table 2. Here, the "removal yield" is the ratio of the weight of the sample after removal to the weight of the sample before removal (or the first sample).

Table 1

Table 2

[0141] From Table 2, it was confirmed that by the method of the present invention, the OIT is extended by surface removal, that is, the heat resistance of the resin is improved. Although the present invention is not bound by the following theory, this effect may be based on the fact that the surface is smoothed in the surface removal process.

[0142] Furthermore, similar experiments were conducted using Samples 2 to 6 (all automotive materials, resin compositions containing propylene polymers). The experimental conditions and results are also shown in the table below. The results of Sample 1 in the table below are reproduced from the results described in Tables 1 and 2.

[0143] Sample 2: Automobile HVAC material crushed to less than 15 mm (resin composition containing propylene polymer (heterophasic propylene polymerization material) and talc) Melt flow rate (MFR) (230 °C, 2.16 kg load): 33.0 g / 10 min Ash content: 13.5 wt% CXIS component (xylene-insoluble component): 97.5 wt% CXS component (xylene-soluble component): 2.5 wt%

[0144] Sample 3: Automobile HVAC material crushed to less than 15 mm (resin composition containing propylene polymer (heterophasic propylene polymerization material) and talc) Melt Flow Rate (MFR) (230°C, 2.16 kg load): 37.0 g / 10 min Ash content: 15.2 wt% CXIS component (xylene-insoluble component): 97.0 wt% CXS component (xylene-soluble component): 3.0 wt%

[0145] Sample 4: Automobile pillar material crushed to under 15 mm (resin composition containing propylene polymer (heterophasic propylene polymerization material), ethylene-1-butene-random copolymer, and talc) Melt Flow Rate (MFR) (230°C, 2.16 kg load): 32.3 g / 10 min Ash content: 2.8 wt% CXIS component (xylene-insoluble component): 83.5 wt% CXS component (xylene-soluble component): 16.5 wt%

[0146] Sample 5: Automobile connector material crushed to under 15 mm (resin composition containing propylene polymer (propylene homopolymer)) Melt Flow Rate (MFR) (230°C, 2.16 kg load): 30.5 g / 10 min Ash content: 0.1 wt% CXIS component (xylene-insoluble component): 99.6 wt% CXS component (xylene-soluble component): 0.4 wt%

[0147] Sample 6: Automobile bumper material crushed to under 15 mm (resin composition containing propylene polymer (heterophasic propylene polymerization material), ethylene-1-butene-random copolymer, ethylene-1-octene-random copolymer, and talc) Melt Flow Rate (MFR) (230°C, 2.16 kg load): 26.3 g / 10 min Ash content: 8.3 wt% CXIS component (xylene-insoluble component): 58.2 wt% CXS component (xylene-soluble component): 41.8 wt%

[0148]

Table 3

[0149] The peeling method described above is shown below.

[0150] Using an electric nare berta (NR-11E manufactured by Office Mine Co., Ltd.), the surface was polished so as to obtain a desired peeling amount (%). For the samples after the surface treatment, the polishing powder adhering to the surface was removed by blowing with compressed air. The method for calculating the peeling amount is as follows. Peeling amount (w) (unit: wt%) = (Surface-treated crushed material (b) after removing polishing powder (unit: g) - Crushed material (a) before surface treatment (unit: g)) / Crushed material (a) before surface treatment (unit: g) × 100

[0151] From Table 3, it was confirmed that by physically removing the surface of the resin material in which the weight ratio of CXS is 2.0 wt% to 40 wt%, the OIT is extended, that is, the heat resistance of the resin is improved.

Claims

1. A method for producing recycled resin, comprising the steps of physically removing the surface of a resin material without coating adhesion and then washing the resin, wherein the resin material without coating adhesion contains a propylene polymer, and the weight ratio of the xylene-soluble component in the resin material, measured by the following method, is 2.0 wt% to 40 wt%, method. <Method for Measuring the Weight Ratio of Xylene-Soluble Component> About 4 g of the resin material is refluxed with boiling xylene for 5 hours using a cylindrical filter paper and a Soxhlet extraction tube. Then, the extract is concentrated under reduced pressure using a rotary evaporator to obtain a polymer component. About 2 g of the obtained polymer component is precisely weighed (this "weight of the polymer component" is designated as "a") and heated and dissolved with boiling xylene for 2 hours. Then, after cooling to 20 °C, it is filtered using a filter paper. The filtered filtrate is concentrated under reduced pressure using a rotary evaporator to obtain a xylene-soluble component. The obtained xylene-soluble component is precisely weighed (hereinafter, the "weight of the xylene-soluble component" is designated as "b"). The weight ratio of the xylene-soluble component in the resin material is calculated by the following formula using the numerical values a and b. Weight ratio of CXS component (wt%) = (b / a) × 100

2. The method according to claim 1, wherein the resin material contains a heterophasic propylene polymerization material.

3. The method according to claim 1, wherein 3 wt% or more of the surface is removed by the removal step.

4. Recycled resin obtained by the method according to claim 1.

5. Recycled resin derived from a resin material without coating adhesion, the surface of which has been physically removed, wherein the resin material without coating adhesion contains a propylene polymer, and the weight ratio of the xylene-soluble component in the resin material, measured by the following method, is 2.0 wt% to 40 wt%, Recycled resin. <Method for Measuring the Weight Ratio of Xylene-Soluble Component> About 4 g of the resin material is refluxed with boiling xylene for 5 hours using a cylindrical filter paper and a Soxhlet extraction tube. Next, the extract is concentrated under reduced pressure using a rotary evaporator to obtain a polymer component. Approximately 2 g of the obtained polymer component is precisely weighed (this "weight of the polymer component" is designated as "a") and heated and dissolved with boiling xylene for 2 hours. Then, after cooling to 20°C, it is filtered using filter paper. The filtered filtrate is concentrated under reduced pressure using a rotary evaporator to obtain a xylene-soluble component. The obtained xylene-soluble component is precisely weighed (hereinafter, the "weight of the xylene-soluble component" is designated as "b"). The weight ratio of the xylene-soluble component in the resin material is calculated by the following formula using the numerical values a and b. Weight ratio of CXS component (wt%) = (b / a) × 100

6. A resin composition comprising the recycled resin according to claim 4.

7. The resin composition according to claim 6, further comprising a virgin propylene polymer.

8. The resin composition according to claim 6, further comprising an ethylene-α-olefin copolymer.

9. The resin composition according to claim 8, comprising a recycled ethylene-α-olefin copolymer as the ethylene-α-olefin copolymer.

10. The resin composition according to claim 6, comprising a filler F.

11. The resin composition according to claim 10, comprising a recycled filler as the filler F.

12. The resin composition according to claim 10, comprising an inorganic filler as the filler F.

13. A molded article comprising the recycled resin according to claim 4 or 5 or the resin composition according to any one of claims 6 to 12.

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