JP5543801B2 - Resin molded products in contact with transition metals - Google Patents

Description

  The present invention relates to a polypropylene resin molded article that contacts a transition metal, a transition metal compound and / or a transition metal ion compound.

Polypropylene resin is lightweight and has excellent properties such as moldability, water resistance, oil resistance, acid resistance, and alkali resistance. However, these metals (metal ions) show a catalytic action due to prolonged contact with copper (including copper ion generating compounds) and other transition metals (including transition metal ion generating compounds), and the polypropylene resin deteriorates. On the other hand, it is known that the cracks are generated and the mechanical strength of the resin is lowered. For this reason, in the use of molded articles that come into contact with these metals (metal ions), generally, a method of blending additives such as copper damage inhibitors and metal deactivators is used. However, these additives have many problems such as being expensive, bleeding out on the surface of the molded product at the time of molding, and the color tone of the molded product significantly changing due to long-term metal deterioration at high temperature. ing.
For example, Patent Document 1 discloses a resin composition in which an amorphous olefin polymer is blended with a copper damage inhibitor.
Patent Document 2 discloses that a polypropylene resin blended with a copper damage inhibitor is used in obtaining a polypropylene resin molded product to which a metal such as copper is attached.
Patent Documents 3 and 4 disclose that a resin composition containing a polypropylene-based resin and a polyphenylene ether-based resin is excellent in resistance to metal deterioration (improvement of crack generation and mechanical strength reduction).
Patent Document 5 discloses a resin composition having improved metal deterioration resistance, in which a metal deactivator is blended with a propylene-based polymer obtained using a metallocene-based catalyst.
Patent Document 6 discloses a resin composition comprising a propylene-based resin and talc, a phenol-based antioxidant, and a pigment, and exhibiting excellent stability against contact heat deterioration with a metal.

JP 2005-325153 A JP 2001-279882 A Japanese Patent Laid-Open No. 10-110069 JP-A-8-73777 JP-A-9-255825 JP-A-8-188683

However, as disclosed in the above patent document, a resin composition having improved metal degradation resistance by adding additives such as copper damage inhibitors or metal deactivators and phenolic antioxidants to polypropylene resins is Still, there is a secondary problem that the volatility of the additive during processing, the bleed-out problem to the surface of the molded product, and the molded product is discolored due to metal deterioration caused by the transition metal at high temperature. .
Moreover, the resin composition which improved the metal deterioration-proof property by mix | blending the polypropylene resin and polyphenylene ether-type resin currently disclosed in the said patent document becomes a transition metal substantially by addition of polyphenylene ether-type resin. Although the resulting metal deterioration resistance is improved, the molded product may be discolored, and the appearance may be hindered depending on the application.

  The present invention has been made in view of the above circumstances, and has the disadvantages of bleeding out when a stabilizer such as a copper damage inhibitor or a metal deactivator is added to a polypropylene resin, or a polyphenylene ether resin is added to a polypropylene resin. An object of the present invention is to obtain a polypropylene resin molded article excellent in metal deterioration resistance and discoloration resistance due to a transition metal, a transition metal compound and / or a transition metal ion compound, in which discoloration associated with the progress of metal deterioration is reduced.

  The inventors of the present invention pay particular attention to the deterioration phenomenon caused by the transition metal (particularly the first transition metal element) of the polypropylene resin molded product, and cause a large crack phenomenon that can be visually confirmed on the surface of the molded product during the deterioration. I focused on. And this drastic deformation (crack) is considered to be a failure caused by some stress in the amorphous phase of the polypropylene resin, and from the viewpoint of mitigating the stress in the amorphous phase, the metal-resistant deterioration of the polypropylene resin molded product We sought to improve the property (improvement of crack generation and mechanical strength reduction). As a result, a molded product of a resin composition in which a hydrogenated block copolymer having a miscible molecular chain in a non-crystalline part of polypropylene is blended with a polypropylene resin can be obtained at a high temperature for a long time due to transition metals. It has been found that it has excellent metal deterioration resistance against deterioration and discoloration resistance after deterioration, and the present invention has been completed.

That is, the present invention is as follows.
[1]
(A) 100 parts by mass of polypropylene resin,
(B) A conjugated diene compound in which at least two polymer blocks A mainly composed of a vinyl aromatic compound and a conjugated diene compound have a 1,2-vinyl bond amount or a 3,4-vinyl bond amount of 50 to 90% 0.5 to 30 parts by mass of a hydrogenated block copolymer obtained by hydrogenating a block copolymer containing at least one polymer block B mainly comprising:
A resin molded product obtained by molding a resin composition comprising
Manganese, cobalt, any one or more metals selected from the group consisting of copper, direct contact transition metals and an ionic compound comprising a compound and / or the metal containing the metal, and / or,
It is any one of an automobile mechanism part, an automobile exterior part, and an automobile interior part in contact with an aqueous solution containing at least one transition metal ion selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and copper. Plastic molded product.
[2]
The component (a) is a crystalline propylene homopolymer and / or a crystalline propylene-ethylene block copolymer, and its melt flow rate (measured according to ASTM D1238 at 230 ° C. and a load of 2.16 Kg) is 0. The resin molded product according to [1], which is 1 to 150 g / 10 minutes.
[3]
The resin molded product according to [1] or [2], wherein the amount of the vinyl aromatic compound bonded to the component (b) is 10 to 60% by mass.
[4]
The component (b) contains at least two polymer blocks A mainly composed of styrene, and at least one polymer block mainly composed of butadiene in which the 1,2-vinyl bond content of butadiene is 70 to 90%. A resin molded article according to any one of [1] to [3], which is a hydrogenated block copolymer obtained by hydrogenating a block copolymer containing B.
[5]
The resin composition is selected from the group consisting of mold release agents, processing aids, flame retardants, anti-drip agents, nucleating agents, UV blockers, dyes, pigments, antioxidants, plasticizers, antistatic agents, and foaming agents. Any one or more selected additives are further included in an amount of 0.1 to 100 parts by mass with respect to 100 parts by mass in total of the component (a) + the component (b). Any one of the resin molded products.
[6]
The resin composition is inorganic salt, glass fiber (long glass fiber, chopped strand glass fiber), cellulose, glass flake, glass bead, long carbon fiber, chopped strand carbon fiber, whisker, mica, clay, talc, magnesium hydroxide. , Magnesium sulfate and its fibers, silica, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, thermal conductive material (graphite, aluminum nitride, boron nitride, alumina, beryllium oxide, silicon dioxide, magnesium oxide, (Aluminum nitrate, barium sulfate), conductive metal fiber, conductive metal flake, carbon black exhibiting conductivity, carbon fiber exhibiting conductivity, at least one selected from the group consisting of carbon nanotubes , Said component (a) + containing the (b) per 100 parts by weight of component 0.1 to 300 parts by weight Further, [1] to [5] a resin molded article according to any one of.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin molded product having excellent metal deterioration resistance at high temperatures (improvement of crack generation and mechanical strength reduction), which is a defect of polypropylene resin, and excellent discoloration resistance due to metal deterioration.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

The resin molded product of this embodiment is
(A) 100 parts by mass of polypropylene resin,
(B) At least two polymer blocks A mainly composed of a vinyl aromatic compound, and mainly a conjugated diene having a 1,2-vinyl bond amount or a 3,4-vinyl bond amount of 50 to 90% of the conjugated diene. 0.5 to 30 parts by mass of a hydrogenated block copolymer obtained by hydrogenating a block copolymer containing at least one polymer block B
It is a resin molded product that is obtained by molding a resin composition containing selenium and directly and / or indirectly in contact with transition metals.

[(A) component]
The polypropylene resin of component (a) that forms the matrix of the resin composition of the present embodiment is not particularly limited, and includes, for example, a crystalline propylene homopolymer; a crystalline propylene homopolymer portion obtained in the first step of polymerization; A propylene-ethylene random copolymer portion obtained by copolymerizing propylene, ethylene and / or at least one other α-olefin (for example, butene-1, hexene-1, etc.) after the second step of polymerization. Examples thereof include crystalline propylene-ethylene block copolymers. The component (a) may be a mixture of the crystalline propylene homopolymer and the crystalline propylene-ethylene block copolymer. These polypropylene resins may be used individually by 1 type, and may use 2 or more types together.

  The method for producing such a polypropylene resin is not particularly limited. For example, in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound, a polymerization temperature of 0 to 100 ° C., a polymerization pressure It is obtained by polymerizing in the range of 3 to 100 atm. At this time, a chain transfer agent such as hydrogen can be added in order to adjust the molecular weight of the polymer. The polymerization method is not particularly limited, and may be either batch type or continuous type.

  Further, solution polymerization in a solvent such as butane, pentane, hexane, heptane, octane, etc .; slurry polymerization; bulk polymerization in a monomer without solvent; gas phase polymerization method in a gaseous monomer, etc. can also be applied.

  Furthermore, in order to increase the isotacticity and polymerization activity of the obtained polypropylene resin, an electron donating compound can be used as an internal donor component or an external donor component as a third component in addition to the polymerization catalyst. The electron donating compound is not particularly limited, and known compounds can be used. For example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate and methyl toluate; phosphorous acid esters such as triphenyl phosphite and tributyl phosphite, and phosphoric acid derivatives such as hexamethylphosphoric triamide An alkoxy ester compound, an aromatic monocarboxylic acid ester and / or an aromatic alkyl alkoxy silane, an aliphatic hydrocarbon alkoxy silane, various ether compounds, various alcohols and / or various phenols.

  The crystalline melting point of the crystalline propylene homopolymer portion of the polypropylene resin is preferably 155 ° C. or higher, more preferably 163 ° C. or higher, and further preferably 165 ° C. or higher. When the crystal melting point is less than 155 ° C., the rigidity and heat resistance (load deflection temperature: DTUL) of the obtained resin molded product tend to be low.

  The crystalline melting point of the crystalline propylene homopolymer portion is a melting point value measured with a differential scanning calorimeter (DSC: for example, DSC-2 type manufactured by Perkin Elmer Co., Ltd.) at a temperature rising rate of 20 ° C./min and a temperature falling rate of 20 ° C./min. It is. Specifically, first, about 5 mg of a sample is kept at 20 ° C. for 2 minutes, then the temperature is raised to 230 ° C. at 20 ° C./minute, kept at 230 ° C. for 2 minutes, and then lowered to 20 ° C. at a temperature drop rate of 20 ° C./minute. Furthermore, after maintaining at 20 ° C. for 2 minutes, the temperature of the top peak of the endothermic peak that appears when the temperature is raised at a rate of temperature increase of 20 ° C./min can be determined as the crystalline melting point. When measuring the crystal melting point with this differential scanning calorimeter (DSC), the crystallization temperature (solidification temperature) peak of the molten polypropylene can be known. At this time, the crystallization temperature of the polypropylene is set in the range of 100 ° C to 130 ° C. Can be confirmed.

  The melt flow rate of the polypropylene resin (MFR: measured at 230 ° C. under a load of 2.16 kg according to ASTM D1238) is preferably 0.1 to 150 g / 10 minutes, more preferably 0.4 to 100 g / 10 minutes, more preferably 0.5 to 80 g / 10 minutes. When the melt flow rate of the polypropylene resin is 0.1 g / 10 min or more, it tends to be a resin composition having an excellent balance between mechanical strength and heat resistance, and when it is 150 g / 10 min or less, moldability and It tends to be a resin composition having an excellent balance of heat resistance. Moreover, when the workability of the obtained resin composition is particularly emphasized, it is preferable to select a polypropylene resin having a melt flow rate of 10 g / 10 min or more.

As the polypropylene resin, the crystalline propylene homopolymer portion has a crystalline melting point of 155 ° C. or higher, a density of 0.905 g / cm ³ or higher, a crystallization temperature of 100 ° C. to 130 ° C., and a melt flow rate of 0.1 to 150 g / 10. Polypropylene resin that is a minute is particularly preferred.

  Further, as the polypropylene resin, in addition to the above polypropylene resin, a polypropylene resin and an α, β-unsaturated carboxylic acid or a derivative thereof in a molten state or a solution state in the presence or absence of a radical generator. You may use the modified polypropylene resin obtained by making it react at the temperature of 30-350 degreeC. Examples of the modified polypropylene resin include a polypropylene resin obtained by grafting or adding 0.01 to 10% by mass of an α, β-unsaturated carboxylic acid or a derivative thereof. The mixing ratio of the polypropylene resin and the modified polypropylene resin is not particularly limited and can be arbitrarily determined.

[Component (b)]
The hydrogenated block copolymer of the component (b) for improving the metal deterioration resistance of the resin molded product and the color change resistance at the time of metal deterioration in this embodiment is at least two polymers mainly composed of a vinyl aromatic compound. A block comprising a block A and at least one polymer block B mainly composed of a conjugated diene compound having a 1,2-vinyl bond amount or a 3,4-vinyl bond amount of 50 to 90% of the conjugated diene compound. It is a hydrogenated block copolymer obtained by hydrogenating the copolymer.

  The structure of the hydrogenated block copolymer is not particularly limited, and for example, ABA type, ABAB type, (AB-) nX type (where n is 1 or more). And X represents a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride or a residue of an initiator such as a polyfunctional organolithium compound.), A-B-A-B- Examples thereof include a hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer having a structure in which block units such as A-type are bonded. Among these, a hydrogenated block copolymer having an A-B-A-B type structure is preferable because it tends to be excellent in fluidity.

  The amount of vinyl aromatic compound bonded in the hydrogenated block copolymer is preferably 10 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 10 to 45% by mass. If the amount of the vinyl aromatic compound bonded in the hydrogenated block copolymer is 10% by mass or more, the mechanical strength tends to be improved, and if it is 60% by mass or less, the balance between heat resistance and mechanical strength. It tends to be excellent.

  The polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block of a vinyl aromatic compound or a vinyl aroma containing more than 50% by mass, preferably 70% by mass or more of a vinyl aromatic compound. It is a copolymer block of a group compound and a conjugated diene compound.

  The polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a conjugated diene compound and vinyl containing more than 50% by mass of the conjugated diene compound, preferably 70% by mass or more. It is a copolymer block with an aromatic compound.

  Examples of the vinyl aromatic compound include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like. Among them, styrene is preferable. These may be used alone or in combination of two or more.

  Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and among them, butadiene is preferable. These may be used alone or in combination of two or more.

  The individual structures of the polymer block A mainly composed of vinyl aromatic compounds and the polymer block B mainly composed of conjugated diene compounds are the distribution of vinyl aromatic compounds or conjugated diene compounds in the molecular chains in the respective polymer blocks. Is random, tapered (in which the monomer component increases or decreases along the molecular chain), partly a block structure of 100% by weight of vinyl aromatic compound or partly a block structure of 100% by weight of conjugated diene compound It may be comprised. In addition, when there are two or more polymer blocks A mainly composed of vinyl aromatic compounds and two polymer blocks B mainly composed of conjugated diene compounds, the respective polymer blocks may have the same structure or different. It may be a structure.

  The polymer block B mainly composed of a conjugated diene compound has a 1,2-vinyl bond amount or 3,4-vinyl bond amount of the conjugated diene compound before hydrogenation of 50 to 90%, more preferably 70 to 90. %.

  The amount of 1,2-vinyl bond or 3,4-vinyl bond of the conjugated diene compound before hydrogenation is particularly important for improving the metal deterioration resistance of the resin molded product and the discoloration resistance at the time of metal deterioration. It becomes a factor. If the 1,2-vinyl bond amount or 3,4-vinyl bond amount of the conjugated diene compound is less than 50%, the effect of improving the resistance to metal deterioration and the discoloration resistance at the time of metal deterioration of the obtained resin molded product is not good. It will be enough. On the other hand, when the 1,2-vinyl bond amount or 3,4-vinyl bond amount of the conjugated diene compound exceeds 90%, industrial production becomes difficult, and the low-temperature impact strength tends to deteriorate.

  As means for adjusting the 1,2-vinyl bond amount or 3,4-vinyl bond amount of the conjugated diene compound to the above range, usually, polar compounds such as ethers, tertiary amines, alkali metal alkoxides are bound. The method of using as a regulator is mentioned. Examples of such polar compounds include diethyl ether, ethylene glycol / dimethyl ether, ethylene glycol / di n-butyl ether, ethylene glycol / n-butyl / tert-butyl ether, ethylene glycol / di-tert-butyl ether, diethylene glycol / dimethyl ether, Triethylene glycol dimethyl ether, tetrahydrofuran, α-methoxymethyltetrahydrofuran, dioxane, 1,2-dimethoxybenzene, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, potassium tert-amyl oxide, potassium tert- A butyl oxide etc. are mentioned, These compounds can be used individually or in mixture of 2 or more types.

  The amount of 1,2-vinyl bond or 3,4-vinyl bond in the conjugated diene compound before hydrogenation can be measured by NMR using nuclear magnetic resonance spectroscopy.

  By performing a hydrogenation reaction on an aliphatic double bond derived from a conjugated diene compound in a block copolymer containing the polymer block A and the polymer block B, a hydrogenated block copolymer is obtained, This can be used as the component (b). The hydrogenation rate with respect to the aliphatic double bond in the block copolymer is preferably 80% or more, more preferably 95% or more. This hydrogenation rate can be measured by nuclear magnetic resonance spectroscopy using NMR.

The hydrogenation catalyst used in the hydrogenation is not particularly limited, and conventionally known catalysts, for example, (1) metals such as Ni, Pt, Pd, and Ru are supported on carbon, silica, alumina, diatomaceous earth, and the like. Supported so-called heterogeneous hydrogenation catalyst, (2) so-called Ziegler-type hydrogenation using an organic acid salt such as Ni, Co, Fe, Cr, or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum A catalyst, (3) a homogeneous hydrogenation catalyst such as a so-called organometallic complex, such as an organometallic compound such as Ti, Ru, Rh, or Zr, can be applied.
Specifically, JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-1-37970, JP-B-1-53851, JP-B-2-9041 Can be applied.

Preferable examples of the hydrogenation catalyst include a mixture of a titanocene compound and a reducing organometallic compound.
As the titanocene compound, for example, a compound described in JP-A-8-109219 can be used. Specific examples include (substituted) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. And compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton.
Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

The temperature condition for carrying out the hydrogenation reaction on the block copolymer is preferably in the range of 0 to 200 ° C, more preferably in the range of 30 to 150 ° C.
The pressure of hydrogen used for the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, and still more preferably 0.3 to 5 MPa.
The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours.
The hydrogenation reaction can be performed by a batch process or a continuous process, and these may be performed alone or in combination.

  (B) The hydrogenated block copolymer includes at least two polymer blocks A mainly composed of styrene and at least 1 mainly composed of butadiene having a 1,2-vinyl bond content of 70 to 90%. A hydrogenated block copolymer obtained by hydrogenating a block copolymer containing the individual polymer blocks B is particularly preferable. A hydrogenated block copolymer obtained by hydrogenating a block copolymer using butadiene as a conjugated diene compound has a lower mechanical strength and lower temperature than a hydrogenated block copolymer using isoprene as a conjugated diene compound. It has excellent characteristics and tends to reduce molecular chain breakage due to heating during processing.

  (B) The number average molecular weight (Mn) of the hydrogenated block copolymer is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and still more preferably 20,000 to 300,000. When the number average molecular weight (Mn) of the hydrogenated block copolymer is 5000 or more, the processability as a solid polymer tends to be easy, and when it is 1000000 or less, the mechanical strength tends to be improved. The number average molecular weight (Mn) can be measured using gel permeation chromatography. Specifically, for example, Showa Denko Co., Ltd. Gel Permeation Chromatography System 21 (Column: Showa Denko Co., Ltd., one KG, one K-800RL, and one K-800R in this order) Connected in series, column temperature: 40 ° C., solvent: chloroform, solvent flow rate: 10 mL / min, sample concentration: 1 g / liter chloroform solution of hydrogenated block copolymer) and standard polystyrene (the molecular weight of standard polystyrene is 3650000) , 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550) are prepared and measured. Both standard polystyrene and hydrogenated block copolymer can be measured by setting the wavelength of UV (ultraviolet rays) of the detection unit to 254 nm.

  (B) The method for producing the hydrogenated block copolymer is not particularly limited. For example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP 54-126255, JP 56-10542, JP 56-62847, JP 56-1000084, JP 2004-269665, British Patent 1130770, US Examples include the methods described in Japanese Patent No. 3281383 and US Pat. No. 3,639,517, and the methods described in British Patent No. 1020720, US Pat. No. 3,333,024 and US Pat. No. 4,501,857.

  Further, as the hydrogenated block copolymer of component (b), in addition to the hydrogenated block copolymer, a hydrogenated block copolymer, an α, β-unsaturated carboxylic acid or a derivative thereof (ester compound) Or an acid anhydride compound (for example, maleic anhydride) in the presence or absence of a radical generator, in a molten state, a solution state or a slurry state, at a temperature of 80 to 350 ° C. A modified hydrogenated block copolymer may be used. Examples of the modified hydrogenated block copolymer include a hydrogenated block copolymer obtained by grafting or adding 0.01 to 10% by mass of an α, β-unsaturated carboxylic acid or a derivative thereof. The mixing ratio of the hydrogenated block copolymer and the modified hydrogenated block copolymer is not particularly limited and can be arbitrarily determined.

  (B) The compounding quantity of a hydrogenated block copolymer is 0.5-30 mass parts with respect to 100 mass parts of (a) polypropylene resin, Preferably it is 1.0-20 mass parts, More preferably, it is 1.0-. 10 parts by mass. When the blending amount of the component (b) is less than 0.5 parts by mass, the metal degradation resistance and the effect of improving the discoloration resistance accompanying the metal degradation become insufficient, and when it exceeds 30 parts by mass, the metal degradation resistance and metal Although it has an effect of improving discoloration resistance due to deterioration, it is not preferable because rigidity, heat resistance, chemical resistance and the like tend to decrease. If the compounding quantity of (b) component exists in the range of 0.5-30 mass parts, it can select arbitrarily in consideration of the rigidity of the resin molded product obtained, heat resistance, toughness, etc.

  The resin composition composed of the above components includes a mold release agent, a processing aid, a flame retardant, an anti-drip agent, a nucleating agent, a UV blocker, a dye, a pigment, an antioxidant, a plasticizer, an antistatic agent, Any one or more additives selected from the group consisting of foaming agents may be further included. These additives are not particularly limited, and those known in the art can be used.

  The lower limit of the amount of the additive is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, with respect to 100 parts by mass in total of the component (a) + component (b). More preferably, it is 0.3 parts by mass or more. The upper limit of the blending amount is 100 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably from the viewpoint of rigidity and heat resistance, with respect to 100 parts by mass in total of the component (a) + (b). 5 parts by mass or less, particularly preferably 3 parts by mass or less. However, in the case of a flame retardant, the upper limit of the blending amount is 100 parts by mass or less, more preferably 70 parts by mass or less, and further preferably 50 parts by mass with respect to 100 parts by mass in total of the components (a) + (b) Or less.

  Examples of the flame retardant include organic phosphate ester compounds, phosphinic acid metal salts, magnesium hydroxide, ammonium polyphosphate flame retardants, melamine flame retardants, triazine flame retardants, aromatic halogen flame retardants, and silicone flame retardants. Examples thereof include at least one selected from the group consisting of a flame retardant and a fluorine-based polymer.

  Resin compositions composed of the above components are inorganic salts, glass fibers (long glass fibers, chopped strand glass fibers), cellulose, glass flakes, glass beads, carbon long fibers, chopped strand carbon fibers, whiskers, mica, clay. , Talc, magnesium hydroxide, magnesium sulfate and its fibers, silica, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, thermal conductive materials (graphite, aluminum nitride, boron nitride, alumina, beryllium oxide, Silicon dioxide, magnesium oxide, aluminum nitrate, barium sulfate), conductive metal fibers, conductive metal flakes, carbon black indicating conductivity, carbon fibers indicating conductivity, carbon nanotubes (hereinafter referred to as “filler composition”). "Both collectively.) May further comprise at least one selected from the.

  The filler component is treated with a surface treatment agent such as a silane coupling agent, a titanate coupling agent, an aliphatic carboxylic acid, an aliphatic metal salt, or an organic treatment with an ammonium salt or the like by an intercalation method. Or a product obtained by treating a resin such as urethane resin or epoxy resin as a binder. The blending amount of the filler component is preferably 0.1 to 300 parts by mass, more preferably 1 to 250 parts by mass, and even more preferably 5 to 100 parts by mass in total of the component (a) + component (b). 200 parts by mass. When the blending amount of the filler component is 0.1 parts by mass or more with respect to a total of 100 parts by mass of the component (a) + the component (b), the mechanical strength is improved and the resulting resin composition There is a tendency that the dimensional accuracy of a resin molded product obtained by molding is improved. On the other hand, if the blending amount of the filler component is 300 parts by mass or less with respect to a total of 100 parts by mass of the component (a) + the component (b), the resin molded product obtained by molding the resulting resin composition There is little sink, the coefficient of linear expansion due to temperature change (−30 ° C. to 120 ° C.) tends to be small, and it tends to be a resin molded product having excellent dimensional accuracy and anisotropy.

Hereinafter, the manufacturing method of the resin composition of this embodiment is demonstrated.
The resin composition can be produced by either a solution blend method or a melt blend method, but as an industrially effective method, a melt blend method using an extruder is particularly preferred.

  Examples of the extruder for melt blending the above components include a single-screw extruder or a multi-screw extruder having two or more screws capable of incorporating a kneading block at an arbitrary position of the screw. The kneading block portion is substantially (L / D) ≧ 1.5, more preferably (L / D) ≧ 5 (where L is the total length of the kneading block, D is the maximum outside of the kneading block) And (π · D · N / h) ≧ 50 (where π = 3.14, D = screw outer diameter corresponding to the metering zone, N = screw rotation speed (rotation / Sec), h = groove depth of the metering zone).

  These extruders have at least a first raw material supply port on the upstream side with respect to the flow direction of the raw material, and at least a second raw material supply port on the downstream side. If necessary, one more downstream of the second raw material supply port. The above raw material supply ports may be provided, and if necessary, a vacuum vent port is provided between these raw material supply ports for degassing, or one between the second raw material supply port and the extruder outlet. The above vacuum vent port may be provided for deaeration.

  As a specific raw material supply method, an extrusion method in which the total amount of the polypropylene resin as the component (a) and the total amount of the hydrogenated block copolymer as the component (b) are supplied together from the first raw material supply port, or the first raw material supply port (A) Component (a) part of the polypropylene resin and (b) component hydrogenated block copolymer all together are supplied together, and the remaining (a) component distributed from the second raw material supply port to the first raw material supply port And a part of the polypropylene resin as the component (a) and a part of the hydrogenated block copolymer as the component (b) are supplied together from the second raw material supply port. An extrusion method in which the remainder of the polypropylene resin as the component (a) and the remainder of the hydrogenated block copolymer as the component (b) distributed together to the raw material supply port can be used. In these extrusion methods, the resin composition is usually melt-kneaded under conditions of an extruder barrel set temperature of 170 to 300 ° C., preferably 200 to 260 ° C., a screw rotation speed of 100 to 1200 rpm, preferably 200 to 800 rpm. Can be manufactured.

  Supply of additives such as mold release agents, processing aids, flame retardants, anti-drip agents, nucleating agents, UV blockers, dyes, pigments, antioxidants, plasticizers, antistatic agents, foaming agents, etc. Either the raw material supply port or the second raw material supply port may be used, and the raw material supply port may be supplied together with other components. In the case of a liquid additive, it can be melt kneaded by an extrusion method in which a plunger pump or a gear pump is used for press-fitting into a press-fitting zone provided in the extruder.

  As a method for supplying the filler component, a method in which the filler component is supplied and melt-kneaded from the second raw material supply port of the extruder in a state where the components (a) and (b) are melt-kneaded is preferable. When the conveying ability of the side feed extruder supplied to the extruder is lowered, which may occur when the filler component is fine powder, the polypropylene resin as the component (a) is supplied from the second raw material supply port onward. And / or an extrusion method in which the component (b) is supplied together with the hydrogenated block copolymer, and a melt component that is supplied together with the filler component and all or part of the component (a) from the first raw material supply port. It is possible to produce a resin composition containing a filler component by an extrusion method.

  The resin composition thus obtained is molded as a resin molded product of various parts by various conventionally known methods such as compression molding, injection molding, extrusion molding, multilayer extrusion molding, profile extrusion molding, and hollow molding. it can.

The resin molded product of the present embodiment can be used as a molded part that directly and / or indirectly contacts transition metals. Here, the term “transition metal” means a transition metal, a transition metal compound and / or a transition metal ion compound.
Here, the transition metal compound is, for example, an organic transition metal such as manganese, titanium, iron, cobalt, chromium, copper, vanadium, nickel, silicon, cerium, samarium, europium, ytterbium, erbium, neodymium, molybdenum, and ruthenium. Metal compounds, composite organometallic compounds containing these transition metals and other metals, metal oxides, composite metal oxides containing these transition metals and other metals, hydroxides and carbonates, acetates, nitrates , Transition metal salts such as phosphates, chlorides and sulfates.
Moreover, a transition metal ion compound means the substance which can perform metal ionization, when these transition metal compounds are made into aqueous solution or strong acid aqueous solution, and these aqueous solution.

  As transition metals, although not particularly limited, any one selected from the group consisting of chromium, manganese, iron, cobalt, nickel, copper from the viewpoint that the effect of improving metal deterioration resistance and discoloration resistance becomes more prominent One or more metals, a compound containing the metal, and / or an ionic compound containing the metal are preferable.

  Examples of the resin molded product that is in direct contact with the transition metal include electric wires and cables in which copper as a metal conductor is coated with the resin molded product. In addition, as a resin molded product that is in direct contact with transition metals, for example, a resin secondary battery in which an aqueous solution containing metal ions (for example, nickel ions) in contact with metal ions through water of a solvent is enclosed. A battery case etc. are mentioned.

  Specific resin molded products include, for example, secondary battery batteries, sheets / films, stretched sheets / films, gasket sealing materials for lithium ion secondary batteries, gasket sealing materials for nickel hydrogen ion secondary batteries, and liquid filters. Examples thereof include polypropylene melt blown nonwoven fabric, automobile mechanism parts, automobile exterior parts, automobile interior parts and the like.

  Examples of automotive mechanism parts include underhood parts, air conditioner housings, heater housings, ducts, fuel tank protectors, connector housings, fuel filter housings, fuel filter caps, cooling fans, fan shrouds, timing belt covers, oil tanks, oil Examples include tank caps, radiator tanks, and under covers. Examples of automotive exterior products include bumpers and bumper beams, low bumper stiffeners, side spoilers, front grills, rear garnishes, door outer handles, pillar covers, door mirror bodies, mat guards, splash boards, Examples include a cowl panel, a wheel cap, various clips, various fasteners, and a lamp housing. Automotive interior components include instrument panels, door trim panels, console boxes, pillar trims, differential grills, meter-related parts (visors and cases), covers, room mirror bodies, seat bags, headrest guides, seat hinge covers, seat belts. Relationship, trunk room cover / box, steering wheel, horn cover, shift lever, shift lever knob, pedals, etc.

  Furthermore, the resin molded product is an electric wire / cable obtained by coating a metal conductor or an optical fiber, a molded substrate for power supply, a light reflecting plate for reflecting a light source, a fuel case for a solid methanol battery, a heat insulating material for a metal pipe, a heat insulating material for a vehicle, Fuel cell water distribution pipes, decorative molded products obtained by metal plating, water cooling tanks, boiler outer cases, and ink printer peripheral components and members. It can be used as molded parts for chassis, water piping, joints, etc.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples, but the present embodiment is not limited to these.

Each component used in the examples and comparative examples is as follows.
(A) Component Polypropylene Resin a-1: Homopolypropylene Crystal Melting Point = 167 ° C., MFR = 0.4
a-2: Homopolypropylene Melting point = 163 ° C., MFR = 6.0
a-3: Homopolypropylene Crystal melting point = 165 ° C, MFR = 16.0
a-4: Homopolypropylene Crystal melting point = 166 ° C., MFR = 70
Here, the crystalline melting point of the polypropylene resin is a melting point value measured with a differential scanning calorimeter (DSC: DSC-2 type manufactured by Perkin Elmer Co., Ltd.) at a heating rate of 20 ° C./min and a cooling rate of 20 ° C./min. . Specifically, first, about 5 mg of a sample is kept at 20 ° C. for 2 minutes, then the temperature is raised to 230 ° C. at 20 ° C./minute, kept at 230 ° C. for 2 minutes, and then lowered to 20 ° C. at a temperature drop rate of 20 ° C./minute. Further, after maintaining at 20 ° C. for 2 minutes, the temperature of the top peak of the endothermic peak that appears when the temperature was raised at a rate of temperature increase of 20 ° C./min was determined as the crystalline melting point.
The MFR (melt flow rate) of the polypropylene resin was measured at 230 ° C. and a load of 2.16 kg according to ASTM D1238.

(B) Hydrogenated block copolymer of component b-1: Polystyrene-hydrogenated polybutadiene-polystyrene (ABA) structure, 44% bonded styrene, number average molecular weight of the whole polymer 93 , 1,000, a molecular weight distribution 1.04, a 1,2-vinyl bond amount of the polybutadiene part before hydrogenation is 77%, and a hydrogenation ratio of the polybutadiene part is 99.9%, and a hydrogenated block copolymer is synthesized, This polymer was designated as (b-1).
Specifically, it was synthesized by the following procedure.
In a cyclohexane solvent in a reactor equipped with a stirrer substituted with nitrogen gas, tetrahydrofuran is added using n-butyllithium as a polymerization initiator and 1,2-vinyl bond content regulator of butadiene, and half of the total styrene used is fed to the reactor. Then, the polystyrene block was polymerized. Thereafter, all butadiene was supplied to the reactor, and butadiene was polymerized based on the living anion group of the polystyrene block chain to synthesize a polymer having a polystyrene-polybutadiene block structure. Further, the remaining half of styrene was supplied to the reactor, and styrene was further polymerized based on the living anion group having a polybutadiene chain at the end, thereby polymerizing a block copolymer having a polystyrene-polybutadiene-polystyrene structure. After completion of the polymerization, the hydrogenation reaction was carried out quantitatively by the method described in US Pat. No. 4,501,857 until the amount of ethylenically unsaturated bonds in the polybutadiene portion was less than 1%. Coalescence was obtained. To this polymer solution after the hydrogenation reaction, 0.3 part of 2,6-di-tert-butyl-p-cresol as a heat deterioration stabilizer was added to 100 g of the polymer, and the cyclohexane as a solvent was removed by heating to remove polystyrene. -A hydrogenated block copolymer (b-1) component having a hydrogenated polybutadiene-polystyrene structure was obtained.

b-2: Polystyrene-hydrogenated polybutadiene-polystyrene structure (ABA), bound styrene content 31% by mass, number average molecular weight 64,000 of the whole polymer, molecular weight distribution 1.07, hydrogen A hydrogenated block copolymer in which the amount of 1,2-vinyl bonds in the polybutadiene portion before addition was 83% and the hydrogenation rate of the polybutadiene portion was 99.9% was synthesized, and this polymer was designated as (b-2).
(B-2) was synthesized by the same method as (b-1) except that the amount of bound styrene, the number average molecular weight of the whole polymer, and the 1,2-vinyl bond amount of the polybutadiene part were as described above.

b-3: Polystyrene-hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene structure (ABAB) having a bound styrene content of 25%, a number average molecular weight of the whole polymer of 38,000, A hydrogenated block copolymer having a molecular weight distribution of 1.06, a 1,2-vinyl bond content of the polybutadiene part before hydrogenation of 79%, and a hydrogenation rate of the polybutadiene part of 99.9% was synthesized. b-3).
The amount of bound styrene, the number average molecular weight of the whole polymer, and the amount of 1,2-vinyl bond in the polybutadiene part are as described above, and polybutadiene / polybutadiene at the end of the polymer sandwiched between two polystyrene chains = 3/1 (weight ratio). Thus, (b-3) was synthesized by the same method as (b-1) except that butadiene was supplied in two parts.

b-4: Polystyrene-hydrogenated polybutadiene-polystyrene structure (ABA), 43% bonded styrene, number average molecular weight 94,000 of the whole polymer, molecular weight distribution 1.03, hydrogenated A hydrogenated block copolymer having a polybutadiene part with a 1,2-vinyl bond content of 38% and a polybutadiene part with a hydrogenation rate of 99.9% was synthesized, and this polymer was designated as (b-4).
(B-4) was synthesized by the same method as (b-1) except that the amount of bound styrene, the number average molecular weight of the whole polymer, and the 1,2-vinyl bond amount of the polybutadiene part were as described above.

(C) Component additive c-1: Commercially available Irganox 1010 (hindered phenol antioxidant manufactured by Ciba Japan): pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate] was defined as (c-1).
c-2: Commercial Irgafos 168 (Piba stabilizer manufactured by Ciba Japan): Tris (2,4-di-t-butylphenyl) phosphite was used as (c-2).
c-3: Commercially available Irganox MD1024 (Ciba Japan copper damage inhibitor): N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine (c -3).

[Reference Examples 1 to 4, Examples 1 to 8, and Comparative Examples 1 to 14]
A twin-screw extruder (ZSK-40; COPERION WERNER & PFLIDEERER) having a first raw material supply port and a second raw material supply port (located at substantially the center of the extruder) set at a temperature of 220 to 250 ° C. and a screw rotation speed of 250 rpm Made in Germany), the components of (a) polypropylene resin, (b) hydrogenated block copolymer, and (c) additive are shown in Tables 1 and 2 as the first raw material supply port of the extruder and The composition of the second raw material supply port was supplied to each raw material supply port and melt kneaded to obtain a resin composition as pellets.
This pellet is supplied to a screw in-line injection molding machine set at 210 to 250 ° C., and a test piece for tensile test under the condition of a mold temperature of 60 ° C. (external shape: full length × full width = 150 mm × 20 mm, test part: thickness (Length × width × length = 4 mm × 10 mm × 80 mm) was injection molded to obtain a test piece having a white color.
In addition, the test piece of polypropylene resin independent obtained here was made into the reference examples 1-4.

[Evaluation of metal deterioration resistance and discoloration resistance]
The evaluation test methods for the resistance to metal degradation at high temperatures (improvement of crack generation and mechanical strength reduction) and the resistance to discoloration associated with metal degradation are as follows.
A copper foil having a size of 40 mm × 25 mm × thickness 0.127 mm was wound around the center of the test part of the test piece obtained by the above injection molding, and the test piece was wrapped with the copper foil by fastening with a binder clip. The upper end of the test piece wrapped with the copper foil was wound with a polyimide film, fastened with a binder clip, suspended on a rack installed in a hot air oven, and a heating test at an oven set temperature of 150 ° C. × 1000 hours was performed. In addition, in order to change how hot air hits, the rack in which the test piece was suspended was rotated 180 degrees every week. After starting the heating test, confirm the occurrence of cracks and breakage of the test pieces wrapped with copper foil, and after 1000 hours, test pieces with no breaks or cracks are subjected to tensile strength test (ISO 527). Tensile elongation was measured. Further, the color of the test piece after 1000 hours from the start of heating was observed to evaluate discoloration resistance.
These results are shown in Tables 1 and 2.

A resin obtained from a resin composition obtained by blending a polypropylene resin with a hydrogenated block copolymer having a 1,2-vinyl bond amount or 3,4-vinyl bond amount of 50% or more of a conjugated diene compound before hydrogenation Molded articles (Examples 1 to 8) are excellent in metal deterioration resistance at 150 ° C. × 1000 hours under copper foil wrap, have no bleed on the surface of the molded article, have a light yellow color, and are excellent in resistance to discoloration. It became clear.
On the other hand, a resin molded product obtained from a resin composition containing a hydrogenated block copolymer in which the amount of 1,2-vinyl bonds or 3,4-vinyl bonds of the conjugated diene compound before hydrogenation is less than 50% (Comparative Examples 1 to 11) are inferior in resistance to metal degradation at 150 ° C. for 1000 hours under copper foil wrap and have no bleeding on the surface of the molded product, but the color is changed from dark yellow to brown. It was also inferior in discoloration resistance.
Moreover, the resin molded product (Comparative Example 12) obtained from the resin composition which mix | blended the copper harm prevention agent (c-3) was excellent in the metal-degradation resistance of 150 degreeC x 1000 hours under copper foil wrap. However, a bleed product was confirmed on the surface of the molded product, and the color was greatly changed to dark brown, resulting in poor discoloration resistance.
In Comparative Example 13 in which the blended amount of the hydrogenated block copolymer was reduced to less than the range of the present embodiment, the results were inferior in metal deterioration resistance and discoloration resistance. Further, in Comparative Example 14 in which the blended amount of the hydrogenated block copolymer exceeds the range of the present embodiment, although the metal deterioration resistance and the discoloration resistance were excellent, the molded product was low in rigidity and soft, and the copper foil In a test at 150 ° C. × 1000 hours under a lap, the molded product was deformed and a decrease in heat resistance was observed.

[Comparative Example 15]
20 parts by mass of poly (2,6-dimethyl-1,4-phenylene ether) having an intrinsic viscosity of 0.41 dL / g measured in chloroform at 30 ° C. was twin-screw extruder (ZSK-40; manufactured by COPERION WERNER & PFLIDEERER, Except having been supplied from the first raw material supply port in Germany), the same components, blending amounts and raw material supply methods as in Example 6 were used, and extrusion was carried out under conditions of a temperature of 220 to 300 ° C. and a screw rotation speed of 250 rpm. Resin pellets in which a polyphenylene ether resin was further added to the component 6 were obtained. A test piece was molded by the above-described method using the obtained resin pellets, and an evaluation test of metal deterioration resistance and discoloration resistance at high temperatures was performed. As a result, the test piece after the deterioration resistance test at 150 ° C. × 1000 hours under the copper foil wrap did not show cracking, but the color tone was dark brown near black and the discoloration resistance was deteriorated. found.

  The resin molded product according to the present invention is excellent in metal deterioration resistance and discoloration resistance associated with metal deterioration even when in contact with transition metals at high temperatures. Has industrial applicability to.

Claims (6)

(A) 100 parts by mass of polypropylene resin,
(B) A conjugated diene compound in which at least two polymer blocks A mainly composed of a vinyl aromatic compound and a conjugated diene compound have a 1,2-vinyl bond amount or a 3,4-vinyl bond amount of 50 to 90% 0.5 to 30 parts by mass of a hydrogenated block copolymer obtained by hydrogenating a block copolymer containing at least one polymer block B mainly comprising:
A resin molded product obtained by molding a resin composition comprising
Manganese, cobalt, any one or more metals selected from the group consisting of copper, direct contact transition metals and an ionic compound comprising a compound and / or the metal containing the metal, and / or,
It is any one of an automobile mechanism part, an automobile exterior part, and an automobile interior part in contact with an aqueous solution containing at least one transition metal ion selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and copper. Plastic molded product. The component (a) is a crystalline propylene homopolymer and / or a crystalline propylene-ethylene block copolymer, and its melt flow rate (measured according to ASTM D1238 at 230 ° C. and a load of 2.16 Kg) is 0. a .1~150g / 10 min, according to claim 1 Symbol placement of the resin molded article. The resin molded product according to claim 1 or 2 , wherein the amount of the vinyl aromatic compound bonded to the component (b) is 10 to 60% by mass. The component (b) contains at least two polymer blocks A mainly composed of styrene, and at least one polymer block mainly composed of butadiene in which the 1,2-vinyl bond content of butadiene is 70 to 90%. The resin molded article according to any one of claims 1 to 3 , which is a hydrogenated block copolymer obtained by hydrogenating a block copolymer containing B. The resin composition is selected from the group consisting of mold release agents, processing aids, flame retardants, anti-drip agents, nucleating agents, UV blockers, dyes, pigments, antioxidants, plasticizers, antistatic agents, and foaming agents. one or more additives or selected, including the component (a) + said (b) further 0.1 parts by weight per 100 parts by weight of the component, any one of claims 1-4 The resin molded product according to 1. The resin composition is inorganic salt, glass fiber (long glass fiber, chopped strand glass fiber), cellulose, glass flake, glass bead, long carbon fiber, chopped strand carbon fiber, whisker, mica, clay, talc, magnesium hydroxide. , Magnesium sulfate and its fibers, silica, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, thermal conductive material (graphite, aluminum nitride, boron nitride, alumina, beryllium oxide, silicon dioxide, magnesium oxide, (Aluminum nitrate, barium sulfate), conductive metal fiber, conductive metal flake, carbon black exhibiting conductivity, carbon fiber exhibiting conductivity, at least one selected from the group consisting of carbon nanotubes , Said component (a) + said (b) per 100 parts by weight of the component further comprises 0.1 to 300 parts by weight, any one of claims of the resin molded article according to claim 1-5.