JP2008101118A - Resin composition and molded product - Google Patents

Abstract

The present invention provides a resin composition that can be produced using a resin composition recovered and recycled from a used resin and that can produce a molded article having excellent elongation at break and impact resistance.
SOLUTION: (a) A conjugated diene compound comprising a recycled resin component containing at least one thermoplastic resin recovered and regenerated from a used resin, and (b) a block copolymer satisfying the following condition (1) Hydrogenated diene block polymer in which 80% or more of units are hydrogenated, and / or (c) Modified hydrogenated diene in which the (b) hydrogenated diene block polymer is modified with at least one functional group A resin composition comprising a block polymer.
(1): It comprises a polybutadiene block (A) having a 1,2-vinyl bond content of 30% or less and a conjugated diene compound unit, and the 1,2-vinyl bond content of the conjugated diene compound unit is more than 70%. A block copolymer represented by a predetermined block structure, comprising a conjugated diene polymer block (B).
[Selection figure] None

Description

  The present invention relates to a resin composition containing a recycled resin component and a molded article, and more specifically, a resin composition containing a recycled resin component and a molded article that can produce a molded article having elongation at break and impact resistance. About.

  In recent years, effective use of resources has been advocated to protect the global environment. One of them is recycling (so-called recycling). There are various items to be recycled, such as resin molded products. Examples of the resin molded product include a plastic packaging container such as a plastic bottle, a bumper, and a battery case. Among these, for example, a plastic packaging container such as a plastic bottle is designated by the Containers and Packaging Recycling Law (Act No. 112). Is subject to recycling.

  However, the recycling of resin molded products has various technical problems, such as those listed below. First, waste materials of resin molded products include thermoplastic or thermosetting resin materials such as polyvinyl chloride, polyethylene, polypropylene, nylon, acrylonitrile, polystyrene, polyamide, polyester, urethane, epoxy, phenol, and the like. Copolymer resin is mixed. Furthermore, not only these resins but also foreign matters such as metal pieces, wood pieces, glass pieces, and fiber scraps are mixed. That is, the waste materials having different melting temperatures are mixed, and when a recycled product is produced as it is, the resulting recycled product is colored due to a decrease in viscosity and various physical properties. Secondly, in order to prevent deterioration of physical properties of the recycled product, a separation process is performed in which the material is separated for each material having a similar melting temperature before the recycling process. However, this separation requires an advanced separation technique and is expensive. In addition, even if a separation process is performed, it is currently impossible to completely avoid coloring and deterioration of physical properties. For example, a PET bottle is made of a transparent single resin without additives and is used at the time of use. The contents are also extremely clean, but the recycled products are colored due to a decrease in viscosity and various physical properties.

  As described above, recycled products of resin molded products are not sufficient for practical use in productivity, quality, and the like, and a recycling system for resin molded products has not yet been established. In such a situation, in order to realize the re-commercialization of the resin molded product, for example, a large amount of plasticizer (for example, oil) or a modifier is blended at the time of manufacturing the recycled product (for example, patent document) 1, Patent Document 2), or the degradation of physical properties of recycled products is prevented by pulverizing waste materials (for example, Patent Document 3).

JP-A-3-277511 JP 2001-26719 A JP-A-8-245756

  However, sufficient physical properties have not been obtained with the recycled products. In particular, there is a problem that the elongation at break is poor and it is weak against external impacts.

  Accordingly, the present invention has been made in view of the above-described problems of the prior art, and the problem is that the present invention is manufactured using a resin composition recovered and recycled from a used resin. Another object of the present invention is to provide a resin composition capable of producing a molded product (recycled product) having excellent elongation at break and impact resistance, and the molded product.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors achieve the above-mentioned problems by blending a specific hydrogenated diene block polymer into a resin composition recovered and regenerated from a used resin. As a result, the present invention has been completed.

  That is, according to the present invention, the following resin composition and molded product are provided.

[1] (a) A conjugated diene compound unit comprising a recycled resin component containing at least one thermoplastic resin recovered and regenerated from a used resin, and (b) a block copolymer satisfying the following condition (1) 80% or more of the hydrogenated diene block polymer hydrogenated and / or (c) the modified hydrogenated diene system in which the (b) hydrogenated diene block polymer is modified with at least one functional group And a block polymer.
(1): It comprises a polybutadiene block (A) having a 1,2-vinyl bond content of 30% or less and a conjugated diene compound unit, and the 1,2-vinyl bond content of the conjugated diene compound unit is more than 70%. The block structure including the conjugated diene polymer block (B) is represented by A- (BA) n or (AB) m (where n and m are integers of 1 or more). A linear or branched block copolymer.

  [2] The resin composition according to [1], wherein the thermoplastic resin is polyethylene (PE) and / or polypropylene (PP).

  [3] The resin composition according to [1] or [2], wherein the block copolymer further includes a vinyl aromatic compound polymer block (C) composed of vinyl aromatic compound units.

  [4] The resin composition according to any one of [1] to [3], wherein the (a) recycled resin component contains a plurality of types of integrated pellet-shaped thermoplastic resins. .

  [5] The resin composition according to any one of the above [1] to [3], wherein the recycled resin component (a) contains a plurality of pellets of the thermoplastic resin separately. .

  [6] The ratio of the polyethylene (PE) and the polypropylene (PP) contained in the (i) recycled resin component is (PE) / (PP) = 5/95 to 95/5 in mass ratio. The resin composition according to any one of [2] to [5].

  [7] The mass ratio of the content ratio of the (a) recycled resin component and the total content of the (b) hydrogenated diene block polymer and the (c) modified hydrogenated diene block polymer. The resin composition according to any one of [1] to [6], wherein (a) / ((b) + (c)) = 99.9 / 0.1 to 70/30.

  [8] A molded article comprising the resin composition according to any one of [1] to [7].

  [9] The molded article according to [8], which is a planter, a building material, a packaging container, a household electrical appliance member, an automobile member, a stationery, or a toy.

  The present invention relates to a resin composition that can be produced using a resin composition recovered and recycled from a used resin, and that can produce a molded product (recycled product) having excellent elongation at break and impact resistance, and its A molded article can be provided.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

The resin composition of the present invention comprises (a) a recycled resin component (hereinafter also referred to as “component (a)”) containing at least one thermoplastic resin recovered and recycled from a used resin, and (b) ) Hydrogenated diene block polymer in which 80% or more of the conjugated diene compound units of the block copolymer satisfying the following condition (1) are hydrogenated (hereinafter also referred to as “(b) component”), And / or (b) the hydrogenated diene block polymer is a modified hydrogenated diene block polymer modified with at least one functional group (hereinafter also referred to as “component (c)”). Is included.
(1): A polybutadiene block (A) having a 1,2-vinyl bond content of 30% or less (hereinafter sometimes referred to as “block (A)”) and a conjugated diene compound unit. A conjugated diene polymer block (B) having a 1,2-vinyl bond content of more than 70% (hereinafter also referred to as “block (B)”), the block structure of which is A- (B A linear or branched block copolymer represented by -A) n or (AB) m (wherein n and m are integers of 1 or more).

(I) Recycled resin components:
(A) The recycled resin component contains at least one thermoplastic resin recovered and regenerated from the used resin. The used resin includes a molded product manufactured using at least one kind of thermoplastic resin as a material, and a thermoplastic resin used for manufacturing the molded product. Examples of the molded article include a packaging film, a packaging container, a planter, a building material, a plastic bottle, a car bumper (automobile member), a stationery, a toy, and the like.

  The thermoplastic resin is not particularly limited as long as it is a thermoplastic resin, and examples thereof include a nonpolar polymer and a polar polymer. Examples of nonpolar polymers include olefin polymers and styrene polymers.

  Examples of styrenic polymers include styrene homopolymer (PS), high impact polystyrene (HIPS), ethylene / styrene copolymer (ESI), acrylonitrile / styrene copolymer (AS), acrylonitrile / butadiene / styrene. Copolymer (ABS), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES), acrylonitrile / chlorinated polystyrene / styrene copolymer (ACS), styrene / methyl methacrylate copolymer (MS), butadiene / styrene -A methyl methacrylate copolymer (MBS), a styrene maleic anhydride copolymer (SMA), etc. can be mentioned.

  Examples of the olefin polymer include polyethylene, polypropylene, poly 1-butene, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer, ethylene / 1-hexene. Copolymer, ethylene / 1-octene copolymer, ethylene / propylene copolymer (EPM), ethylene / propylene / nonconjugated diene copolymer (EPDM), ethylene / 1-butene copolymer (EBM), ethylene -Ethylene / α-olefin / (non-conjugated diene) copolymer such as 1-butene / non-conjugated diene copolymer (EBDM), polar group-containing ethylene / α-olefin copolymer, and metal cross-linked product thereof, ethylene・ Vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene -A methyl acrylate copolymer, an ethylene methyl methacrylate copolymer, an ethylene butyl acrylate copolymer, etc. can be mentioned.

  Examples of the polar polymer include acrylic polymers. Examples of acrylic polymers include poly (meth) acrylate methyl, poly (meth) ethyl acrylate, poly (meth) acrylate butyl, poly (meth) acrylate 2-ethylhexyl, poly (meth) acrylate cyclohexyl Etc.

  In addition to these acrylic polymers, aromatic polycarbonate, polymethacrylonitrile, polyacetal, polyoxymethylene, ionomer, chlorinated polyethylene, coumarone / indene resin, regenerated cellulose, petroleum resin, cellulose derivative, alkali cellulose, cellulose Ester, Cellulose acetate, Cellulose acetate butyrate, Cellulose xanthate, Cellulose nitrate, Cellulose ether, Carboxymethyl cellulose, Cellulose ether ester, Fluororesin, FEP, Polychlorotrifluoroethylene, Polytetrafluoroethylene, Polyvinylidene fluoride, Polyfluoride Fats such as vinyl, nylon 11, nylon 12, nylon 6, nylon 6,10, nylon 6,12, nylon 6,6, nylon 4,6, etc. Aromatic polyamide, polyphenylene isophthalamide, polyphenylene terephthalamide, metaxylylene diamine, polyimide, polyphenylene ether, polyphenylene sulfide, polyether ether ketone, polyamide imide, polyarylate, polyvinylidene chloride, polyvinyl chloride, chlorination Mention may be made of aromatic polyesters such as polyethylene, chlorosulfonated polyethylene, polysulfone, polyethersulfone, polysulfonamide, polyvinyl alcohol, polyvinyl ester, polyisobutyl vinyl ether, polymethyl vinyl ether, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate.

  Among these, the thermoplastic polymer used in large quantities is the olefin polymer (polyolefin). Among olefin polymers, particularly, polyethylene (PE) and / or polypropylene (PP) are used in large quantities.

  For example, when the thermoplastic resin contained in the component (a) is the polyethylene (PE) and polypropylene (PP), the ratio is (PE) / (PP) = 5 / 95- It is preferably 95/5. More preferably, it is 10/90 to 90/10, and particularly preferably 15/85 to 85/15. When either PE or PP is less than 5% by mass, good elongation at break and impact strength (impact resistance) tend not to be obtained.

  (I) Although there is no restriction | limiting in particular in the shape of a component, For example, it can be set as a pellet form, a sheet form, and powder form. Generally, pellets are used, and handling is facilitated by the pellets. Furthermore, the component (a) preferably contains a plurality of integrated thermoplastic resins. A commercially available thing can also be used for such (I) component. As a commercial item, the brand name "PE / PP pellet" by Hiroshima Prefecture Recycle Center etc. can be mentioned, for example.

  In addition, (a) component may contain multiple types of thermoplastic resins as separate bodies. A commercially available thing can also be used for such (I) component. As a commercial item, the brand name "recycled PP", the brand name "recycled PE", etc. by the Hokupere company can be mentioned, for example. Thus, it can adjust to arbitrary compounding ratios by setting it as a different body for every kind of thermoplastic resin.

(B) Hydrogenated diene block polymer:
(B) The hydrogenated diene block polymer is obtained by hydrogenating 80% or more of the conjugated diene compound unit of the block copolymer that satisfies the following condition (1).
(1): It comprises a polybutadiene block (A) having a 1,2-vinyl bond content of 30% or less and a conjugated diene compound unit, and the 1,2-vinyl bond content of the conjugated diene compound unit is more than 70%. The block structure including the conjugated diene polymer block (B) is represented by A- (BA) n or (AB) m (where n and m are integers of 1 or more). A linear or branched block copolymer.

Block copolymer:
As described above, the block copolymer satisfies the following condition (1).
(1): A polybutadiene block (A) having a 1,2-vinyl bond content of 30% or less (hereinafter sometimes referred to as “block (A)”) and a conjugated diene compound unit. A conjugated diene polymer block (B) having a 1,2-vinyl bond content of more than 70% (hereinafter sometimes referred to as “block (B)”), the block structure of which is A- (BA ) N or (AB) m (wherein n and m are integers of 1 or more), a linear or branched block copolymer.

Polybutadiene block (A):
The polybutadiene block (A) is a polymer block having a 1,2-vinyl bond content of 30% or less, and (b) a block copolymer which is a pre-hydrogenated copolymer of a hydrogenated diene block polymer. Configure. Block (A) becomes a crystalline block rich in polyethylene chain by hydrogenation. The 1,2-vinyl bond content in the block (A) is preferably 25% or less, more preferably 20% or less. If the 1,2-vinyl bond content in the block (A) is more than 30%, the crystallinity of the block (A) tends to be lowered, and an amorphous rubber-like block segment tends to be formed. Further, the block (A) has a function of reducing the adhesion between pellets and maintaining the shape when the component (b) is processed into a pellet, for example. By the way, when the crystallinity of a block (A) falls, there exists a tendency for the adhesion at the time of making it a pellet to increase, and to become easy to block. Therefore, processing productivity at the time of blending with component (a) may be significantly reduced.

Conjugated diene polymer block (B):
The block (B) is a polymer block composed of a conjugated diene compound unit, and the 1,2-vinyl bond content of the conjugated diene compound unit is more than 70%. This block (B) constitutes a block copolymer which is a copolymer before hydrogenation of (b) hydrogenated diene block polymer.

  Examples of the conjugated diene compound unit of the block (B) include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1 , 3-hexadiene, 4,5-diethyl-1,3-octadiene, chloroprene and other conjugated diene compounds. Among these, those derived from 1,3-butadiene, isoprene, and 1,3-pentadiene are preferable, can be used industrially, and have excellent physical properties.

  Further, the block (B) needs to have a 1,2-vinyl bond content of the conjugated diene compound unit of more than 70%. Preferably it is 75 to 95%, more preferably 75 to 85%. If the vinyl bond content is 70% or less, (i) compatibility with the recycled resin component deteriorates, and good elongation at break and impact resistance tend not to be obtained.

Vinyl aromatic compound polymer block (C):
The block copolymer preferably further contains a vinyl aromatic compound polymer block (C) composed of vinyl aromatic compound units (hereinafter sometimes referred to as “block (C)”). . The vinyl aromatic compound unit constituting the block (C) is, for example, styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p. Examples thereof include those derived from vinyl aromatic compounds such as aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, and vinylpyridine. Among these, those derived from styrene and α-methylstyrene are preferable.

  The composition ratio of the block (A) and the block (B) in the block copolymer is not particularly limited, but is preferably (A) / (B) = 45/55 to 10/90 by mass ratio. . More preferably, (A) / (B) = 40/60 to 15/85. When it is less than 45/55, the compatibility between PE and PP deteriorates, and the molded product tends to become brittle. When it exceeds 10/90, the binding force of the block (A) decreases, and when pellets are formed. There is a tendency to increase the adhesion of and to facilitate blocking. Therefore, the processing productivity at the time of blending with the component (a) tends to be remarkably reduced.

  Further, when the block copolymer contains the block (C), the composition ratio of the block (A), the block (B), and the block (C) in the block copolymer is not particularly limited, The mass ratio is preferably (A) / (B) / (C) = 12/85/3 to 40/45/15. More preferably, (A) / (B) / (C) = 20/75/5 to 30/60/10.

  The block copolymer preferably has a weight average molecular weight (Mw) of 5,000 or more, more preferably 10,000 or more, and particularly preferably 15,000 or more. If it is less than 5,000, there exists a tendency for favorable fracture elongation property and impact strength property not to be obtained for a molded article.

  The block copolymer has a linear or branched block structure represented by A- (BA) n or (AB) m. However, n and m are integers of 1 or more. Moreover, when the said block copolymer contains a block (C), the block structure is a linear or branched form represented by A- (BC) x or (ABC) y. It is preferable that However, x and y are integers of 1 or more. A indicates the block (A), B indicates the block (B), and C indicates the block (C). In addition, the block copolymer has other polymer blocks other than the above blocks (A) to (C), for example, a polymer in which a conjugated diene compound is hydrogenated, the end of the block copolymer, or the block. One or two or more may be copolymerized in the copolymer chain.

  Further, the component (b) is one in which 80% or more of the conjugated diene compound unit of the block copolymer is hydrogenated, preferably 90% or more, more preferably 95% or more. It is. When the hydrogenation rate is less than 80%, durability such as weather resistance and heat resistance tends to be not obtained. The double bond derived from the conjugated diene compound in the conjugated diene compound unit is composed of 1,2- and 3,4-vinyl bonds as side chain double bonds and 1,4-as main chain double bonds. In the present invention, “80% or more of conjugated diene compound units are hydrogenated” means that 80% or more of these double bonds are hydrogenated.

(B) Weight average molecular weight (Mw) of hydrogenated diene block polymer:
The weight average molecular weight of the component (b) is preferably 40,000 to 700,000, more preferably 70,000 to 500,000, and particularly preferably 100,000 to 400,000. If it is less than 40,000, the resulting molded article tends to have poor impact resistance. On the other hand, when it exceeds 700,000, the fluidity is remarkably lowered and the moldability tends to be inferior.

  (B) The melt flow rate (MFR) of the hydrogenated diene block polymer is preferably 1.0 to 10 g / 10 min, more preferably 1.5 to 7.0 g / 10 min, particularly preferably. 2.0 to 5.0 g / 10 min. There exists a possibility that the fluidity | liquidity of a composition may fall that a melt flow rate (MFR) is less than 1.0 g / 10min. On the other hand, when the melt flow rate (MFR) exceeds 10 g / 10 minutes, the impact resistance of the obtained molded product may be inferior. Here, in this specification, the “melt flow rate (MFR)” is a value obtained by measuring the melt flow rate under conditions of 230 ° C. and 21.2 N load in accordance with JIS K7210.

(B) Synthesis of hydrogenated diene block polymer:
The synthesis method of the component (b) is not particularly limited. For example, using a polymerization initiator in an organic solvent, the block (A) is subjected to living anion polymerization, and then the block (B) is subjected to living anion polymerization. There is a method of hydrogenating the resulting block copolymer.

  As the organic solvent, for example, a hydrocarbon solvent such as pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene, and xylene can be used.

  As a polymerization initiator, an organic alkali metal compound is mentioned, for example. Among these, an organolithium compound is preferable. Examples of the organic lithium compound include organic monolithium compounds, organic dilithium compounds, and organic polylithium compounds. Specific examples thereof include ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, hexamethylene dilithium, butadienyl lithium, and isoprenyl dilithium. It is done. And a polymerization initiator can be mix | blended in the quantity of 0.02-0.2 mass part per 100 mass parts of monomers for comprising (B) component.

  Further, the vinyl bond content of the conjugated diene compound unit can be adjusted by varying the components of the micro-adjusting agent. Furthermore, the weight average molecular weight can be adjusted by varying the amount of polymerization initiator such as n-butyllithium.

  Examples of micro modifiers include Lewis bases such as ethers and amines, specifically diethyl ether, tetrahydrofuran, propyl ether, butyl ether, higher ethers, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, and the like. Examples of the polyethylene glycol ether derivatives and amines include tertiary amines such as tetramethylethylenediamine, pyridine, and tributylamine, which are used together with the organic solvent. Furthermore, the polymerization reaction is usually carried out at −30 ° C. to 150 ° C. Furthermore, the polymerization may be carried out while controlling at a constant temperature, or may be carried out at an elevated temperature without removing heat.

The component (b) is obtained by hydrogenating the block copolymer polymerized as described above. For example, hydrogenation to a block copolymer can be accomplished by dissolving the block copolymer in an inert solvent and in the presence of a hydrogenation catalyst at 20-150 ° C. under 1-100 kg / cm ² of pressurized hydrogen. It can be carried out. Examples of the inert solvent used for hydrogenation include hydrocarbon solvents such as hexane, heptane, cyclohexane, benzene, toluene, and ethylbenzene, or polar solvents such as methyl ethyl ketone, ethyl acetate, ethyl ether, and tetrahydrofuran.

Further, as the hydrogenation catalyst, dicyclopentadienyl titanium halide, organic carboxylate nickel, hydrogenation catalyst comprising organic carboxylate nickel and organometallic compounds of Groups I to III of the periodic table, carbon, silica, Nickel, platinum, palladium, ruthenium, rhenium, rhodium metal catalyst supported on diatomaceous earth, cobalt, nickel, rhodium, ruthenium complex, lithium aluminum hydride, p-toluenesulfonyl hydrazide, and Zr-Ti-Fe-V -Cr alloy, Zr-Ti-Nb-Fe -V-Cr alloy, and a hydrogen storage alloy such as LaNi ₅ alloys.

  Among these hydrogenation catalysts, a catalyst comprising an organic carboxylate of organolithium and cobalt, for example, a catalyst comprising n-butyllithium and cobalt octate is preferred. In this case, the Li / Co ratio (molar ratio) = 2.0 to 2.5 / 1 is appropriate. (B) The hydrogenation rate of the double bond of the conjugated diene compound unit of the component can be adjusted by changing the hydrogenation catalyst, the addition amount of the hydrogenation compound, the hydrogen pressure during the hydrogenation reaction, or the reaction time. it can. Isolation of the component (b) can be easily carried out by removing the catalyst residue from the hydrogenated block copolymer solution and adding a phenol-based or amine-based anti-aging agent. Alternatively, for example, a method in which acetone or alcohol is added to a hydrogenated block copolymer solution to cause precipitation, or the hydrogenated block copolymer solution is stirred in or poured into hot water to distill off the solvent. The component (b) can also be isolated by a method or the like.

  The component (b) further containing the block (C) is a living anion polymerization of the block (A) using a polymerization initiator in an organic solvent, followed by a living anion polymerization of the block (B), Furthermore, after obtaining a block copolymer by carrying out living anion polymerization of the block (C), it can obtain by hydrogenating.

(C) Modified hydrogenated diene block polymer:
It is also possible to use (c) a modified hydrogenated diene block polymer in which at least one functional group is introduced into the (b) component instead of the (b) component or together with the (b) component. Examples of the functional group include a carboxyl group, an acid anhydride group, an epoxy group, a (meth) acryloyl group, an amino group, an alkoxysilyl group, a hydroxyl group, an isocyanate group, and an oxazoline. Among these, an amino group is preferable.

  Examples of the component (c) include the following copolymers ((a) to (f)). Here, the proportion of the functional group in the component (c) is usually preferably 0.001 to 10 mol%, preferably 0.005 to 8 mol% with respect to the molecules constituting the component (b). More preferably, it is 0.01-5 mol%.

  (A) A copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound in the presence of an organic alkali metal compound having an amino group, and hydrogenating the obtained copolymer.

  (B) A copolymer obtained by copolymerizing a vinyl aromatic compound, a conjugated diene compound, and an unsaturated monomer having an amino group in the presence of an organic alkali metal compound, and hydrogenating the obtained copolymer. Coalescence.

  (C) A vinyl aromatic compound and a conjugated diene compound are copolymerized in the presence of an organic alkali metal compound, and a copolymer obtained by reacting an alkoxysilane compound with an active point of the obtained copolymer is obtained. A copolymer obtained by hydrogenating a copolymer.

  (D) A copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound in the presence of an organic alkali metal compound and reacting an epoxy compound or a ketone compound with the active point of the obtained copolymer. A copolymer obtained by hydrogenating the copolymer.

  (E) A copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound in the presence of an organic alkali metal compound and hydrogenating the resulting polymer, a (meth) acryloyl group-containing compound, an epoxy group A copolymer obtained by reacting at least one selected from a containing compound and maleic anhydride in a solution or a kneader such as an extruder.

(F) A vinyl aromatic compound and a conjugated diene compound are copolymerized in the presence of an organic alkali metal compound, and epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, benzene as a coupling agent -1,2,4-triisocyanate, diethyl oxalate, diethyl malonate, diethyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, pyromellitic anhydride, etc. A copolymer having a functional group such as —OH group, —NH—CO— group, —NH— group, —NH ₂ group or the like introduced at the center of the chain.

  The content ratio of the (a) recycled resin component of the resin composition of the present invention, and (b) the hydrogenated diene block polymer and (c) the modified hydrogenated diene block polymer are in a mass ratio, (I) / ((b) + (c)) = 70/30 to 99.9 / 0.1 is preferable. More preferably, the mass ratio is (A) / ((B) + (C)) = 80/20 to 99.8 / 0.2, and particularly preferably (A) / ((B) + ( C)) = 85/15 to 99.7 / 0.3. When the content is less than 70/30, the mechanical strength tends to decrease. When it exceeds 99.9 / 0.1, there is a tendency that good fracture elongation and impact strength are not obtained in the molded product.

Other compositions:
In the resin composition of the present invention, an extender oil, a crosslinking agent, a bituminous product, a flame retardant, an antioxidant, a colorant, an ultraviolet absorber, a heat stabilizer, and an anti-aging agent are added, as long as the purpose is not impaired. Other additives such as an agent, a processing aid, a light resistance (weather) agent, and an antibacterial agent can be added.

  As the extender oil, an aromatic extender oil, a naphthenic extender oil, a paraffin extender oil and the like are generally known.

  Among these, preferable aromatic extender oils include Diana Process Oil AC-12, AC460, AH-16, AH-16 (all trade names) manufactured by Idemitsu Kosan Co., Ltd., and ExxonMobil manufactured by ExxonMobil. , Mobilzol K, 22 and 130 (both trade names), Kyoishi Process X50, X100 and X140 (both trade names) manufactured by Nippon Mining & Co., Ltd., Resox No. 3. Deutrex 729UK (all trade names), manufactured by Nippon Oil (former Nippon Oil), Komolex 200, 300, 500, 700 (all trade names), manufactured by ExxonMobil Process oil 110, 120 (both are trade names), Mitsubishi 34 Heavy Process Oil, Mitsubishi 44 Heavy Process Oil, Mitsubishi 38 Heavy Process Oil, Mitsubishi 39 Heavy Process Oil (Non-Mitsubishi Petroleum) Can also be mentioned.

  Preferred naphthenic extender oils include Diana Process Oil NS-24, NS-100, NM-26, NM-280, NM-280, NP-24 (all trade names), Exxon, manufactured by Idemitsu Kosan Co., Ltd. Naplex 38 (trade name) manufactured by Mobil Corporation, Fukkor FLEX # 1060N, # 1150N, # 1400N, # 1400N, # 2040N, # 2050N (all trade names) manufactured by Nippon Oil Corporation (former Fuji Kosan) Manufactured by Nikko Kyoishi Co., Ltd., Kyoishi Process R25, R50, R200, R1000 (all trade names), Shell Chemical Co., Ltd., Shelf Rex 371JY, 371N, 451, N-40, 22, 22R, 32R, 100R, 100S, 100S, 100SA, 220RS, 220S, 260, 320R, 680 (all Product name), Nippon Oil (formerly Nippon Oil) 's Koumorex No. 2 process oil (trade name), ExxonMobil's Esso Process Oil L-2, 765 (both trade names), Nippon Oil And Mitsubishi 20 Light Process Oil (trade name) manufactured by (former Mitsubishi Oil).

  Further, as preferable paraffinic extension oils, Diana Process Oil PW-90, PW-380, PS-32, PS-90, PS-430 (all trade names) manufactured by Idemitsu Kosan Co., Ltd. Fukkor Process P-100, P-200, P-300, P-400, P-500 (all trade names) manufactured by Nippon Oil (former Fuji Kosan), manufactured by Nippon Mining & Co., Ltd. , Kyoishi Process P-200, P-300, P-500, Kokeishi EPT750, 1000, Kokeishi Process S90 (all trade names), manufactured by Shell Chemical Co., Lebrex 26, 100, 460 (all trade names), Esso Process Oil 815, 845, B-1 and Naplex 32 (all trade names) manufactured by ExxonMobil, Mitsubishi 10 manufactured by Nippon Oil (former Mitsubishi Oil) Rye Mention may be made of the process oil (trade name), and the like. Of these extension oils, paraffinic extension oils are preferably used.

  The content of the extending oil is 1 to 3000 parts by weight, preferably 10 to 1000 parts by weight, and more preferably 50 to 100 parts by weight with respect to 100 parts by weight of the sum of the components (A), (B), and (C). It is in the range of 300 parts by mass, and the optimum content varies depending on the purpose of use. In addition, when the content of the extending oil exceeds 3000 parts by mass with respect to 100 parts by mass of the total of the components (A), (B), and (C), the mechanical strength of the molded product is reduced. If the amount is less than 1 part by mass, a sufficient reforming effect may not be exhibited.

  Examples of the crosslinking agent include radical initiators such as organic peroxides and organic azo compounds. As a specific example, 1,1-bis (t-butylperoxy) -3,3,5- Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) ) Cyclododecane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) butane, Peroxyketals such as n-butyl-4,4-bis (t-butylperoxy) valerate; di-t-butyl peroxide, dicumyl peroxide, t-butyl group Ruperoxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, α, α′-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis ( dialkyl peroxides such as t-butylperoxy) hexane and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide Diacyl peroxides such as decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-trioyl peroxide; -Butyl peroxyacetate, t-butyl peroxy -Oxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl- Peroxyesters such as 2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, and cumylperoxyoctate; and t-butylhydroperoxide, List hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 1,1,3,3-tetramethylbutyl peroxide Can do.

  Among these crosslinking agents, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2 , 5-bis (t-butylperoxy) hexane or 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 is preferred.

  It is preferable that the usage-amount of a crosslinking agent is 0.01-10 mass parts with respect to 100 mass parts of total amounts of (I) component, (B) component, and (C) component, and 0.05-3 mass. More preferably, it is part. If it is less than 0.01 part by mass, crosslinking may be insufficient. If it exceeds 10 parts by mass, the mechanical strength of the resulting molded product tends to be reduced. In addition, the following polyfunctional monomer may be contained in the used crosslinking agent as a crosslinking adjuvant as needed.

  As such a polyfunctional monomer, those having a radical polymerizable functional group are preferable, and those having a vinyl group as a functional group are particularly preferable. Although the number of functional groups is 2 or more, it is effective particularly when it has 3 or more functional groups. Specific examples of preferred polyfunctional monomers include divinylbenzene, triallyl isocyanurate, triallyl cyanurate, diacetone acrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate. , Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diisopropenylbenzene, p-quinonedioxime, p, p'-dibenzoylquinonedioxime, phenylmaleimide, allyl methacrylate, N, N'-m -Phenylene bismaleimide, diallyl phthalate, tetraallyloxyethane and the like can be mentioned. In particular, triallyl isocyanurate is preferable. A plurality of these polyfunctional monomers may be used in combination. The polyfunctional monomer is preferably used in an amount of 1 to 80% by mass, more preferably 10 to 50% by mass with respect to the crosslinking agent. If it is less than 1% by mass, crosslinking may be insufficient, and if it exceeds 80% by mass, the mechanical strength of the resulting molded article may be reduced.

  Examples of the bitumen include straight asphalt or blown asphalt frequently used in automobile vibration damping materials, and compounds of these and inorganic substances. Examples of the flame retardant include a halogen-based flame retardant, a phosphorus-based flame retardant, and an inorganic flame retardant. In consideration of the dioxin problem, a phosphorus-based flame retardant and an inorganic flame retardant containing no halogen are preferable.

  Phosphorus flame retardants include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol-bis- (diphenyl phosphate), 2-ethylhexyl diphenyl phosphate, dimethylmethyl phosphate , Triallyl phosphate, etc., or a condensate thereof, ammonium phosphate, or a condensate thereof, diethyl N, N-bis (2-hydroxyethyl) aminomethylphosphonate, and the like. Examples of the inorganic flame retardant include magnesium hydroxide, aluminum hydroxide, zinc borate, barium borate, kaolin clay, calcium carbonate, alunite, basic magnesium carbonate, calcium hydroxide and the like. In addition, the flame retardant includes a so-called flame retardant auxiliary that exhibits a low flame retardancy effect itself but exhibits a synergistically superior effect when used in combination with other flame retardants.

Production of resin composition:
Examples of the method for obtaining the resin composition of the present invention include a method of melt kneading the component (a), the component (b), and / or the component (c). In melt kneading, a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, a planetary mixer, a roll, or the like can be used. These kneading apparatuses may be sealed or open. Moreover, if the kneading apparatus is a type of apparatus whose internal atmosphere can be replaced by an inert gas, it is preferable because thermal deterioration of components during melt-kneading can be suppressed. The kneading temperature is a temperature at which all the components to be mixed are melted, and is usually 100 to 300 ° C.

Manufacture of molded products:
The molded product of the present invention is obtained by injection molding, two-color injection molding, extrusion molding, rotational molding, press molding, hollow molding, sandwich molding, compression molding, vacuum molding, powder (powder slush) molding, It can be produced in a desired shape by a known method such as double flash molding, lamination molding, calendar molding, blow molding or the like. In addition, in order to further impart softness to the molded article of the present invention, oil and plasticizer can be added as a softening agent during production. Aromatic, naphthenic, or paraffinic oils can be used as this oil. Moreover, as a plasticizer, a phthalate type, an adipate type, a sebacate type, a phosphate type, a polyether type, a polyester type, etc. can be used. As a molded article, a planter, a building material, a packaging container, a household appliance member, an automobile member, a stationery, a toy etc. are mentioned, for example.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values in an Example and the evaluation method are shown below.

[Vinyl bond content]: The vinyl bond content (%) was calculated by the Morero method using infrared analysis.

[Hydrogenation rate]: The hydrogenation rate (%) of the hydrogenated diene copolymer was calculated from 100 MHz, ¹ H-NMR spectrum using ethylene tetrachloride as a solvent.

[Melt flow rate (MFR)]: In accordance with JIS K7210, the melt flow rate was measured under conditions of 230 ° C. and 21.2 N load.

[Weight average molecular weight of hydrogenated diene copolymer (Mw)]: Determined in terms of polystyrene using gel permeation chromatography (room temperature GPC, column: GMH-XL, manufactured by Tosoh Corporation).

[Elongation at break (%)]: In accordance with JIS K7113, the elongation at break (%) of a molded product formed from the resin composition was measured.

[Charpy impact test]: A Charpy impact test was performed in accordance with JIS K7111, and the impact resistance (kJ / m ² ) of a molded product formed from the resin composition was measured.

(Synthesis Example 1)
Production of hydrogenated diene block polymer (H-1):
Add 5 kg of cyclohexane, 900 g of 1,3-butadiene, and 0.08 g of n-butyllithium to an autoclave with an internal volume of 10 liters. After a polymerization conversion of 30% at 50 ° C., add 200 g of tetrahydrofuran, and further polymerize. went. After the polymerization is completed, the reaction solution is brought to 70 ° C., 1.5 g of n-butyllithium, 1.5 g of 2,6-t-butyl-p-cresol, 0.5 g of bis (cyclopentadienyl) titanium dichloride, And 2 g of diethylaluminum chloride were added and reacted at a hydrogen pressure of 10 kg / cm ² for 1 hour. This reaction solution was mixed in a large amount of methyl alcohol, and the precipitated solid was collected and dried in a vacuum dryer to obtain a hydrogenated diene block polymer (H-1).

  The resulting hydrogenated diene block polymer (H-1) had a hydrogenation rate of 98%, a weight average molecular weight of 300,000, and a melt flow rate (230 ° C., 2.16 kg) of 2.5 g / 10 min. The 1,2-butadiene bond content of 1,3-butadiene measured at the end of the first stage 1,3-butadiene block polymerization was 10%, and the first stage 1,3-butadiene block polymerization was completed. As a result of calculation from the 1,2-vinyl bond content measured at the time and the 1,2-vinyl bond content in the first stage, the 1,2-vinyl bond in the 1,3-butadiene block in the second stage The content was calculated as 80%. The block structure was (AB) m. The physical property value measurement results are shown in Table 1.

(Synthesis Example 2)
Production of hydrogenated diene block polymer (H-2):
Add 5 kg of cyclohexane, 837 g of 1,3-butadiene and 0.08 g of n-butyllithium to an autoclave with an internal volume of 10 liters. After a polymerization conversion of 30% at 50 ° C., add 200 g of tetrahydrofuran, and further polymerize. After reaching a polymerization conversion rate of 100%, 63 g of styrene was added for further polymerization. After the polymerization is completed, the reaction solution is brought to 70 ° C., 1.5 g of n-butyllithium, 1.5 g of 2,6-t-butyl-p-cresol, 0.5 g of bis (cyclopentadienyl) titanium dichloride, And 2 g of diethylaluminum chloride were added and reacted at a hydrogen pressure of 10 kg / cm ² for 1 hour. This reaction solution was mixed in a large amount of methyl alcohol, and the precipitated solid was collected and dried in a vacuum dryer to obtain a hydrogenated diene block polymer (H-2).

  The resulting hydrogenated diene block polymer (H-2) had a hydrogenation rate of 98%, a weight average molecular weight of 200,000, and a melt flow rate (230 ° C., 2.16 kg) of 5.5 g / 10 min. The 1,2-butadiene bond content of 1,3-butadiene measured at the end of the first stage 1,3-butadiene block polymerization was 12%, and the first stage 1,3-butadiene block polymerization was completed. As a result of calculation from the 1,2-vinyl bond content measured at the time and the 1,2-vinyl bond content in the first stage, the 1,2-vinyl bond in the 1,3-butadiene block in the second stage The content was calculated as 70%. The block structure was ABC. The physical property value measurement results are shown in Table 1.

(Synthesis Example 3)
Production of hydrogenated diene block polymer (H-3):
In an autoclave having an internal volume of 10 liters, 5 kg of cyclohexane, 900 g of 1,3-butadiene and 2,2,5,5-tetramethyl-1- (3-lithiopropyl) -1-aza-2,5-disilacyclopentane 14.5 g and n-butyllithium 0.08 g were added, and after reaching a polymerization conversion rate of 30% at 50 ° C., 200 g of tetrahydrofuran was added, and further polymerization was performed. After the polymerization is completed, the reaction solution is brought to 70 ° C., 1.5 g of n-butyllithium, 1.5 g of 2,6-t-butyl-p-cresol, 0.5 g of bis (cyclopentadienyl) titanium dichloride, And 2 g of diethylaluminum chloride were added and reacted at a hydrogen pressure of 10 kg / cm ² for 1 hour. This reaction solution was mixed in a large amount of methyl alcohol, and the precipitated solid was collected and dried in a vacuum dryer to obtain a hydrogenated diene block polymer (H-3).

  The resulting hydrogenated diene block polymer (H-3) had a hydrogenation rate of 98%, a weight average molecular weight of 250,000, and a melt flow rate (230 ° C., 2.16 kg) of 3.0 g / 10 min. The 1,2-butadiene bond content of 1,3-butadiene measured at the end of the first stage 1,3-butadiene block polymerization was 10%, and the first stage 1,3-butadiene block polymerization was completed. As a result of calculation from the 1,2-vinyl bond content measured at the time and the 1,2-vinyl bond content in the first stage, the 1,2-vinyl bond in the 1,3-butadiene block in the second stage The content was calculated as 78%. The block structure is (AB) m, and the functional group of the modified hydrogenated diene block polymer (H-3) is an amino group. The physical property value measurement results are shown in Table 1.

(Synthesis Example 4)
Production of hydrogenated diene block polymer (H-4):
Add 5 kg of cyclohexane, 837 g of 1,3-butadiene, and 0.08 g of n-butyllithium to an autoclave with an internal volume of 10 liters. After a polymerization conversion of 25% at 50 ° C., add 200 g of tetrahydrofuran and further polymerize. After reaching a polymerization conversion rate of 100%, 63 g of styrene and 14.5 g of 2,2,5,5-tetramethyl-1- (3-lithiopropyl) -1-aza-2,5-disilacyclopentane were Addition and further polymerization. After the polymerization is completed, the reaction solution is brought to 70 ° C., 1.5 g of n-butyllithium, 1.5 g of 2,6-t-butyl-p-cresol, 0.5 g of bis (cyclopentadienyl) titanium dichloride, And 2 g of diethylaluminum chloride were added and reacted at a hydrogen pressure of 10 kg / cm ² for 1 hour. This reaction solution was mixed in a large amount of methyl alcohol, and the precipitated solid was collected and dried in a vacuum dryer to obtain a hydrogenated diene block polymer (H-4).

  The resulting hydrogenated diene block polymer (H-4) had a hydrogenation rate of 98%, a weight average molecular weight of 150,000, and a melt flow rate (230 ° C., 2.16 kg) of 4.0 g / 10 min. The 1,2-butadiene bond content of 1,3-butadiene measured at the end of the first stage 1,3-butadiene block polymerization was 11%, and the first stage 1,3-butadiene block polymerization was completed. As a result of calculation from the 1,2-vinyl bond content measured at the time and the 1,2-vinyl bond content in the first stage, the 1,2-vinyl bond in the 1,3-butadiene block in the second stage The content was calculated as 75%. The block structure is ABC, and the functional group of the modified hydrogenated diene block polymer (H-4) is an amino group. The physical property value measurement results are shown in Table 1.

(Example 1)
10 parts of the above hydrogenated diene copolymer (H-1) and 90 parts of the trade name “PE / PP pellets” manufactured by Hiroshima Recycling Center are put in a 40 mmφ extruder (manufactured by Ikegai Co., Ltd.) and heated to 230 ° C. These were kneaded into strands, and then cut with a pelletizer to obtain a pellet-shaped resin composition.

  The obtained pellet-shaped resin composition was press-molded using an electrothermal pressure press molding machine under conditions of a mold temperature of 230 ° C., a pressure heating time of 10 minutes, and a pressure cooling time of 5 minutes. A molded product was prepared and evaluated for physical properties. The physical property value evaluation results are shown in Table 2. The "PE / PP pellet" contains about 48.5 parts of PE, about 51 parts of PP, and about 0.5 parts of other impurities.

  In Tables 2 and 3, “Recycled PE” is a product name “Recycled PE” manufactured by Hokupele, “Recycled PP” is a product name “Recycled PP” manufactured by Hokupele, and “R-1” is a product manufactured by JSR. The names “EP02P” and “R-2” are trade names “Modiper A1200” manufactured by Nippon Oil & Fats, and “R-3” are product names “Modiper A6200” manufactured by Japan Oils and Fats.

(Examples 2 to 10, Comparative Examples 1 to 9)
The sheet-like molded products of Examples 2 to 10 and Comparative Examples 1 to 9 are prepared in the same manner as in Example 1 except that the formulation shown in Tables 2 and 3 is used, and the physical property values are evaluated. It was. Tables 2 and 3 show the physical property value evaluation results.

  As shown in Table 2 and Table 3, the molded products produced using the resin compositions of Examples 1 to 10 are superior to the molded products produced using the resin compositions of Comparative Examples 1 to 9. It is clear that it has excellent elongation at break and impact resistance.

  The molded article manufactured using the resin composition of the present invention is suitable as, for example, a planter, a building material, a packaging container, a household appliance member, an automobile member, a stationery, or a toy.

Claims (9)

(B) a recycled resin component containing at least one thermoplastic resin recovered and recycled from the used resin;
(B) A hydrogenated diene block polymer in which 80% or more of the conjugated diene compound units of the block copolymer satisfying the following condition (1) are hydrogenated, and / or
(C) The (b) hydrogenated diene block polymer is a modified hydrogenated diene block polymer modified with at least one functional group;
A resin composition comprising:
(1): a polybutadiene block (A) having a 1,2-vinyl bond content of 30% or less;
A conjugated diene polymer block (B) comprising a conjugated diene compound unit, wherein the conjugated diene compound unit has a 1,2-vinyl bond content of more than 70%,
A linear or branched block copolymer whose block structure is represented by A- (BA) n or (AB) m (where n and m are integers of 1 or more). .   The resin composition according to claim 1, wherein the thermoplastic resin is polyethylene (PE) and / or polypropylene (PP).   The resin composition according to claim 1 or 2, wherein the block copolymer further comprises a vinyl aromatic compound polymer block (C) comprising a vinyl aromatic compound unit.   The resin composition according to any one of claims 1 to 3, wherein (i) the recycled resin component contains a plurality of integrated pellet-like thermoplastic resins.   The resin composition according to any one of claims 1 to 3, wherein the recycled resin component (a) is a pellet containing a plurality of pellets of the thermoplastic resin.   The ratio of the polyethylene (PE) and the polypropylene (PP) contained in the (i) recycled resin component is (PE) / (PP) = 5/95 to 95/5 in mass ratio. The resin composition as described in any one of 2-5.   The content ratio of the (a) recycled resin component and the total content ratio of the (b) hydrogenated diene block polymer and the (c) modified hydrogenated diene block polymer are expressed in terms of mass ratio. ) / ((B) + (c)) = 99.9 / 0.1 to 70/30 The resin composition according to any one of claims 1 to 6.   A molded article comprising the resin composition according to any one of claims 1 to 7.   The molded article according to claim 8, which is a planter, a building material, a packaging container, a household electrical appliance member, an automobile member, a stationery, or a toy.