Resin composition and molded article

Abstract

To provide a resin composition capable of shortening the cleaning time of a screw, a cylinder and a die.SOLUTION: A resin composition comprising an adhesive thermoplastic resin (A) and a silylated polyolefin (B) represented by the following formula (1), wherein the mass ratio of the content of the silylated polyolefin (B) to the content of the adhesive thermoplastic resin (A) in the resin composition is 0.0001 to 0.3: (In the above formula (1), A1, A2 and A3 are each independently a polyolefin chain or a hydrocarbyl group having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. M is an integer of 1 to 10,000. When a plurality of A3 are present, each A3 may be the same or different. However, at least one of A1, A2, and A3 represents a polyolefin chain. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a molded article. [Background technology]

[0002] Taking advantage of their excellent processability, thermoplastic resins are used in a wide variety of products, including electrical and electronic components, packaging materials, and general household goods, as well as press-molded products, injection-molded products, extrusion-molded products such as films and sheets, and hollow-molded products. Their applications are expanding, and designs are becoming increasingly diverse. As a result, the demand for small-lot, high-mix production of molded products is increasing, necessitating frequent changes in resin materials in thermoplastic resin processing equipment. When changing resin materials, disassembling and cleaning the processing equipment each time is essential to eliminate the impact of residue from the previous thermoplastic resin substrate on the molding of the new thermoplastic resin substrate. However, this requires cooling, disassembly, cleaning, assembly, and heating of the processing equipment, which reduces productivity and increases costs. Therefore, to maintain productivity, resin compositions have traditionally been used as cleaning agents. Cleaning agents clean the interior of processing equipment without disassembly; they are simply supplied from the resin supply and discharged from the processing equipment along with the molding resin. Cleaning agents are also effective when disassembling the processing equipment. That is, after molding, the thermoplastic resin substrate remains inside the thermoplastic resin processing equipment, and when it is cooled for disassembly, the molten resin solidifies, hindering removal of the screw, cylinder, and die. However, if a detergent is used to remove the thermoplastic resin substrate from inside the processing equipment, removal of the screw, etc. becomes easier during disassembly.

[0003] The cleaning agent has a cleaning effect by mechanically scraping out the resin composition remaining inside the thermoplastic resin processing equipment, particularly the screw, cylinder, and die of the extruder or injection molding machine (purging effect) and wiping effect. Known cleaning agent compositions include a polyethylene resin crosslinked to a gel fraction of 35 to 90% (Patent Document 1) and a thermoplastic resin, particularly a resin composition comprising a polyethylene resin and a thermoplastic ultra-high molecular weight resin (Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 61-4413 [Patent Document 2] Japanese Patent Application Publication No. 8-155969 Summary of the Invention [Problem to be solved by the invention]

[0005] As a result of investigations by the present inventors, it became clear that when an adhesive thermoplastic resin is used as the thermoplastic resin, the resin adhering to the screw, cylinder, and die cannot be sufficiently removed by the above-mentioned cleaner alone. The present invention has been made in view of the above circumstances, and provides a resin composition that allows screws, cylinders, and dies to be easily cleaned. [Means for solving the problem]

[0006] According to the present invention, there are provided the following resin compositions and molded articles. [1] an adhesive thermoplastic resin (A); and a silylated polyolefin (B) represented by the following formula (1): the mass ratio of the content of the silylated polyolefin (B) to the content of the adhesive thermoplastic resin (A) in the resin composition is 0.0001 to 0.3; Resin composition. [ka] (In the above formula (1), A 1 , A 2and A 3 are each independently a polyolefin chain or a hydrocarbon group having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. m is an integer of 1 to 10,000. A 3 If there are multiple A 3 may be the same or different, provided that A 1 , A 2 , A 3 At least one of these represents a polyolefin chain.) [2] The adhesive thermoplastic resin (A) includes a thermoplastic resin containing no polar group or a thermoplastic resin containing a polar group, The resin composition according to [1]. [3] the thermoplastic resin not containing a polar group is a polyamide, The thermoplastic resin containing a polar group is an ethylene-unsaturated carboxylic acid copolymer. The resin composition according to [2]. [4] the mass ratio of the content of the silylated polyolefin (B) to the content of the adhesive thermoplastic resin (A) in the resin composition is 0.0005 to 0.005; The resin composition according to any one of [1] to [3]. [5] A molded article comprising the resin composition according to any one of [1] to [4]. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a resin composition that can shorten the cleaning time for the screw, cylinder, and die. DETAILED DESCRIPTION OF THE INVENTION

[0008] The resin composition and molded article according to this embodiment will be described in detail below, but the present invention is not limited to the following embodiment in any way and can be implemented with appropriate modifications within the scope of the object of the present invention. In this embodiment, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. In the numerical ranges described in stages in this embodiment, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this embodiment, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in an example.

[0009] 1.Resin composition The resin composition according to this embodiment contains an adhesive thermoplastic resin (A) and a silylated polyolefin (B) represented by the following formula (1), and the mass ratio of the content of the silylated polyolefin (B) to the content of the adhesive thermoplastic resin (A) in the resin composition is 0.0001 to 0.3.

[0010] [ka] In the above formula (1), A 1 , A 2 and A 3 are each independently a polyolefin chain or a hydrocarbon group having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. m is an integer of 1 to 10,000. A 3 If there are multiple A 3 may be the same or different, provided that A 1 , A 2 , A 3 At least one of these represents a polyolefin chain.

[0011] The present inventors surmise that silicones and the like, which are generally used as processing aids, have low affinity with thermoplastic resins, and therefore cannot sufficiently suppress the increase in shear stress at high shear rates during kneading, and that the surface smoothness of the resulting resin composition is insufficient. On the other hand, the silylated polyolefin (B) has a high affinity with the adhesive thermoplastic resin (A). Therefore, the present inventors presume that by adding an appropriate amount of silylated polyolefin (B), a resin composition containing the adhesive thermoplastic resin (A) and the silylated polyolefin (B) has a high surface silicon concentration and reduced surface free energy, and therefore adhesion of the adhesive thermoplastic resin to the screw, cylinder, and die can be sufficiently suppressed even after use.

[0012] Furthermore, since the highly polar silyl groups have low affinity with the adhesive thermoplastic resin (A), they are arranged toward the outside of the surface of the resin composition, and since the olefin moieties of the silylated polyolefin (B) have high affinity with the adhesive thermoplastic resin (A), the olefin moieties interact with the adhesive thermoplastic resin (A). This makes it difficult for the silylated polyolefin (B) to fall off from the surface of the resin composition, and the inventors presume that as a result, adhesion of the adhesive thermoplastic resin to the screw, cylinder, and die can be sufficiently suppressed even after use.

[0013] In the resin composition according to this embodiment, the mass ratio of the content of the silylated polyolefin (B) to the content of the adhesive thermoplastic resin (A) in the resin composition is 0.0001 to 0.3, preferably 0.0002 to 0.1, more preferably 0.0003 to 0.05, and even more preferably 0.0005 to 0.005.

[0014] In the resin composition according to this embodiment, the total content of the adhesive thermoplastic resin (A) and the silylated polyolefin (B) may be 10% by mass or more when the entire resin composition is taken as 100% by mass.

[0015] The shape of the resin composition according to this embodiment is not particularly limited, but examples thereof include pellets, bales, and blocks.

[0016] Hereinafter, each component constituting the resin composition according to this embodiment will be described.

[0017] <Adhesive thermoplastic resin (A)> The adhesive thermoplastic resin (A) refers to a resin that adheres to the screw, cylinder, and die of a molding machine after mixing. Specific examples include polyamide resins, (meth)acrylic resins, silicone resins, urethane resins, olefin resins, and styrene resins. The adhesive thermoplastic resin (A) preferably contains a thermoplastic resin containing no polar groups or a thermoplastic resin containing polar groups.

[0018] (Thermoplastic resin not containing polar groups) "Not containing polar groups" means that there are no polar groups at the ends of the molecule (polar groups are present only in the main chain). Examples of polar groups here include carboxylic acids or their derivatives (acid anhydrides, esters, amides, imides, metal salts, etc.), epoxy groups, hydroxyl groups, halogens, and amino groups.

[0019] Examples of thermoplastic resins that do not contain a polar group include polyolefins, polyamides, polyesters, polyacetals, styrene-based (co)polymers, polycarbonates, polyphenylene oxides, and rubber components. Among these, it is preferable that the material contains polyamide, and it is more preferable that the material is polyamide.

[0020] Examples of polyamides include aliphatic polyamides such as polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyundecane amide (nylon 11), and polydodecanamide (nylon 12); and polytrimethylhexamethylene tetracarbonate having an aromatic ring derived from an aromatic dicarboxylic acid. Examples of the polyamide resin include aromatic polyamides such as polyhexamethylene isophthalamide, polyhexamethylene terephthalic / isophthalamide, aromatic polyamides having an aromatic ring derived from an aromatic diamine, such as polymetaxylylene adipamide, polyundecamethylene terephthalamide, polyundecamethylene hexahydroterephthalamide, and alicyclic polyamides such as polybis(4-aminocyclohexyl)methanedodecamide and polybis(3-methyl-4-aminocyclohexyl)methanedodecamide. The polyamide resin may be used alone or in combination of two or more.

[0021] These polyamides preferably have an intrinsic viscosity (IV) measured at 25° C. in a solvent of 98% concentrated sulfuric acid in the range of 0.1 to 20 (dl / g).

[0022] (Thermoplastic resin containing polar groups) The thermoplastic resin containing a polar group is preferably an olefin polymer containing a polar group.

[0023] Examples of the olefin polymer containing a polar group include ethylene and olefins having 3 to 20 carbon atoms. Examples of the olefins having 3 to 20 carbon atoms include linear α-olefins having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; and branched α-olefins having preferably 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, such as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, and 3-ethyl-1-hexene. The above olefins may be one type or a combination of two or more types.

[0024] Examples of the polar group include carboxylic acid or its derivatives (acid anhydride, ester, amide, imide, metal salt, etc.), epoxy group, hydroxyl group, halogen, and amino group.

[0025] Examples of methods for producing an olefin polymer containing a polar group include a method in which a monomer containing a polar group is graft-modified onto an olefin polymer.

[0026] Examples of monomers containing polar groups are given below.

[0027] The monomer containing a carboxylic acid or a derivative thereof includes an unsaturated carboxylic acid and a derivative thereof.

[0028] Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. Derivatives of unsaturated carboxylic acids include acid anhydrides, esters, amides, imides, and metal salts. Specifically, examples thereof include maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, Examples of the acrylic acid-N-monoethylamide include maleic acid-N,N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N,N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monoethylamide, fumaric acid-N,N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N,N-dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, and potassium methacrylate. Of these, it is preferable to use maleic anhydride.

[0029] Examples of monomers containing an epoxy group include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylethyl (meth)acrylate, 3,4-epoxycyclohexylpropyl (meth)acrylate, and allyl glycidyl ether. Examples of the hydroxyl group-containing monomer include linear hydroxylated α-olefins having 2 to 20, preferably 2 to 10, carbon atoms, such as vinyl alcohol, allyl alcohol, hydroxylated 1-butene, hydroxylated 1-pentene, hydroxylated 1-hexene, hydroxylated 1-octene, hydroxylated 1-decene, hydroxylated 1-dodecene, hydroxylated 1-tetradecene, hydroxylated 1-hexadecene, hydroxylated 1-octadecene, and hydroxylated 1-eicosene; and branched hydroxylated α-olefins preferably having 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, such as hydroxylated α-olefins 4-methyl-1-pentene, hydroxylated 3-methyl-1-pentene, hydroxylated 3-ethyl-1-pentene, hydroxylated 4,4-dimethyl-1-pentene, hydroxylated 4-methyl-1-hexene, hydroxylated 4,4-dimethyl-1-hexene, hydroxylated 4-ethyl-1-hexene, and hydroxylated 3-ethyl-1-hexene.

[0030] Specific examples of halogen-containing monomers include halogenated α-olefins having an atom of Group 17 of the periodic table, such as chlorine, bromine, or iodine, such as halogenated vinyl, halogenated-1-butene, halogenated-1-pentene, halogenated-1-hexene, halogenated-1-octene, halogenated-1-decene, halogenated-1-dodecene, halogenated-1-tetradecene, halogenated-1-hexadecene, halogenated-1-octadecene, and halogenated-1-eicosene, which are linear halogenated α-olefins having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. -olefins; for example, branched halogenated α-olefins preferably having 5 to 20 carbon atoms, more preferably 5 to 10 carbon atoms, such as halogenated-3-methyl-1-butene, halogenated-4-methyl-1-pentene, halogenated-3-methyl-1-pentene, halogenated-3-ethyl-1-pentene, halogenated-4,4-dimethyl-1-pentene, halogenated-4-methyl-1-hexene, halogenated-4,4-dimethyl-1-hexene, halogenated-4-ethyl-1-hexene, and halogenated-3-ethyl-1-hexene, can be mentioned.

[0031] Examples of the amino group-containing monomer include unsaturated amines such as allylamine, 5-hexenamine, and 6-heptenamine.

[0032] Examples of the olefin polymer include homopolymers and copolymers of the above-mentioned olefins. For example, ethylene homopolymers, propylene homopolymers, copolymers of ethylene and an α-olefin having 3 to 10 carbon atoms, and copolymers of propylene and an α-olefin having 4 to 10 carbon atoms can be mentioned. Various known methods can be used to graft copolymerize a polar group-containing monomer onto an olefin polymer to produce a modified product, such as a method of graft copolymerization by heating an olefin polymer and a polar group-containing monomer in the presence or absence of a solvent, with or without the addition of a radical initiator.

[0033] The graft amount of the polar group-containing monomer is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, per 100 parts by mass of the polar group-containing olefin polymer, and can be adjusted by changing the graft ratio of the polar group-containing monomer to the polyolefin. Alternatively, the graft amount of the entire modified product can be adjusted by mixing a modified product having a high polar group content with a modified product having a low polar group content or an unmodified product.

[0034] As another method for producing an olefin polymer containing a polar group, an olefin polymer containing a polar group can also be produced by copolymerizing the above-mentioned monomer having a polar group with the above-mentioned olefin.

[0035] Examples of the monomer having a polar group are as described above. The copolymerization can be carried out by various known methods.

[0036] The copolymer is preferably an ethylene-unsaturated carboxylic acid copolymer, and more preferably a copolymer of ethylene and acrylic acid, or a copolymer of ethylene and methacrylic acid.

[0037] The copolymerization ratio (molar ratio) of the polar group-containing monomer to the olefin is preferably polar group-containing monomer:olefin=0.5:99.5 to 30:70, more preferably 1:99 to 20:80. Furthermore, a plurality of copolymers having different polar group contents may be mixed.

[0038] Another method for producing an olefin polymer containing a polar group is to react the melt of the olefin polymer by treating it with oxygen or an oxygen-containing gas mixture (which may optionally further contain ozone). The resulting reaction product (oxidatively modified olefin polymer) contains many oxygen-containing functional groups, such as carboxylic acid, ester, carbonyl, and hydroxyl groups. The reaction method is not particularly limited, and known methods such as those described in JP-A-11-80252 can be used.

[0039] The number average molecular weight of the polar group-containing polyolefin determined by gel permeation chromatography (GPC) is preferably from 100 to 500,000, more preferably from 500 to 30,000, and even more preferably from 1500 to 100,000. As a specific method for GPC measurement, for example, the method described later in the Examples can be adopted.

[0040] The polar group-containing olefin polymer used in this embodiment does not substantially contain silicon atoms. That is, the content of silicon atoms is preferably 0 to 100 ppm, and more preferably 0 to 50 ppm. The adhesive thermoplastic resin (A) may be produced using raw materials derived from biomass.

[0041] <Silylated polyolefin (B)> The silylated polyolefin (B) according to this embodiment is represented by the following formula (1). [ka]

[0042] In the above formula (1), A 1 , A 2 and A 3 are each independently a polyolefin chain or a hydrocarbon group having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. m is an integer of 1 to 10,000. A 3 If there are multiple A 3 may be the same or different, provided that A 1 , A 2 , A 3 At least one of these represents a polyolefin chain.

[0043] Above A 1 , A 2 and A 3 The polyolefin chain in the above formula is a polymer chain containing a structural unit derived from an olefin having 2 to 50 carbon atoms, for example.

[0044] Specific examples of the olefin having 2 to 50 carbon atoms include ethylene and α-olefins having 3 to 50 carbon atoms (such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1-pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, 3,4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and vinylcyclohexane).

[0045] The polyolefin chains may be homopolymer chains or copolymer chains. For example, the polyolefin chain may be a copolymer chain of ethylene and an α-olefin having 3 to 20 carbon atoms, and in the copolymer chain of ethylene and an α-olefin having 3 to 20 carbon atoms, when all structural units are taken as 100 mol %, the structural units derived from the α-olefin having 3 to 20 carbon atoms may be more than 0 mol % but not more than 20 mol %.

[0046] The polyolefin chain may optionally contain structural units derived from other olefins, such as olefins containing an internal double bond (e.g., cis-2-butene), vinylidene compounds (e.g., isobutene), arylvinyl compounds (e.g., styrene), arylvinylidene compounds (e.g., α-methylstyrene), vinylidene compounds substituted with functional groups (e.g., methyl methacrylate), aliphatic cyclic olefins containing an internal double bond (e.g., 5-methyl-2-norbornene, tetracyclododecene, cyclopentadiene, dicyclopentadiene), cyclic olefins containing an aromatic ring (e.g., indene), and linear or cyclic polyenes (e.g., butadiene, isoprene, ethylidene norbornene, vinyl norbornene).

[0047] The content of structural units derived from other olefins may be 0 to 10 mol % when all structural units constituting the polyolefin chain are taken as 100 mol %.

[0048] The polyolefin chain may have a number average molecular weight of 100 to 500,000 as determined by the GPC method described below.

[0049] The polyolefin chain may have a molecular weight distribution (Mw / Mn) in the range of 1.1 to 3.0 as determined by the GPC method described below.

[0050] GPC measurement method: GPC measurement is performed at a temperature of 140°C using orthodichlorobenzene as a solvent, and analytical values ​​(weight average molecular weight (Mw), number average molecular weight (Mn) and Mw / Mn) can be obtained as polyethylene-equivalent values. The measurement can be carried out under the following conditions: The molecular weight can be determined by preparing a calibration curve using commercially available monodisperse standard polystyrene and then calculating it based on the following conversion method. Apparatus: Gel permeation chromatograph Alliance GPC2000 (Waters) Solvent: o-dichlorobenzene Column: TSKgel column (Tosoh Corporation) x 4 Flow rate: 1.0ml / min Sample: 0.15 mg / mL Lo-dichlorobenzene solution Temperature: 140℃ Molecular weight conversion: PS conversion / general calibration method For general-purpose calibration calculations, the coefficients of the Mark-Houwink viscosity equation shown below can be used. Modulus of polystyrene (PS): KPS = 1.38 x 10 -4 ,aPS=0.70 Coefficient of polyethylene (PE): KPE = 5.06 x 10 -4 ,aPE=0.70

[0051] In the above formula (1), A 1 , A 2 and A 3 are each independently a polyolefin chain or a hydrocarbon group having 1 to 20 carbon atoms, and R is a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, an arylalkyl group, an alkenyl group, and an aryl group.

[0052] Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, octyl, decyl, and octadecyl groups; and cycloalkyl groups such as cyclopentyl, cyclohexyl, and norbornyl groups. Examples of the arylalkyl group include a benzyl group, a phenylethyl group, and a phenylpropyl group. Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group. Examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a naphthyl group.

[0053] In the above formula (1), m is an integer of 1 to 10,000.

[0054] In the above formula (1), A 3 If there are multiple A 3 may be the same or different.

[0055] In the above formula (1), A 1 , A 2 , A 3 At least one of these represents a polyolefin chain.

[0056] In the above formula (1), m is 2 or more, and A 3 At least one of the other A 3 When different from the above, there are multiple types of units represented by the following formula (2), but the order in which they are arranged is not particularly limited, and they may be arranged in blocks or randomly.

[0057] [ka]

[0058] The above formula (1) may be a structure represented by the following (1A), (1B) or (1C). (1A) In the above formula (1), A 1 and A 2 is a polyolefin chain, and A 3 is a hydrocarbon group having 1 to 20 carbon atoms. (1B) In the above formula (1), A 1 , A 2 one of which is a polyolefin chain and the other is a hydrocarbon group having 1 to 20 carbon atoms, 3 is a hydrocarbon group having 1 to 20 carbon atoms. (1C) In the above formula (1), A 1 and A2 is a hydrocarbon group having 1 to 20 carbon atoms, and A 3 at least one of which is a polyolefin chain.

[0059] In the silylated polyolefin (B) according to this embodiment, the silicone chain / polyolefin chain (mass ratio) is not particularly limited, but may be, for example, 5 / 95 to 99 / 1.

[0060] The method for producing the silylated polyolefin (B) according to this embodiment is not particularly limited, but it can be produced, for example, by the method described in paragraphs 0089 to 0145 and 0196 to 0207 of WO 2012 / 098865.

[0061] The content of the silylated polyolefin (B) in the resin composition according to this embodiment is not particularly limited, but may be 0.005% by mass to 30% by mass when the entire resin composition is taken as 100% by mass.

[0062] The silylated polyolefin (B) may be produced using a raw material derived from biomass.

[0063] <Other additives> The resin composition according to the present embodiment may optionally contain various known additives used in the production of polyolefin products, provided that the purpose of the present invention is not impaired. Examples of such additives include softeners, antioxidants, processing aids, activators, reaction inhibitors, colorants, dispersants, flame retardants, plasticizers, antioxidants, UV absorbers, antistatic agents, lubricants, antifungal agents, surfactants, etc.

[0064] 2. Molded body The molded article according to the present embodiment includes the resin composition according to the present embodiment. The molded article according to the present embodiment may have any shape, and may be a film, a sheet, a nonwoven fabric, or a foam.

[0065] The molded article according to this embodiment can be molded from the resin composition according to this embodiment by a known method, such as various melt extrusion methods such as T-die molding, inflation molding, foam extrusion molding, profile extrusion molding, electric wire extrusion molding, tube extrusion molding, and pipe extrusion molding, injection molding, or compression molding.

[0066] 3.Applications Examples of uses of the molded article of this embodiment include, but are not limited to, the following.

[0067] The molded articles can be preferably used as packaging materials for various foods, daily commodities, and industrial products, as well as medical containers, and can also be used as exterior components for buildings, such as outdoor fences, wood decks, parbolas (grape trellises), and lattices, interior components for interior walls, floors, ceilings, and furniture, as well as play equipment.

[0068] The molded article can also be used as a shock-absorbing material. Examples of shock-absorbing materials include health products, nursing care products (e.g., fall prevention films, mats, and sheets), shock-absorbing pads, protectors and protective equipment (e.g., helmets and guards), sports goods (e.g., sports grips), sports protective gear, rackets, balls, transportation equipment (e.g., shock-absorbing grips for transportation, shock-absorbing sheets), industrial materials (e.g., vibration-damping pallets, shock-absorbing dampers, shock-absorbing materials for footwear, shock-absorbing foams, and shock-absorbing films), and automobile shock-absorbing materials (e.g., bumper shock-absorbing materials, cushioning materials).

[0069] Furthermore, the molded article can be used for automotive interior components such as instrument panels, console boxes, meter covers, door lock bezels, steering wheels, power window switch bases, center clusters, dashboards, roof linings, cowl side trims, door trim substrates, deck trims, inner panels, pillar garnishes, rear packages, package trays, switch bases, quarter panels, seat structural materials, seat backboards, armrest core materials, ceiling substrates, wall materials, floor materials, shock absorbing materials, and sound absorbing materials; weather strips, bumpers, bumper guards, side mudguards, body panels, cowlings, fenders, spoilers, front grilles, strut mounts, wheel caps, center pillars, door frames, etc. and various other applications, such as: automotive exterior components such as mirrors, center ornaments, side moldings, door moldings, window moldings, windows, headlamp covers, taillamp covers, and windshield parts; various front panels for AV equipment; surface decorative materials such as buttons and emblems; various parts such as housings, display windows, and buttons for mobile phones; exterior materials for furniture; architectural interior materials such as walls, ceilings, and floors; architectural exterior materials such as exterior walls such as siding, fences, roofs, gates, and gable boards; surface decorative materials for furniture such as window frames, doors, handrails, thresholds, and lintels; various displays, lenses, mirrors, goggles, window glass, and other optical components; interior and exterior components for various vehicles other than automobiles, such as trains, airplanes, and ships; and various other applications, such as packaging containers, packaging materials, prizes, and small items.

[0070] The molded article is suitable for use in many fields, such as electrical insulating materials, industrial parts, building materials, leisure materials, agricultural implements, marine or fishing equipment, and the like. In particular, housing components and building materials such as baseboards, surface decorative panels, door materials, exterior wall materials, vanity units, counter materials, foundation support boards, window frames, wall materials, trim boards, handrails, handles, structural materials, civil engineering square timber, pillars, floor pillars, decorative pillars, earthquake-resistant materials, wallpaper, fixtures and ceiling materials, underlayment materials, tatami mats, floors, concrete panels, scaffolding materials, insulation boards, soundproofing boards, furniture box ceilings, doors, front and back panels, shelf boards, sleeve boards, fascia boards, deck boards, back boards, seat boards, kitchen components, waterproofing materials, mildew-proofing materials, antiseptic materials, shutter boards, sleeve boards, wainscoting, side boards, bathroom units, floor pans, bathroom ceilings, bathroom walls, It can also be used in baths, buckets, sanitary equipment, toilet seats, toilet covers, home appliances, radio and television receivers, cabinets, stereo cabinets, amplifier cabinets, speakers, speaker boxes, piano organ main boards, main roofs, rolled roofs, upper and lower rolled boards, buoyancy bodies (foam) for life jackets, surfboards, cold weather glove materials, fishing equipment (floats, decorative balls, fish attracting balls, artificial baits), camping equipment, agricultural films, gardening poles, greenhouse poles or fasteners for fixing poles, marine fenders, flotation devices, etc.

[0071] The molded article can also be used in small transportation means such as bicycles and electrically assisted bicycles, escalators, elevators, etc., aviation materials such as manned aircraft, unmanned aircraft, ultra-high-speed passenger aircraft, rockets, and artificial satellites, transportation means such as fuel cell vehicles, hydrogen cell vehicles, and linear motor cars, various play equipment, various robot components, various infrastructures such as traffic lights, electric wires, water pipes, gas pipes, and optical fibers, liquid crystal panels, solar cells, antennas, transistors, office equipment interiors, office equipment housings, toilet lighting fixtures, umbrellas, raincoats, heat insulation materials, flooring, paints, barrier agents, hydrophilic / hydrophobic control agents, papermaking materials, tires, dampers, hoses, various rubber materials such as vibration-isolating rubber, food and beverage containers, materials for 3D printers, liquid filters, air filters, semiconductor filters, various nonwoven fabric materials, musical instruments, acoustic materials, wigs, watches, gravestones, eyeglasses, sunglasses, wearable devices, etc.

[0072] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0073] The present invention will be specifically described below based on examples, but the present invention is not limited to these examples.

[0074] 1. Measurement and evaluation methods (1) Weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of silylated polyolefin (B) A calibration curve was prepared using commercially available monodisperse standard polystyrene. The weight average molecular weight (Mw), number average molecular weight (Mn), and Mw / Mn were calculated as polyethylene equivalent values ​​using the following conversion method. Apparatus: Gel permeation chromatograph Alliance GPC2000 (Waters) Solvent: o-dichlorobenzene Column: Four TSKgel columns manufactured by Tosoh Corporation connected in series ·Flow rate: 1.0ml / min Sample: 0.15 mg / mL Lo-dichlorobenzene solution ·Temperature: 140℃ Molecular weight conversion: PS conversion / general calibration method The coefficients of the Mark-Houwink viscosity equation shown below were used for the general-purpose calibration calculation. Modulus of polystyrene (PS): KPS = 1.38 x 10 -4 ,aPS=0.70 Coefficient of polyethylene (PE): KPE = 5.06 x 10 -4 ,aPE=0.70

[0075] (2) Ease of peeling adhesive thermoplastic resin (A) The single-screw extruder for T-die melt extrusion film molding used to produce the resin compositions obtained by the methods described in Examples 1 and 2 and Comparative Examples 1 and 2 below was disassembled, and the adhesive thermoplastic resin adhering to the screw, cylinder, and die was evaluated for ease of peeling according to the following criteria. No adhesion:◎ Scraping with a jig within 3 times: YES Scraping with a jig 4 to 9 times: △ Scraping with a jig 10 times or more: ×

[0076] 2.Raw materials The raw materials used in the examples and comparative examples are shown below. (1) Adhesive thermoplastic resin (A) As adhesive thermoplastic resin (A-1), density 940 kg / m 3 An ethylene / methacrylic acid copolymer (Nucrel® grade AN4221C, manufactured by Dow Mitsui Polychemicals Co., Ltd.) with a melting point of 94°C, MFR (190°C, 2.16 kg load) of 10 g / 10 min, and acid content of 12% was used. As adhesive thermoplastic resin (A-2), density 1130 kg / m 3 Nylon 6 (Amilan (registered trademark) grade CM1041-LO manufactured by Toray Industries, Inc.) with a water absorption rate of 1.8% (24 hours, 23°C) measured according to ISO 62 was used.

[0077] (2) Thermoplastic resin for cleaning Thermoplastic resin (1) for cleaning, density 900 kg / m 3 PP (Prime Polypro (registered trademark) grade F327 manufactured by Prime Polymer Co., Ltd.) having a melting point of 138°C and MFR (230°C, 2.16 kg load) of 2.16 g / 10 min was used. Thermoplastic resin (2) for cleaning, density 956 kg / m 3 The material used was HDPE (grade HD7000F manufactured by Exxon Chemical Company) with a melting point of 135°C and a MFR (190°C, 2.16 kg load) of 0.05 g / 10 min.

[0078] (3) Silylated polyolefin (B) [Synthesis Example 1] (Synthesis of polyethylene with a vinyl group at one end) An ethylene polymer (P-1) having a vinyl group at one end was synthesized according to the method described in Synthesis Example 2 of WO 2012 / 098865. 1 H-NMR analysis revealed that the polymer obtained was homopolyethylene, and contained a double bond at only one end. The physical properties of this ethylene polymer (P-1) (single unit) containing a vinyl group at one end were as follows: Melting point (Tm) 127℃ Mw=4770, Mw / Mn=2.25 (GPC) Terminal unsaturation rate 97%

[0079] [Synthesis Example 2] (Preparation of Platinum Catalyst Composition (C-1)) In a 50 ml sample tube equipped with a magnetic stirrer tip, 0.50 g of platinum(II) chloride was suspended in 10 ml of hydrosilane A (HS(A), manufactured by Gelest, Inc., DMS-H11) having the following structure, and the suspension was stirred at room temperature under a nitrogen stream. After stirring for 190 hours, approximately 0.4 ml of the reaction solution was sampled with a syringe and filtered using a 0.45 μm PTFE filter. The filtrate was collected in a 10 ml sample tube, yielding a platinum catalyst composition (C-1) with a platinum concentration of 3.8 mass%. Hydrosilane A (HS(A)): HSi(CH3)2O-(-Si(CH3)2-O-)n-Si(CH3)2H (n=12-13)

[0080] [Synthesis Example 3] (Introduction of polyethylene with terminal vinyl groups into hydrosilane) A 300 ml two-neck flask was charged with 25.1 g (11.8 mmol) of the ethylene polymer (P-1) having a vinyl group at one end obtained in [Synthesis Example 1], and under a nitrogen atmosphere, 6.7 g (5.9 mmol; equivalent to 11.8 mmol as Si-H groups) of hydrosilane A (HS(A)) and 150 μl (1.4 × 10 in terms of Pt) of (C-1a) obtained by diluting the platinum catalyst composition (C-1) prepared in [Synthesis Example 2] 200 times with hydrosilane A (HS(A)). -6(mmol) was further charged. The two-neck flask was placed in an oil bath whose internal temperature had been raised to 130°C and stirred. After about 3 minutes, the polymer melted. After 6 hours, the flask was cooled, and about 200 ml of methanol was added. The contents were transferred to a 300 ml beaker and stirred for 2 hours. The solid was then filtered, washed with methanol, and dried at 60°C under reduced pressure of 2 hPa or less, yielding 33.1 g of a white solid silylated polyolefin (B-1). NMR analysis showed that the yield of the obtained silylated polyolefin (B-1) was 98%, the olefin conversion was 100%, and the isomerization rate was 2%. The MFR was above the upper limit of measurement (MFR>100g / 10min), and the polyorganosiloxane content in (B-1) calculated from the molecular formula was 23% by mass.

[0081] [Example 1] A dry blend of 100 parts by weight of adhesive thermoplastic resin (A-1) and 0.1 parts by weight of silylated polyolefin (B-1) was placed in the hopper of a single-screw extruder for T-die melt extrusion film molding. A molten web was extruded from the T-die at a molding temperature of 210°C and a throughput of 1.95 kg / h, and the film was withdrawn for 2 hours. The film thickness was 100 μm. Subsequently, cleaning thermoplastic resin (1) or thermoplastic resin (2) was placed in the hopper of the same extruder, and the interior was purged at a molding temperature of 240°C for 1 hour. The ease of peeling of adhesive thermoplastic resin (A-1) was evaluated according to the method described above. The results are summarized in Table 1.

[0082] [Example 2] A dry blend of 100 parts by weight of adhesive thermoplastic resin (A-2) and 0.1 parts by weight of silylated polyolefin (B-1) was vacuum-dried at 80°C for 6 hours. The dried resin was placed in the hopper of a single-screw extruder for T-die melt extrusion film molding. A molten web was extruded from the T-die at a molding temperature of 280°C and a throughput of 1.95 kg / h, and the film was withdrawn for 2 hours. The film thickness was 100 μm. Subsequently, cleaning thermoplastic resin (2) was placed in the hopper of the same extruder. The interior was purged at a molding temperature of 280°C for 1 hour, and the ease of peeling of adhesive thermoplastic resin (A-2) was evaluated according to the method described above. The results are summarized in Table 1.

[0083] [Comparative Example 1] Except for not using the silylated polyolefin (B-1), the same procedure as in Example 1 was carried out. The results are shown in Table 1.

[0084] Comparative Example 2 The same procedure as in Example 2 was carried out except that the silylated polyolefin (B-1) was not used. The results are shown in Table 1.

[0085] [Table 1]

Claims

1. An adhesive thermoplastic resin (A), and a silylated polyolefin (B) represented by the following formula (1): the mass ratio of the content of the silylated polyolefin (B) to the content of the adhesive thermoplastic resin (A) in the resin composition is 0.0001 to 0.3; Resin composition. 【Chemistry 1】 (In the above formula (1), A １ , A ２ and A ３ are each independently a polyolefin chain or a hydrocarbon group having 1 to 20 carbon atoms. R is a hydrocarbon group having 1 to 20 carbon atoms. Each R may be the same or different. m is an integer from 1 to 10,000. A ３ If there are multiple A ３ may be the same or different. １ , A ２ , A ３ At least one of these represents a polyolefin chain.

2. The adhesive thermoplastic resin (A) includes a thermoplastic resin containing no polar group or a thermoplastic resin containing a polar group, The resin composition according to claim 1.

3. the thermoplastic resin not containing a polar group is a polyamide, The thermoplastic resin containing a polar group is an ethylene-unsaturated carboxylic acid copolymer. The resin composition according to claim 2.

4. the mass ratio of the content of the silylated polyolefin (B) to the content of the adhesive thermoplastic resin (A) in the resin composition is 0.0005 to 0.005; The resin composition according to any one of claims 1 to 3.

5. A molded article comprising the resin composition according to any one of claims 1 to 4.

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