Resin composition, molded product and method for producing resin composition

Abstract

To provide a resin composition with superior surface smoothness that can suppress an increase in shear stress even with an increased shear rate through a reduction in resistance on the flow channel wall during melt extrusion.SOLUTION: A resin composition contains a thermoplastic resin (A) and a silylated polyolefin (B) represented by formula (1). (In formula (1), A1, A2 and A3 independently represent a polyolefin chain or a C1-20 hydrocarbon group. R is a C1-20 hydrocarbon group. Each R may be the same or different. m is an integer of 1-10,000. When there are a plurality of A3, each A3 may be the same or different, where at least one of A1, A2, and A3 is a polyolefin chain.)SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Thermoplastic resins are widely used in electrical and electronic components, packaging materials, general household goods, and the like, due to their light weight, moldability, and toughness. Patent Document 1 discloses a thermoplastic resin composition containing a thermoplastic resin and a silicone polymer having a polyorganosiloxane structure. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 11-172117 Summary of the Invention [Problem to be solved by the invention]

[0004] As a result of the study by the present inventor, it was found that in the process of producing the thermoplastic resin composition of Patent Document 1, when the thermoplastic resin and the silicone polymer having a polyorganosiloxane structure are kneaded, if the shear rate is increased, the shear stress becomes too large, and therefore the production speed is insufficient. It was also found that if the shear rate is increased, the surface of the obtained thermoplastic resin composition becomes rough. The present invention has been made in consideration of the above circumstances, and provides a resin composition which can suppress an increase in shear stress even when the shear rate is increased during kneading, and which has excellent surface smoothness. [Means for solving the problem]

[0005] According to the present invention, there are provided a resin composition, a molded article, and a method for producing a resin composition, which are described below. 1. A thermoplastic resin (A); and a silylated polyolefin (B) represented by the following formula (1): Resin composition. [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. 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 resin composition according to 1., wherein the thermoplastic resin (A) contains a polyolefin. 3. The resin composition according to 1. or 2., wherein the silylated polyolefin (B) is a processing aid. 4. The resin composition according to any one of 1. to 3., wherein the mass ratio of the content of the silylated polyolefin (B) to the content of the thermoplastic resin (A) in the resin composition is 0.0001 to 0.3. 5. The resin composition according to any one of 1. to 4., further comprising a filler (C). 6. A molded article comprising the resin composition according to any one of 1. to 5. 7. A method for producing a resin composition according to any one of 1. to 5., adding a silylated polyolefin (B) as a processing aid to a thermoplastic resin (A); and a melt-kneading step. Effect of the Invention

[0006] According to the present invention, by reducing the resistance on the wall surface of a flow channel during melt extrusion, an increase in shear stress can be suppressed even when the shear rate is increased, and a resin composition having excellent surface smoothness can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The resin composition, molded article, and method for producing the resin composition according to this embodiment will be described in detail below. However, the present invention is not limited to the following embodiment, and can be practiced with appropriate modifications within the scope of the object of the present invention. In this embodiment, a numerical range expressed using "~" means a range including the numerical values ​​described before and after "~" as the lower and upper limits. In the numerical ranges described in stages in this embodiment, the upper or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in this embodiment, the upper or lower limit described in a certain numerical range may be replaced with a value shown in the examples.

[0008] 1.Resin composition The resin composition according to this embodiment contains a thermoplastic resin (A) and a silylated polyolefin (B) represented by the following formula (1).

[0009] [ka]

[0010] 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. 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 adequately 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 thermoplastic resin (A). Therefore, the present inventors presume that by adding an appropriate amount of the silylated polyolefin (B), a resin composition containing the thermoplastic resin (A) and the silylated polyolefin (B) has a high surface silicon concentration and a suppressed surface free energy, so that an increase in shear stress when the shear rate increases during kneading can be sufficiently suppressed, and the obtained resin composition has excellent surface smoothness. In addition, the highly polar silyl group has low affinity with the thermoplastic resin (A), and is therefore arranged toward the outside of the surface of the resin composition, and the olefin portion of the silylated polyolefin (B) has high affinity with the thermoplastic resin (A), and therefore the olefin portion interacts with the thermoplastic resin (A). This makes it difficult for the silylated polyolefin (B) to fall off from the surface of the resin composition, and as a result, the present inventors presume that the increase in shear stress when the shear rate increases during melt extrusion can be sufficiently suppressed, and the obtained resin composition has excellent surface smoothness.

[0012] In the resin composition according to this embodiment, the mass ratio of the content of the silylated polyolefin (B) to the content of the thermoplastic resin (A) in the resin composition is preferably 0.0001 to 0.3, and is preferably 0.3 or less, more preferably 0.1 or less, even more preferably 0.05 or less, even more preferably 0.01 or less, even more preferably 0.005 or less, and even more preferably 0.001 or less.

[0013] In the resin composition according to this embodiment, the total content of the 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.

[0014] The shape of the resin composition according to the present embodiment is not particularly limited, but examples thereof include pellets, veils, and chunks.

[0015] In addition, when a film is formed using the resin composition according to this embodiment containing the thermoplastic resin (A) and the silylated polyolefin (B), the generation of lumps is suppressed, and the appearance of the film is excellent.

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

[0017] <Thermoplastic resin (A)> Examples of the thermoplastic resin (A) include polyolefins, polyamides, polyesters, polyacetals, styrene-based (co)polymers, acrylic resins, polycarbonates, polyphenylene oxides, chlorine resins such as polyvinyl chloride and polyvinylidene chloride, vinyl acetate resins, ethylene-(meth)acrylic acid ester copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, or ionomers thereof, vinyl alcohol resins, thermoplastic urethane-based elastomers, and rubber components.

[0018] The thermoplastic resin (A) preferably comprises a polyolefin.

[0019] Examples of polyolefins include olefin homopolymers such as polyethylene, polypropylene, poly-1-butene, and polymethylbutene, as well as ethylene-α-olefin random copolymers, propylene-ethylene random copolymers, and ethylene-α-olefin-non-conjugated polyene copolymers. The types and proportions of the structural units constituting each type of polyolefin are as follows: 13 It can be identified by C-NMR.

[0020] (Ethylene polymer) The polyolefin may be, for example, an ethylene-based polymer, which may be an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms.

[0021] Specific examples of ethylene homopolymers include ultra-high molecular weight polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, and the like.

[0022] On the other hand, when the ethylene-based polymer is a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, the proportion of structural units derived from ethylene may be 91.0 mol % to 99.9 mol %. On the other hand, the proportion of structural units derived from an α-olefin having 3 or more carbon atoms may be 0.1 mol % to 9.0 mol % (the total amount of structural units derived from ethylene and structural units derived from an α-olefin having 3 or more carbon atoms is taken as 100 mol %).

[0023] Examples of the α-olefins having 3 to 12 carbon atoms include linear or branched α-olefins such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. The structural unit derived from these α-olefins may be contained either alone or in combination of two or more kinds.

[0024] (Propylene polymer) The polyolefin may be a propylene homopolymer (polypropylene) or a propylene-based polymer of propylene and ethylene or an α-olefin having 4 to 12 carbon atoms (hereinafter referred to as a propylene-α-olefin copolymer).

[0025] When the propylene-based polymer is a copolymer of propylene and ethylene, the proportion of structural units derived from propylene can be 60 mol % to 99.5 mol % (the total amount of structural units derived from propylene and structural units derived from ethylene is taken as 100 mol %).

[0026] When the propylene-based polymer is a copolymer of propylene and an α-olefin having 4 to 12 carbon atoms, examples of the α-olefin having 4 to 12 carbon atoms include linear or branched α-olefins such as 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene. In this case, the propylene-α-olefin copolymer may contain an olefin other than the α-olefin having 4 to 12 carbon atoms. The structural unit derived from these α-olefins may be contained either alone or in combination of two or more kinds.

[0027] When the propylene-based polymer is a copolymer of propylene and an α-olefin having 4 to 12 carbon atoms, the proportion of structural units derived from propylene may be 60 mol % to 90 mol %, while the proportion of structural units derived from an α-olefin having 4 to 12 carbon atoms may be 10 mol % to 40 mol % (the total amount of structural units derived from propylene and structural units derived from an α-olefin having 4 to 12 carbon atoms is taken as 100 mol %).

[0028] The melting point (Tm) of the propylene / α-olefin copolymer as determined by DSC may be, for example, 60°C to 120°C.

[0029] (Ethylene-α-olefin-non-conjugated polyene copolymer) The polyolefin may be an ethylene-α-olefin-non-conjugated polyene copolymer. The copolymer may be a copolymer of ethylene, an α-olefin having 3 to 12 carbon atoms, and a non-conjugated polyene.

[0030] Examples of the α-olefins include linear or branched α-olefins having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene.

[0031] Examples of the non-conjugated polyene include cyclic or linear non-conjugated polyenes. Examples of cyclic non-conjugated polyenes include cyclopentene, cycloheptene, norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, norbornadiene, methyltetrahydroindene, and tetracyclododecene. Examples of linear non-conjugated polyenes include 1,4-hexadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 4-ethylidene-1,7-undecadiene, etc. The structural units derived from these non-conjugated polyenes may be contained in one type or in two or more types.

[0032] Examples of the ethylene-α-olefin-non-conjugated polyene random copolymer include ethylene-propylene-diene terpolymer (EPDM).

[0033] (Other polyolefins) Furthermore, as the polyolefin, a propylene / α-olefin / non-conjugated polyene copolymer, a 1-butene / α-olefin / non-conjugated polyene copolymer, or the like may be used.

[0034] Furthermore, as the polyolefin, a known ethylene / cyclic olefin copolymer (COC) and a cyclic olefin polymer (COP) may be used.

[0035] The thermoplastic resin (A) may be produced using a raw material derived from biomass.

[0036] <Silylated polyolefin (B)> The silylated polyolefin (B) according to this embodiment is represented by the following formula (1).

[0037] [ka]

[0038] 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. 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.

[0039] Above A 1 , A 2 and A 3 The polyolefin chain in the above formula is, for example, a polymer chain containing a structural unit derived from an olefin having 2 to 50 carbon atoms.

[0040] Specific examples of the olefin having 2 to 50 carbon atoms include ethylene and α-olefins having 3 to 50 carbon atoms (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, vinylcyclohexane, etc.).

[0041] The polyolefin chain may be a homopolymer chain or a copolymer chain. 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 an α-olefin having 3 to 20 carbon atoms may be more than 0 mol % and 20 mol % or less.

[0042] The polyolefin chain may also contain structural units derived from other olefins, if desired. Examples of other olefins include olefins containing internal double bonds such as cis-2-butene, vinylidene compounds such as isobutene, arylvinyl compounds such as styrene, arylvinylidene compounds such as α-methylstyrene, vinylidene compounds substituted with functional groups such as methyl methacrylate, aliphatic cyclic olefins containing internal double bonds such as 5-methyl-2-norbornene, tetracyclododecene, cyclopentadiene, and dicyclopentadiene, cyclic olefins containing aromatic rings such as indene, and linear or cyclic polyenes such as butadiene, isoprene, ethylidene norbornene, and vinyl norbornene. 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 %.

[0043] The polyolefin chain may have a number average molecular weight of 100 to 500,000 as determined by the GPC method described below.

[0044] 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.

[0045] GPC measurement method: The 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 in terms of polyethylene. The measurement can be carried out under the following conditions. The molecular weight can be calculated based on the following conversion method using a calibration curve prepared using commercially available monodisperse standard polystyrene. Apparatus: Gel permeation chromatograph Alliance GPC2000 (Waters) Solvent: o-dichlorobenzene Column: TSKgel column (Tosoh Corporation) x 4 Flow rate: 1.0ml / min Sample: 0.15mg / 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. Polystyrene (PS) coefficient: KPS = 1.38 x 10 -4 ,aPS=0.70 Coefficient of polyethylene (PE): KPE = 5.06 x 10 -4 ,aPE=0.70

[0046] 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.

[0047] Examples of the alkyl group include linear or branched alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group, and an octadecyl group; and cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a norbornyl group. 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.

[0048] In the above formula (1), m is an integer from 1 to 10,000.

[0049] In the above formula (1), A 3 If there are multiple A 3 may be the same or different.

[0050] In the above formula (1), A 1 , A 2 , A 3 At least one of these represents a polyolefin chain.

[0051] 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, a plurality of types of units represented by the following formula (2) are present, but the order in which they are arranged is not particularly limited and may be in a block or random order.

[0052] [ka]

[0053] 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.

[0054] In the silylated polyolefin (B) according to this embodiment, the silicone chain / polyolefin chain (mass ratio) is not particularly limited, and may be, for example, 5 / 95 to 99 / 1.

[0055] 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 methods described in paragraphs 0089 to 0145 and paragraphs 0196 to 0207 of WO 2012 / 098865.

[0056] 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.

[0057] The silylated polyolefin (B) may be produced using a raw material derived from biomass.

[0058] The silylated polyolefin (B) may be used as a processing aid, which provides excellent processability even though the composition is fluorine-free.

[0059] <Filler (C)> The resin composition according to the present embodiment may further contain a filler (C) as desired, within the scope of the present invention. Resin compositions containing a filler tend to generate die boogers at the die outlet (lip portion) during the molding process, and it is desirable to suppress this. By using the resin composition according to the present embodiment, it is possible to suppress the generation of die boogers. The term "eye burr" used during melt extrusion molding of a resin composition refers to the resin composition that accumulates near the lip between the lip of a die and the resin composition that flows due to extrusion. Here, the lip of the die means the part of the extruder that discharges the resin composition to the atmosphere. Eye burr may be formed by concentrating resin components that are poorly compatible with the matrix resin or low-viscosity components in the resin composition and accumulating them on the lip. In addition, when fillers are included in the resin composition, the interaction between these fillers and the matrix resin is weak, and the friction between the inner surface of the flow path near the outlet of the lip and the flowing resin composition in contact with it may cause the fillers to separate from the resin composition and accumulate on the lip side. As a result, the following problems caused by eye burr may occur. When the die lip is left to accumulate for a long time, the oxygen in the air accelerates the oxidation of the die lip, which can lead to deterioration. The die lip can fall off during molding and adhere to the molded product, causing defects in the appearance of the molded product, which can be problematic. Furthermore, if the die lip generates in a short time or in large quantities, molding operations must be stopped and time must be spent cleaning the die lip, which can lead to reduced production efficiency.

[0060] The filler (C) includes, for example, one or more types selected from the group consisting of inorganic fillers and organic fillers. There are no limitations on the inorganic filler as long as it can be kneaded with the resin, and examples include oxide ceramics such as silicon oxide (silica), titanium oxide (titania), aluminum oxide (alumina), magnesium oxide (magnesia), and iron oxide; nitride ceramics such as boron nitride and aluminum nitride; carbide ceramics such as silicon carbide and boron carbide; inorganic fillers obtained by crushing natural ores such as calcium carbonate, talc, and mica; and metal materials such as aluminum, various aluminum alloys, copper, various copper alloys, magnesium alloys, various nickel alloys, various iron alloys, tungsten, molybdenum, and tantalum. The inorganic filler may have functionality, and examples of such inorganic fillers include inorganic fillers that function as flame retardants, such as aluminum hydroxide and magnesium hydroxide; inorganic fillers that function as fillers, such as carbon black, barium sulfate, and various glasses; and inorganic fillers that function as pigments (inorganic pigments), such as zinc oxide.

[0061] There are no limitations on the organic filler as long as it can be kneaded into the resin, and examples of the organic filler include organic fillers (organic pigments) that function as pigments, such as phthalocyanine pigments; various natural fibers, such as wood flour, pulp, and cellulose nanofibers; and synthetic fibers, such as nylon fibers.

[0062] When the resin composition according to this embodiment contains a filler (C), the content of the filler (C) in the resin composition according to this embodiment is not particularly limited, but may be 1% by mass to 80% by mass, 10% by mass to 60% by mass, or 20% by mass to 70% by mass, when the entire resin composition is taken as 100% by mass.

[0063] <Other additives> The resin composition according to the present embodiment may contain various known additives used in the production of polyolefin products, if desired, within the scope of the present invention. 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. Manufacturing method of resin composition The method for producing a resin composition according to the present embodiment includes a step of adding a silylated polyolefin (B) as a processing aid to a thermoplastic resin (A) and a step of melt-kneading the resin, thereby reducing the resistance on the flow channel wall during melt extrusion and sufficiently suppressing an increase in shear stress when the shear rate increases. The preferred ranges of the composition and physical properties of the thermoplastic resin (A) and the silylated polyolefin (B) used are the same as those exemplified as the preferred ranges for the resin composition.

[0065] 3. 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. The molded article according to the present embodiment can be molded from the resin composition according to the present 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, and compression molding.

[0066] 4.Applications Examples of applications of the molded article of the present embodiment include, but are not limited to, the following.

[0067] The molded article can be preferably used as packaging materials for various foods, daily necessities, and industrial products, medical containers, and can also be used as exterior materials such as outdoor fences, wood decks, parboras (grapevine trellises), and lattices for buildings, interior materials such as interior wall materials, floor materials, ceiling materials, and furniture materials, and other play equipment.

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

[0069] Furthermore, the above molded article can be used for various applications including 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 base materials, deck trims, inner panels, pillar garnishes, rear packages, package trays, switch bases, quarter panels, seat structural materials, seat backboards, armrest core materials, ceiling base materials, 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 The material can also be used for a variety of applications, including 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, etc.; surface decorative materials such as buttons and emblems; various parts such as housings, display windows, and buttons for mobile phones, etc.; 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, including various packaging containers such as bottles, cosmetic containers, and trinket boxes, packaging materials, and miscellaneous goods such as prizes and small items.

[0070] The molded article is also suitable for use in many fields, such as electrical insulating materials, industrial part materials, building materials, leisure parts, agricultural implement parts, marine or fishing equipment parts, and the like. In particular, as housing components and building materials, 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, fittings and ceiling materials, undercoating materials, tatami mats, floors, concrete panels, scaffolding materials, insulation boards, soundproofing boards, furniture box ceilings, doors, front and back panels, shelves, sleeve boards, fascia boards, deck boards, back panels, seat boards, kitchen components, waterproofing materials, anti-mildew materials, preservatives, storm shutter boards, sleeve boards, wainscoting, side panels, bathroom units, floor pans, bathroom ceilings, bathroom walls, It can also be applied to baths, buckets, sanitary equipment, toilet seats, toilet covers, home appliances, radio / television receivers, cabinets, stereo cabinets, amplifier cabinets, speakers, speaker boxes, main panels of piano organs, main roofs, rolled roofs, upper and lower scroll panels, buoyancy bodies (foam) in life jackets, surfboards, cold weather glove materials, fishing equipment (floats, decorative balls, fish-attracting balls, artificial bait), camping equipment, agricultural films, gardening posts, vinyl greenhouse posts or fasteners for fixing posts, marine fenders, floats, etc.

[0071] The molded article can also be used in small vehicles such as bicycles and electrically assisted bicycles, escalators, elevators, and the like, manned aircraft, unmanned aircraft, ultra-high-speed passenger aircraft, rockets, and artificial satellites, and other aviation materials, vehicles such as fuel cell vehicles, hydrogen battery vehicles, and linear motor cars, various playground 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 automation equipment interiors, office automation equipment housings, toilet lighting fixtures, umbrellas, raincoats, heat insulating materials, flooring, paints, barrier agents, hydrophilic / hydrophobic control agents, papermaking materials, tires, dampers, hoses, and 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, glasses, sunglasses, and wearable terminals.

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

[0073] The present invention will be described in detail below with reference to 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 ​​based on the following conversion method. Apparatus: Gel permeation chromatograph Alliance GPC2000 (Waters) Solvent: o-dichlorobenzene Column: Four TSKgel columns (Tosoh Corporation) connected in series ·Flow rate: 1.0ml / min Sample: 0.15mg / mL Lo-dichlorobenzene solution ·Temperature: 140℃ Molecular weight conversion: PS conversion / general calibration method For the general-purpose calibration calculation, the coefficients of the Mark-Houwink viscosity equation shown below were used. Polystyrene (PS) coefficient: KPS = 1.38 x 10 -4 ,aPS=0.70 Coefficient of polyethylene (PE): KPE = 5.06 x 10 -4 ,aPE=0.70

[0075] (2) Relationship between shear rate and shear stress, and the shear rate that causes roughness of the strand The shear stress of each resin composition was measured using the following capillary viscometer under the following measurement conditions. Then, the extruded strand was obtained, and the surface was observed to determine the shear rate at which the strand was roughened due to melt fracture. The presence or absence of roughness of the strand was observed using a digital microscope VHX-1000 (manufactured by Keyence Corporation) at a magnification of 100 times. Capillary viscometer: Toyo Seiki Capillograph 1D, barrel inner diameter = 9.55 mm Capillary nozzle: Flow path cross-sectional shape = circular, flow path length L = 15 mm, flow path inner diameter D = 0.5 mm Piston extrusion speed (unit: mm / min): 5 → 7.5 → 10 → 15 → 20 → 30 → 50 → 75 → 100 → 150 ·Measurement temperature: 210℃

[0076] (3) Appearance when made into a film The films obtained by the methods described in Example 2 and Comparative Example 3 below were cut into rectangular sizes (MDxTD=260x170mm), and the number of bumps in each piece of film with a diameter of 0.2mm or more was counted using a magnifying glass with a scale that can be magnified 10 times. If the bumps were deformed into an oval shape, the length in the long axis direction was measured as the bump size.

[0077] (4) Method for evaluating eye discharge When resin compositions were produced by the methods described in Example 3 and Comparative Example 4 below, the vicinity of the T-die lip of a single-screw extruder for T-die melt extrusion film molding was photographed, and the length and number of hemispherical lump-like pinholes adhering to the vicinity of the 300 mm wide T-die lip were measured in the MD direction. Then, the number of pinholes with a MD length of 1 mm or more was used to evaluate the quality according to the following criteria. 5 or less:〇 6~20 pieces:△ 21 or more: ×

[0078] 2.Raw materials The raw materials used in the examples and comparative examples are shown below. (1) Thermoplastic resin (A) As thermoplastic resin (A-1), density is 918 kg / m 3 The LLDPE used was Evolu (registered trademark) grade SP2040 manufactured by Prime Polymer Co., Ltd., having a melting point of 116° C. and MFR (190° C., 2.16 kg load) of 3.8 g / 10 min. As thermoplastic resin (A-2), density is 903kg / m 3 The LLDPE used was Evolue (registered trademark) grade SP0510 manufactured by Prime Polymer Co., Ltd., having a melting point of 98° C. and MFR (190° C., 2.16 kg load) of 1.2 g / 10 min. As thermoplastic resin (A-3), density is 918kg / m 3 The LLDPE used was Evolue (registered trademark) grade SP2020 manufactured by Prime Polymer Co., Ltd., having a melting point of 116° C. and MFR (190° C., 2.16 kg load) of 2.3 g / 10 min.

[0079] (2) Silylated polyolefin (B) [Synthesis Example 1] (Synthesis of polyethylene with a vinyl group at one end) An ethylene polymer containing a vinyl group at one end (P-1) was synthesized according to the method described in Synthesis Example 2 of WO 2012 / 098865. 1 The H-NMR measurement revealed that the obtained polymer was homopolyethylene and contained a double bond only at one end. The physical properties of this ethylene-based polymer (P-1) (single unit) containing a double bond at one end were as follows: Melting point (Tm) 127℃ Mw=4770, Mw / Mn=2.25 (GPC) Terminal unsaturation rate 97%

[0080] [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 chloride (II) was suspended in hydrosilane A (HS(A), manufactured by Gelest, Inc., DMS-H11) (10 ml) having the following structure, and stirred at room temperature under a nitrogen stream. After stirring for 190 hours, about 0.4 ml of the reaction solution was collected with a syringe, and filtered using a 0.45 μm PTFE filter to collect the filtrate in a 10 ml sample tube, thereby obtaining a platinum catalyst composition (C-1) having 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)

[0081] [Synthesis Example 3] (Introduction of polyethylene having 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) containing 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 of Si-H groups) of hydrosilane A (HS(A)) and 150 μl (1.4 × 10 in terms of Pt) of the platinum catalyst composition (C-1) prepared in [Synthesis Example 2] diluted 200 times with hydrosilane A (HS(A)) (C-1a). -6 The two-neck flask was then 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 to obtain 33.1 g of a white solid silylated polyolefin (B-1). As a result of NMR analysis, the yield of the obtained silylated polyolefin (B-1) was 98%, the olefin conversion rate 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.

[0082] (3) Inorganic filler masterbatch As the inorganic filler master batch (M-1), a 60% TiO2 / polyethylene master batch (MFP-TILD1 manufactured by Sanpuku Kogyo Co., Ltd., specific gravity approximately 1.72, MFR (190°C, 10 kgf) approximately 10 g / 10 min) was used.

[0083] [Example 1] 100 parts by mass of thermoplastic resin (A-1) was dry-blended with 0.1 parts by mass of silylated polyolefin (B-1) as a processing aid, and melt-mixed in a twin-screw extruder (L / D=60, Toshiba Machine TEM-26SS) at a cylinder temperature of 200°C to obtain resin composition (D-1). The relationship between shear rate and shear stress and the shear rate at which strand roughness occurred were evaluated by the above method. Table 1 shows the shear rate at which strand roughness occurred, and Table 2 shows the relationship between shear rate and shear stress.

[0084] [Example 2] 100 parts by mass of thermoplastic resin (A-2) was dry-blended with 0.1 parts by mass of silylated polyolefin (B-1) as a processing aid, and the mixture was put into the hopper of the single-screw extruder for T-die melt extrusion film molding described above, and a molten web was extruded from the T-die at a screw speed of 71 rpm, cooled on a cooling roll, and taken off at a take-off speed of 2 m / min. The thickness of the film was 85 μm. The appearance of the obtained film was evaluated when it was made into a film by the above method. The results are shown in Table 3.

[0085] The conditions of the single screw extruder were as follows: the cylinder inner diameter was 20 mm. The screw had a full flight shape, an effective length / diameter ratio (L / D) of 28, and a compression ratio of 3.0. The surface of the screw was finished with mirror-finished hard chrome plating. The T-die conditions were as follows: the lip width was 300 mm, and it was a coat hanger type. The flow passage surface of the T-die was finished with hard chrome plating. The take-off machine was equipped with a temperature-controlled cooling roll (roll diameter 200 mm, hard chrome-plated mirror finish). The temperatures from the extruder cylinder to the die and the temperature of the temperature-adjusted cooling roll were set as follows. Extruder cylinder to die temperature: C1 / C2 / C3 / adapter / die = 175 / 210 / 210 / 210 / 210℃ Temperature-controlled cooling roll setting temperature: 30℃

[0086] [Example 3] A dry blend of 10 parts by mass of thermoplastic resin (A-1), 48.3 parts by mass of thermoplastic resin (A-3), 41.7 parts by mass of inorganic filler master batch (M-1) and 0.1 parts by mass of silylated polyolefin (B-1) as a processing aid was placed in a hopper after cleaning the lip of the single-screw extruder for T-die melt extrusion film molding described above, and a molten web was extruded from the T-die at a screw speed of 82 rpm and allowed to drip downward in the vertical direction. 30 minutes after the start of extrusion, a photograph was taken near the exit (lip) of the T-die, and the size and number of hemispherical eye burrs attached near the lip of the T-die were measured and evaluated by the above method. The results are shown in Table 4. The conditions of the single screw extruder were as follows: the cylinder inner diameter was 20 mm. The screw had a full flight shape, an effective length / diameter ratio (L / D) of 28, and a compression ratio of 3.0. The surface of the screw was mirror-finished with hard chrome plating. The conditions of the T-die were as follows: the lip width was 300 mm, and it was a coat hanger type. The flow passage surface of the T-die, including the lip, was hard chrome plated and finished to a mirror finish. The temperatures from the extruder cylinder to the die and the temperature of the temperature-adjusted cooling roll were set as follows. Extruder cylinder to die temperature: C1 / C2 / C3 / adapter / die = 185 / 210 / 210 / 210 / 210℃

[0087] [Comparative Example 1] Except for not using the silylated polyolefin (B-1), the same operation as in Example 1 was carried out. Table 1 shows the shear rate at which roughening occurred in the strands, and Table 2 shows the relationship between the shear rate and the shear stress.

[0088] [Comparative Example 2] The same operation as in Example 1 was carried out, except that a silicone master batch (GENIOPLAST, PELLET S manufactured by Wacker Asahi Kasei Silicone Co., Ltd.) was used instead of the silylated polyolefin (B-1). The shear rate at which roughness occurred in the strands is shown in Table 1, and the relationship between the shear rate and the shear stress is shown in Table 2.

[0089] [Comparative Example 3] The same operation as in Example 2 was carried out except that the silylated polyolefin (B-1) was not used. The thickness of the obtained film was 85 μm. The obtained film was used to prepare a film by the above-mentioned method, and the appearance was evaluated. The results are shown in Table 3.

[0090] [Comparative Example 4] The same procedure as in Example 3 was carried out, except that the silylated polyolefin (B-1) was not used. The results are shown in Table 4.

[0091] [Table 1]

[0092] [Table 2]

[0093] [Table 3]

[0094] [Table 4]

Claims

1. A thermoplastic resin (A); and a silylated polyolefin (B) represented by the following formula (1): 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 them represents a polyolefin chain.

2. The resin composition according to claim 1 , wherein the thermoplastic resin (A) comprises a polyolefin.

3. The resin composition according to claim 1 or 2, wherein the silylated polyolefin (B) is a processing aid.

4. The resin composition according to any one of claims 1 to 3, wherein the mass ratio of the content of the silylated polyolefin (B) to the content of the thermoplastic resin (A) in the resin composition is 0.0001 to 0.

3.

5. The resin composition according to any one of claims 1 to 4, further comprising a filler (C).

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

7. A method for producing the resin composition according to any one of claims 1 to 5, adding a silylated polyolefin (B) as a processing aid to a thermoplastic resin (A); and a melt-kneading step.

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