Block Polymers

Abstract

To provide a block polymer imparting an excellent mechanical strength to a thermoplastic resin, especially, a polyolefin resin.SOLUTION: A block polymer (X) has at least two polyolefin structures derived from the following polyolefin (B) as a constitutional unit, where the polyolefin structures derived from the polyolefin (B) are bonded to each other through the following binder (γ). Polyolefin (B): containing α-olefin having 3 to 8 carbon atoms as a constituent monomer, and having isotacticity of the α-olefin part of 1% or more and less than 65%, and a number average molecular weight of 1,000-200,000. Binder (γ): at least one selected from the group consisting of an unsaturated (poly)carboxylic acid (anhydride) (C), a hydroxyl group-containing compound (F), an epoxy group-containing compound (P), an isocyanate group-containing compound (L) and an aminocarboxylic acid (H).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a block polymer. [Background technology]

[0002] Polyolefin resins are excellent in moldability, rigidity, electrical insulation, etc., and are inexpensive, so they are widely and generally used as films, fibers, and other molded products of various shapes. In addition, various modifiers for polyolefin resins have been developed, and modifiers containing low-molecular-weight polyolefins have been proposed for the purpose of improving pigment dispersibility and mechanical strength (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2015-117362 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0004] However, even the above techniques have not been fully satisfactory in terms of mechanical strength. An object of the present invention is to provide a block polymer that imparts excellent mechanical strength to a thermoplastic resin, particularly a polyolefin resin. [Means for solving the problem]

[0005] The present inventors have conducted extensive research to solve the above problems and have arrived at the present invention. That is, the present invention relates to a block polymer (X) having at least two polyolefin structures derived from the following polyolefin (B) as constituent units, and the polyolefin structures derived from the polyolefin (B) are bonded via the following binder (γ). Polyolefin (B): contains an α-olefin having 3 to 8 carbon atoms as a constituent monomer, has an isotacticity of the α-olefin portion of 1% or more and less than 65%, and has a number average molecular weight of 1,000 to 200,000; Binder (γ): at least one selected from the group consisting of unsaturated (poly)carboxylic acid (anhydride) (C), a hydroxyl group-containing compound (F), an epoxy group-containing compound (P), an isocyanate group-containing compound (L), and an aminocarboxylic acid (H); Effect of the Invention

[0006] The block polymer (X) of the present invention has the following effects. (1) It imparts excellent mechanical strength (tensile strength, impact strength, etc.) to the molded article of the thermoplastic resin composition (Z). (2) It gives recycled polyolefin resin (YR) excellent mechanical strength. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] <Polyolefin (B)> The polyolefin (B) in the present invention contains an α-olefin having 3 to 8 carbon atoms as a constituent monomer, the α-olefin portion has an isotacticity of 1% or more and less than 65%, and a number average molecular weight of 1,000 to 200,000.

[0008] In the following, "α-olefin having 3 to 8 carbon atoms" may be referred to as "α-olefin". Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene. Among the above α-olefins, propylene is preferred from the viewpoint of isotacticity, which will be described later.

[0009] The polyolefin (B) may contain other monomers as constituent monomers in addition to the α-olefin. In this case, the weight of the other monomers is preferably 70% by weight or less, more preferably 30% by weight or less, and even more preferably 10% by weight or less, based on the weight of all the monomers constituting the polyolefin (B).

[0010] Examples of other monomers constituting the polyolefin (B) include ethylene, 2-butene, isobutene, α-olefins having a carbon number (hereinafter sometimes abbreviated as C) of 9 to 30 (1-decene, 1-dodecene, etc.), and unsaturated monomers having a carbon number of 4 to 30 other than α-olefins (for example, vinyl acetate). Of the above other monomers, ethylene is preferred, and of (B), a propylene / ethylene copolymer is preferred.

[0011] The isotacticity of the α-olefin portion of the polyolefin (B) is preferably 1% or more and less than 65%, more preferably 1 to 50%, and particularly preferably 1 to 35%, from the viewpoint of mechanical strength. The isotacticity of the α-olefin portion of the above polyolefin (B) tends to be directly reflected in the isotacticity of the α-olefin portion of the acid-modified polyolefin (BE), hydroxyl-modified polyolefin (BG), aminocarboxylic acid-modified polyolefin (BJ), epoxy-modified polyolefin (BQ), and isocyanate-modified polyolefin (BM) in which (B) is bonded to the binder (γ) described below.

[0012] The above isotacticity is 13It can be calculated using C-NMR (nuclear magnetic resonance spectroscopy). In general, when the α-olefin is propylene, the side chain methyl group, and when the α-olefin is 1-butene, 1-pentene, 1-hexene, 1-heptene, or 1-octene, the side chain methylene group next to the main chain methine group are affected by the stereoconfiguration (meso or racemo) of both adjacent (triad), both adjacent (pentad) of the triad, and even both adjacent (septad) of the pentad, and are known to have peaks observed at different chemical shifts. Therefore, the evaluation of stereoregularity is generally performed for the pentad, and the isotacticity in the present invention is also calculated based on the evaluation of the pentad.

[0013] That is, when the α-olefin is propylene, 13 Regarding the carbon peaks derived from the side chain methyl groups in propylene obtained by C-NMR, when the α-olefin is 1-butene, 1-pentene, 1-hexene, 1-heptene, or 1-octene, 13 Regarding the carbon peaks derived from the side chain methylene groups adjacent to the main chain methine groups in the α-olefins obtained by C-NMR, the pentad peak intensity of the α-olefin part of polyolefin (B) is shown as (H). In the case of isotactic polyolefins in which the pentad is formed only of mesostructure, the α-olefin is propylene, and in the case of α-olefins of 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene, the methyl group is shown. 13 When the peak intensity derived from a side-chain methylene group adjacent to a main-chain methine group in an α-olefin obtained by C-NMR is taken as (Ha), the isotacticity is calculated by the following formula: Isotacticity (%) = [(Ha) / Σ(H)] × 100 (1)

[0014] The conditions for measuring the isotacticity in the present invention are as follows. Equipment: JEOL Ltd. ECZ400R Measurement mode: Proton decoupling method Pulse width: 8μsec Pulse repetition time: 4.6sec Relaxation time: 3.0sec Accumulation count: 10,000 times Solvent: orthodichlorobenzene Reference material: Tetramethylsilane Sample concentration: 10mg / mL ·Measurement temperature: 120℃

[0015] The number average molecular weight (Mn) of the polyolefin (B) is preferably from 1,000 to 200,000, more preferably from 1,500 to 100,000, and particularly preferably from 2,000 to 50,000, from the viewpoint of mechanical strength.

[0016] In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be measured by GPC (gel permeation chromatography). In the present invention, the conditions for measuring Mn by GPC are as follows. Apparatus: High temperature gel permeation chromatography ["AllianceGPCV2000", Waters, Inc.] Detector: Refractive index detector Solvent: orthodichlorobenzene Reference material: Polystyrene Sample concentration: 3mg / ml Column stationary phase: PLgel 10μm, MIXED-B 2 columns in series [Manufactured by Polymer Laboratories, Inc.] Column temperature: 135℃

[0017] The number of double bonds per 1,000 carbon atoms in the polyolefin (B) [the number of carbon-carbon double bonds at the molecular terminals and / or in the molecular chain of the polyolefin (B)] is preferably 0.2 to 20, more preferably 0.5 to 18, and still more preferably 1.0 to 15, from the viewpoints of the productivity and mechanical strength of the block polymer (X) described below. Here, the number of double bonds is 1 It can be obtained from the H-NMR spectrum. That is, the peaks in the spectrum are assigned, and the relative value between the number of double bonds in polyolefin (B) and the number of carbon atoms in polyolefin (B) is obtained from the integral value derived from the double bonds at 4.5 to 6 ppm of polyolefin (B) and the integral value derived from polyolefin (B), and the number of double bonds in the molecular terminal and / or molecular chain per 1,000 carbons of polyolefin (B) is calculated. The number of double bonds in the examples described later follows this method.

[0018] The method for producing the polyolefin (B) in the present invention may, for example, be as follows. (1) A method of thermally degrading a high molecular weight (preferably Mn of 60,000 to 800,000, more preferably Mn of 80,000 to 250,000) polyolefin (B0). (2) A method of polymerizing a monomer containing an α-olefin in the presence of a polymerization catalyst.

[0019] Of the above (1) and (2), from the viewpoint of productivity, (1) is preferred.

[0020] The thermal degradation method includes a method of heating the high molecular weight polyolefin (B0) (1) in the absence of an organic peroxide, for example, at 300 to 450°C for 0.5 to 10 hours, and (2) in the presence of an organic peroxide [for example, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane], for example, at 180 to 300°C for 0.5 to 10 hours. Among these, from the industrial viewpoint and from the viewpoint of productivity of the block polymer (X), the method (1) is preferred, which can easily give a polymer having a larger number of double bonds at the molecular terminals and / or in the molecular chain.

[0021] In the polyolefin (B), the number of double bonds per 1,000 carbon atoms tends to increase as the thermal degradation temperature in the thermal degradation step increases or the thermal degradation time increases. Furthermore, the smaller the Mn of the high molecular weight polyolefin (B0), the higher the thermal degradation temperature, or the longer the thermal degradation time, the smaller the Mn of the polyolefin (B) tends to be. Furthermore, the higher the isotacticity of the high molecular weight polyolefin (B0), the higher the isotacticity of the polyolefin (B) tends to be. The polyolefin (B) may be used alone or in combination of two or more kinds.

[0022] <Block polymer (X)> The block polymer (X) of the present invention has at least two polyolefin structures derived from the following polyolefin (B) as constituent units, and has a structure in which the polyolefin structures derived from the polyolefin (B) are bonded via the following binder (γ). Polyolefin (B): contains an α-olefin having 3 to 8 carbon atoms as a constituent monomer, has an isotacticity of the α-olefin portion of 1% or more and less than 65%, and has a number average molecular weight of 1,000 to 200,000; Binder (γ): at least one member (preferably at least two members) selected from the group consisting of unsaturated (poly)carboxylic acid (anhydride) (C), hydroxyl group-containing compound (F), epoxy group-containing compound (P), isocyanate group-containing compound (L) and aminocarboxylic acid (H);

[0023] In addition, the block polymer (X) of the present invention is useful as a modifier for a thermoplastic resin (Y) described below (particularly a modifier for a polyolefin resin), and can improve the mechanical strength (tensile strength, impact strength, etc.) of the thermoplastic resin (Y). That is, the block polymer (X) is a block polymer in which the polyolefin (B) and the polyolefin (B) are bonded via the binder (γ).

[0024] From the viewpoint of balance of mechanical strength, the Mn (number average molecular weight) of the block polymer (X) is preferably from 3,000 to 500,000, more preferably from 4,000 to 300,000, and particularly preferably from 5,000 to 150,000.

[0025] The block polymer (X) has a structure in which a polyolefin structure derived from the polyolefin (B) and a polyolefin structure derived from the polyolefin (B) are bonded via the following binder (γ). Binder (γ): at least one member (preferably at least two members) selected from the group consisting of unsaturated (poly)carboxylic acid (anhydride) (C), hydroxyl group-containing compound (F), epoxy group-containing compound (P), isocyanate group-containing compound (L) and aminocarboxylic acid (H); Of the above binders (γ), a combination of an unsaturated (poly)carboxylic acid (anhydride) (C) [sometimes referred to as unsaturated carboxylic acid (anhydride) (C)] with at least one selected from the group consisting of a hydroxyl group-containing compound (F) and an aminocarboxylic acid (H) is preferred.

[0026] The structure of the block polymer (X) is preferably any one of the following (1) to (3), more preferably (1) or (2), and particularly preferably (1). (1): [(B)-(γ)]n-(B) type block polymer (n = 1 to 6) (2): [(B)-(γ)]n-(B)-(γ) type block polymer (n = 1 to 6) (3): (γ)-[(B)-(γ)]n-(B)-(γ) type block polymer (n = 1 to 6) In the above (1) to (3), n is preferably 1 to 2, and more preferably n=1.

[0027] The Mn of the block polymer (X) and the structure of the block polymer (X) can be appropriately adjusted by the Mn and weight of (B) and the type, weight and reaction conditions of the binder (γ) described below.

[0028] Examples of the method for producing the block polymer (X) include the following. The acid-modified polyolefin (BE), hydroxyl-modified polyolefin (BG), aminocarboxylic acid-modified polyolefin (BJ), isocyanate-modified polyolefin (BM), and epoxy-modified polyolefin (BQ), which will be described later, are reacted under known conditions.

[0029] For example, acid-modified polyolefin (BE) is a reaction product of polyolefin (B) and unsaturated (poly)carboxylic acid (anhydride) (C); hydroxyl-modified polyolefin (BG) is a reaction product of acid-modified polyolefin (BE) and hydroxyl-containing compound (F) or polyolefin (B) and hydroxyl-containing compound (F); aminocarboxylic acid-modified polyolefin (BJ) is a reaction product of acid-modified polyolefin (BE) and aminocarboxylic acid (H); isocyanate-modified polyolefin (BM) is a reaction product of hydroxyl-modified polyolefin (BG) and isocyanate-containing compound (L); and epoxy-modified polyolefin (BQ) is a reaction product of polyolefin (B) and epoxy-containing compound (P).

[0030] That is, the combination of the binder (γ) is, for example, A combination of (C) and (F), A combination of (C), (F) and (H), A combination of (C), (F) and (L), A combination of (C), (F) and (P), A combination of (C) and (H), A combination of (C), (H) and (P), A combination of (C), (H), (F) and (L), A combination of (C), (H), (F) and (P), A combination of (C) and (P), A combination of (F) and (H), A combination of (F) and (L), and a combination of (F) and (P). Of the above, the combination of (C), (F) and (H) is preferred.

[0031] The block polymer (X) can be produced, for example, by the following method. (1) An acid-modified polyolefin (BE) is reacted with a hydroxyl-modified polyolefin (BG), forming an ester bond. (2) Aminocarboxylic acid-modified polyolefin (BE) is reacted with hydroxyl-modified polyolefin (BG), forming amide bonds and / or imide bonds and ester bonds.

[0032] (3) Hydroxyl-modified polyolefin (BG) is reacted with isocyanate-modified polyolefin (BM), forming amide bonds and / or imide bonds and urethane bonds. (4) Acid-modified polyolefin (BE) is reacted with epoxy-modified polyolefin (BQ), forming an ester bond.

[0033] (5) Aminocarboxylic acid modified polyolefin (BE) is reacted with epoxy group modified polyolefin (BQ), where amide bonds and / or imide bonds and ester bonds are formed. (6) Hydroxyl-modified polyolefin (BE) is reacted with epoxy-modified polyolefin (BQ), forming an ether bond.

[0034] <Acid-modified polyolefin (BE)> The acid-modified polyolefin (BE) is, for example, a reaction product between a polyolefin (B) and an unsaturated (poly)carboxylic acid (anhydride) (C). In the above reaction, a radical initiator (f) (dicumyl peroxide, etc.) may be used.

[0035] The unsaturated carboxylic acid (anhydride) (C) is an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic acid anhydride. The unsaturated carboxylic acid (anhydride) (C) is preferably a monocarboxylic acid having 3 to 24 carbon atoms [sometimes abbreviated as C] and one polymerizable unsaturated group, a C4 to 24 polycarboxylic acid having one polymerizable unsaturated group, and / or a C4 to 24 polycarboxylic acid anhydride having one polymerizable unsaturated group.

[0036] Among the unsaturated (poly)carboxylic acids (anhydrides) (C), examples of the unsaturated monocarboxylic acids include aliphatic monocarboxylic acids (C3-24, e.g., acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid), alicyclic monocarboxylic acids (C6-24, e.g., cyclohexene carboxylic acid); examples of the unsaturated poly(2-3 or more) carboxylic acids or their anhydrides include unsaturated dicarboxylic acids or their anhydrides [aliphatic dicarboxylic acids or their anhydrides (C4-24, e.g., maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and their anhydrides), alicyclic dicarboxylic acids or their anhydrides (C8-24, e.g., cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptene dicarboxylic acid, methyltetrahydrophthalic acid, and their anhydrides)], etc. The unsaturated carboxylic acids (anhydrides) (C) may be used alone or in combination of two or more.

[0037] Among the above (poly)unsaturated carboxylic acid (anhydrides) (C), from the viewpoints of reactivity with the polyolefin (B) and mechanical strength, unsaturated dicarboxylic acid anhydrides are preferred, and maleic anhydride is more preferred.

[0038] From the viewpoint of productivity of (X), the acid-modified polyolefin (BE) has an acid value (mgKOH / g) of preferably 1 to 100 mgKOH / g (hereinafter only numerical values ​​are shown), more preferably 3 to 75, and particularly preferably 5 to 50. The acid value here is a value measured in accordance with JIS K0070. The acid value can be appropriately adjusted by the amount of double bonds in the polyolefin (B), the weight of the polyolefin (B), and the type and weight of the unsaturated carboxylic acid (anhydride) (C).

[0039] <Hydroxyl group modified polyolefin (BG)> The hydroxyl-modified polyolefin (BG) is, for example, a reaction product of the acid-modified polyolefin (BE) with a hydroxyl-containing compound (F), or a reaction product of polyolefin (B) with a hydroxyl-containing compound (F).

[0040] The hydroxyl-containing compound (F) has at least one hydroxyl group in the molecule and has a functional group other than the hydroxyl group that can react with the acid-modified polyolefin (BE) or the polyolefin (B). Examples of the hydroxyl group-containing compound (F) include 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 2- or 3-hydropiperazine, 2-, 3- or 4-aminocyclohexanol, 2-, 3- or 4-aminophenol, 2- or 3-amino-p-cresol, 2- or 4-amino-m-cresol, 3- or 4-amino-o-cresol, and 2-mercaptoethanol. Among the above (F), from the viewpoint of reactivity, preferred are 2-aminoethanol, 3-aminopropanol, 4-aminobutanol and 2-mercaptoethanol, and more preferred are 2-aminoethanol and 2-mercaptoethanol.

[0041] From the viewpoint of productivity of (X), the hydroxyl value of the hydroxyl-modified polyolefin (BG) is preferably 1 to 100 mgKOH / g (hereinafter, only numerical values ​​are shown), more preferably 3 to 75, and particularly preferably 5 to 50. The hydroxyl value here is a value measured in accordance with JIS K0070. The hydroxyl value can be appropriately adjusted by, for example, the type and weight of the acid-modified polyolefin (BE) and the type and weight of the hydroxyl group-containing compound (F).

[0042] <Epoxy modified polyolefin (BQ)> The epoxy group-modified polyolefin (BQ) is, for example, a reaction product between the polyolefin (B) and an epoxy group-containing compound (P).

[0043] The epoxy group-containing compound (P) has at least one epoxy group in the molecule and has a functional group other than the epoxy group that can react with the polyolefin (B).

[0044] Examples of the epoxy group-containing compound include glycidyl acrylate and glycidyl methacrylate.

[0045] From the viewpoint of productivity of (Q), the epoxy equivalent (g / eq) of the epoxy group-modified polyolefin (BQ) is preferably 500 to 100,000 g / eq (hereinafter, only numerical values ​​are shown), more preferably 650 to 50,000, and particularly preferably 800 to 20,000. The epoxy equivalent here is a value measured in accordance with JIS K7236. The epoxy equivalent can be appropriately adjusted by the type and weight of the polyolefin (B) and the type and weight of the epoxy group-containing compound (P).

[0046] <Isocyanate-modified polyolefin (BM)> The above-mentioned isocyanate group-modified polyolefin (BM) is, for example, a reaction product between the above-mentioned hydroxyl group-modified polyolefin (BG) and an isocyanate group-containing compound (L).

[0047] The isocyanate group-containing compound (L) has at least one isocyanate group in the molecule. Examples of the isocyanate group-containing compound (L) include hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate.

[0048] The isocyanate group content (wt%) of the isocyanate group-modified polyolefin (BM) is preferably 0.04 to 8.5% (hereinafter only numerical values ​​are shown), more preferably 0.08 to 6.0, and particularly preferably 0.2 to 5.0, from the viewpoint of productivity of (M). The isocyanate group content here is a value measured in accordance with JIS K1603. The isocyanate group content can be appropriately adjusted by the type and weight of the hydroxyl group-modified polyolefin (BG) and the type and weight of the isocyanate group-containing compound (L).

[0049] <Aminocarboxylic acid modified polyolefin (BJ)> The aminocarboxylic acid-modified polyolefin (BJ) is, for example, a reaction product of the acid-modified polyolefin (BE) and an aminocarboxylic acid (H).

[0050] Examples of the aminocarboxylic acid (H) include 12-aminododecanoic acid and 6-aminohexanoic acid.

[0051] The acid value (mgKOH / g) of the aminocarboxylic acid modified polyolefin (BJ) is preferably 1-100 mgKOH / g (hereinafter only numerical values ​​are shown), more preferably 3-75, and particularly preferably 5-50, from the viewpoint of productivity of (X). The acid value can be appropriately adjusted by adjusting the type and weight of the acid-modified polyolefin (BE) and the type and weight of the aminocarboxylic acid (H).

[0052] The block polymer of the present invention imparts excellent mechanical strength (tensile strength, impact strength) to a molded article of the thermoplastic resin composition (Z) described below, and further imparts excellent mechanical strength to the recycled polyolefin resin (YR). Therefore, it can be suitably used as a modifier for thermoplastic resins, particularly as a modifier for polyolefin resins.

[0053] <Thermoplastic resin composition (Z)> The thermoplastic resin composition (Z) of the present invention contains the above block polymer (X) and a thermoplastic resin (Y).

[0054] The weight ratio [(X) / (Y)] of the block polymer (X) to the thermoplastic resin (Y) in the thermoplastic resin composition (Z) of the present invention is preferably 0.01 / 99.99 to 50 / 50, more preferably 1 / 99 to 30 / 70, and particularly preferably 3 / 97 to 20 / 80, from the viewpoints of the modifying properties of the block polymer (X) and the mechanical strength of a molded article described later.

[0055] The thermoplastic resin (Y) includes those other than the above (X), such as polyolefin resins (polypropylene, low density polyethylene, high density polyethylene), polystyrene resins, polyester resins, and nylon resins. Of the above thermoplastic resins (Y), polyolefin resins are preferred.

[0056] As described above, recycled polyolefin resin (YR) is also suitable as thermoplastic resin (Y). The (YR) is a polyolefin resin that has been once molded and then crushed, pulverized, pelletized, or otherwise processed.

[0057] From the viewpoints of the mechanical strength of the molded article and the compatibility with the block polymer (X), the Mn of the thermoplastic resin (Y) is preferably from 10,000 to 500,000, more preferably from 20,000 to 400,000, and further preferably from 80,000 to 300,000.

[0058] The thermoplastic resin composition (Z) of the present invention may further contain, if necessary, one or more additives (N) selected from the group consisting of fillers (N1), colorants (N2), matting agents (N3), antistatic agents (N4), dispersants (N5), flame retardants (N6), foaming agents (N7), antioxidants (N8), ultraviolet absorbers (N9) and plasticizers (N10) within the scope of not impairing the effects of the present invention.

[0059] Examples of the filler (N1) include organic fillers (for example, wood flour, cellulose) and inorganic fillers (for example, calcium carbonate, talc, glass fiber, carbon fiber). Among these fillers (N1), from the viewpoint of mechanical strength, inorganic fillers are preferred, and calcium carbonate is more preferred. The amount of (N1) used based on the total weight of the thermoplastic resin composition (Z) is, for example, 50% by weight or less, preferably 3 to 50% by weight, and more preferably 5 to 40% by weight.

[0060] The total amount of (N2) to (N10) used in the thermoplastic resin composition (Z) of the present invention is, for example, 30% by weight or less, based on the total weight of the block polymer (X), and preferably 1 to 20% by weight from the viewpoints of functional expression of (N) and industrial applications.

[0061] The amount of each additive (N) other than (N1) used based on the total weight of the thermoplastic resin composition (Z) is, for example, 10% by weight or less, preferably 1 to 5% by weight; (N3) is, for example, 20% by weight or less, preferably 1 to 10% by weight; (N4) is, for example, 10% by weight or less, preferably 1 to 5% by weight; (N5) is, for example, 20% by weight or less, preferably 0 to 15% by weight, and more preferably 0 to 10% by weight; (N6) is, for example, 15% by weight or less, preferably 3 to 10% by weight; (N7) is, for example, 1 to 20% by weight or less, preferably 5 to 15% by weight; (N8) is, for example, 3% by weight or less, preferably 0.01 to 1% by weight; (N9) is, for example, 3% by weight or less, preferably 0.01 to 1% by weight; and (N10) is, for example, 20% by weight or less, preferably 5 to 15% by weight.

[0062] In addition, when the additives are the same and overlap among (N1) to (N10), each additive is not used in an amount that exerts the corresponding additive effect regardless of the effect as an additive of the other additives, but the amount used is adjusted according to the purpose of use, taking into consideration that the effect of the other additives is obtained at the same time.

[0063] The method for producing the thermoplastic resin composition (Z) of the present invention includes the following steps: (1) A method in which the total amounts of the thermoplastic resin (Y) and the block polymer (X), and optionally (N), are mixed together in one batch to prepare a resin composition (lump-sum method); (2) A method (masterbatch method) in which a part of the thermoplastic resin (Y), the whole amount of the block polymer (X), and, if necessary, a part or the whole amount of the additive (N) are mixed to prepare a masterbatch resin composition containing a high concentration of the block polymer (X), and then the remaining thermoplastic resin (Y) and, if necessary, the remaining additive (N) are added and mixed to obtain a resin composition. From the viewpoint of the mixing efficiency of the block polymer (X), the method (2) is preferred.

[0064] <Molded products> The molded article of the present invention is a molded product of the above thermoplastic resin composition (Z). That is, the molded article of the present invention is obtained by molding the above thermoplastic resin composition (Z). Examples of the molding method include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.), and any method incorporating means such as single-layer molding, multi-layer molding, or foam molding can be used depending on the purpose. Examples of the form of the molded product include plate-like, sheet-like, film-like, fiber (including nonwoven fabric, etc.), etc. EXAMPLES

[0065] The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the examples, "parts" refers to parts by weight. In the examples, the number average molecular weight (Mn), the amount of double bonds in the polyolefin, the isotacticity, the acid value, the hydroxyl value, the epoxy equivalent, and the isocyanate group content were measured by the above-mentioned methods.

[0066] <Production Example 1> A reaction vessel was charged with 100 parts of a high molecular weight polyolefin (B0-1) [trade name "Vistamaxx6102", manufactured by ExxonMobil, the same applies below], and while aerating nitrogen into the liquid phase, the mixture was heated and melted using a mantle heater, and thermally degraded at 350°C for 10 minutes while stirring, to obtain polyolefin (B-1). The polyolefin (B-1) had an Mn of 30,000, the number of double bonds in the molecular terminals and / or molecular chains per 1,000 carbons was 0.5, and the isotacticity was 28%.

[0067] <Production Examples 2 to 5> Each polyolefin (B) was obtained by carrying out thermal degradation in the same manner as in Production Example 1, except that the high molecular weight polyolefin (B0), temperature, and time were changed according to Table 1. The results are shown in Table 1.

[0068] [Table 1]

[0069] <Production Example 6> In a reaction vessel, 100 parts of polyolefin (B-1) and 1 part of maleic anhydride (C-1) were charged, and the mixture was heated to 200°C under nitrogen aeration and stirred for 10 hours. After that, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa, the same applies below) to obtain an acid-modified polyolefin (BE-1). The acid-modified polyolefin (BE-1) had an acid value of 2.0, Mn of 30,100, and isotacticity of 28%.

[0070] <Production Examples 7 to 10> The reactions were carried out in the same manner as in Production Example 6, except that the polyolefin (B), unsaturated carboxylic acid (anhydride) (C), and radical initiator (f) were changed according to Table 2, to obtain each acid-modified polyolefin (BE). The results are shown in Table 2.

[0071] [Table 2]

[0072] <Production Example 11> In a reaction vessel, 100 parts of polyolefin (B-3), 6 parts of glycidyl methacrylate (P-1), and 1 part of dicumyl peroxide (f-1) were added and stirred for 10 hours. After that, the unreacted glycidyl methacrylate was distilled off under reduced pressure (1.5 kPa, the same applies below) to obtain an epoxy-modified polyolefin (BQ-1). The epoxy group-modified polyolefin (BQ-1) had an epoxy equivalent of 2,500, Mn of 3,200, and isotacticity of 50%.

[0073] [Table 3]

[0074] <Production Example 12> In a reaction vessel, 100 parts of acid-modified polyolefin (BE-1) and 1 part of 2-aminoethanol (F-1) were charged, and the mixture was heated to 180°C under nitrogen aeration and stirred for 10 hours. After that, stirring was continued for 10 hours under reduced pressure (1.5 kPa, the same applies below) to obtain a hydroxyl-modified polyolefin (BG-1). The hydroxyl-modified polyolefin (BG-1) had a hydroxyl value of 2.0, Mn of 30,500, and isotacticity of 28%.

[0075] <Production Example 13> Each hydroxyl group-modified polyolefin (BG) was obtained by carrying out the reaction in the same manner as in Production Example 12, except that the acid-modified polyolefin (BE) was changed according to Table 4. The results are shown in Table 4.

[0076] <Production Example 14> In a reaction vessel, 100 parts of acid-modified polyolefin (BE-3) and 10 parts of 12-aminododecanoic acid (H-1) were charged, and the mixture was heated to 180°C under nitrogen aeration and stirred for 10 hours. After that, stirring was continued for 10 hours under reduced pressure (1.5 kPa, the same applies below) to obtain aminocarboxylic acid-modified polyolefin (BJ-1). The aminocarboxylic acid modified polyolefin (BJ-1) had an acid value of 22.2, Mn of 3,400, and isotacticity of 50%.

[0077] <Production Examples 15-16> Each aminocarboxylic acid-modified polyolefin (BJ) was obtained by carrying out the reaction in the same manner as in Production Example 14, except that the acid-modified polyolefin (BE) and the aminocarboxylic acid (H) were changed according to Table 4. The results are shown in Table 4.

[0078] [Table 4]

[0079] <Production Example 17> In a reaction vessel, 100 parts of polyolefin (B-1), 1 part of 2-mercaptoethanol (F-2), and 200 parts of xylene were charged, and the mixture was heated to 160°C under nitrogen aeration, and 1 part of 1,1'-azobis(cyclohexane-1-carbonitrile) (f-1) was charged, and stirring was continued for 10 hours. After that, xylene and unreacted 2-mercaptoethanol were distilled off under reduced pressure (1.5 kPa, the same applies below) to obtain a hydroxyl group-modified polyolefin (BG-3). The hydroxyl-modified polyolefin (BG-3) had a hydroxyl value of 2.0, Mn of 30,100, and isotacticity of 28%.

[0080] [Table 5]

[0081] <Production Example 18> In a reaction vessel, 100 parts of hydroxyl group-modified polyolefin (BG-2), 8 parts of diphenylmethane diisocyanate (L-1), and 200 parts of xylene were charged, and the mixture was heated to 150°C under nitrogen aeration and stirred for 10 hours. After that, the xylene and unreacted diphenylmethane diisocyanate were distilled off under reduced pressure (1.5 kPa, the same applies below) to obtain an isocyanate group-modified polyolefin (BM-1). The isocyanate group-modified polyolefin (BM-1) had an isocyanate group content of 0.71, Mn of 11,000, and isotacticity of 27%.

[0082] [Table 6]

[0083] <Example 1> A reaction vessel was charged with 10 parts of (BJ-1), 100 parts of (BG-1), and 0.1 parts of dibutyltin as an esterification catalyst, and after replacing with nitrogen, the mixture was heated to 200°C under nitrogen aeration to dissolve. Stirring was continued at 200°C for 3 hours. After that, the mixture was reacted under reduced pressure (1.5 kPa, the same applies below) for 5 hours, and then removed from the reaction vessel to obtain a block polymer (X-1). In addition, (X-1) had an Mn of 42,000 and an acid value of 0.01.

[0084] <Examples 2 to 3> Each block polymer (X) was obtained by carrying out the reaction in the same manner as in Example 1, except that the raw materials used in Example 1 were changed according to Table 7. The results are shown in Table 7.

[0085] <Example 4> A reaction vessel was charged with 25 parts of (BM-1), 100 parts of (BG-3), 200 parts of xylene, and 0.1 parts of bismuth tris(2-ethylhexaate) as a urethane catalyst, and after replacing with nitrogen, the mixture was heated to 150°C under nitrogen aeration to dissolve. Stirring was continued at 150°C for 3 hours. After that, the xylene was distilled off under reduced pressure (1.5 kPa, the same applies below), and the mixture was removed from the reaction vessel to obtain a block polymer (X-4). In addition, (X-4) had an Mn of 62,000 and a hydroxyl value of 0.02.

[0086] <Example 5> Each block polymer (X) was obtained by carrying out the reaction in the same manner as in Example 4, except that the raw materials used in Example 4 were changed according to Table 7. The results are shown in Table 7.

[0087] <Example 6> A reaction vessel was charged with 100 parts of (BJ-2), 100 parts of (BQ-1), and 0.1 parts of the epoxidation catalyst diazabicycloundecene, and after replacing with nitrogen, the mixture was heated to 150°C under nitrogen aeration to dissolve. After stirring for 3 hours at 150°C, the mixture was removed from the reaction vessel to obtain (X-6). In addition, (X-6) had an Mn of 9,500 and an acid value of 0.01.

[0088] The results for each block polymer (X) are shown in Table 7. For comparison, polyolefin (B-1) was used as a block polymer.

[0089] [Table 7]

[0090] <Examples 7 to 12, Comparative Examples 1 to 2> According to the compounding composition (parts) in Table 8, each block polymer (X) and thermoplastic resin (Y) were melt-kneaded in a twin-screw extruder [product name "KZW45TW", manufactured by Technobel Co., Ltd.] at 230°C and 100 rpm to obtain each thermoplastic resin composition (Z). Each thermoplastic resin composition (Z) was injection molded using an injection molding machine (trade name "PS40E5ASE", manufactured by Nissei Plastics Co., Ltd.) at a nozzle temperature of 230°C and a mold temperature of 50°C, and evaluated according to the evaluation method described below. The results are shown in Table 8.

[0091] <Evaluation method> (1) Tensile strength The tensile strength was evaluated by measuring according to JIS K7171. <Evaluation criteria> ◎:30MPa or more ○: 25MPa or more and less than 30MPa △: 20MPa or more and less than 25MPa ×: Less than 20MPa

[0092] (2) Impact resistance The Izod impact value was measured in accordance with JIS K7110. <Evaluation criteria> ◎: 3.0 kJ / m 2 End ○: 1.5 kJ / m 2 More than 3.0kJ / m 2 less than △: 1.0 kJ / m 2 More than 1.5kJ / m 2 less than ×:1.0kJ / m 2 less than

[0093] [Table 8]

[0094] <Examples 13 to 18, Comparative Examples 3 to 4> According to the compounding composition (parts) in Table 9, each block polymer (X) and thermoplastic resin (YR-1) [recycled polyolefin resin, product name "PP Crushed", manufactured by Miki Plastics Co., Ltd.] were melt-kneaded in a twin-screw extruder [product name "KZW45TW", manufactured by Technobel Co., Ltd.] at 230°C and 100 rpm to obtain each thermoplastic resin composition (Z). After pelletizing, the mixture was injection molded using an injection molding machine (product name "PS40E5ASE", manufactured by Nissei Plastics Co., Ltd.) at a nozzle temperature of 230°C and a mold temperature of 50°C to prepare test pieces, which were then evaluated according to the evaluation methods described below. The results are shown in Table 9.

[0095] (1) Tensile strength The tensile strength was evaluated by measuring according to JIS K7171. <Evaluation criteria> ◎:25MPa or more ○: 20MPa or more and less than 25MPa △: 15MPa or more and less than 20MPa ×: Less than 15MPa (2) Impact resistance The Izod impact value was measured in accordance with JIS K7110. <Evaluation criteria> ◎: 2.5kJ / m 2 End ○: 1.2 kJ / m 2 More than 2.5kJ / m2 less than △: 0.8kJ / m 2 More than 1.2kJ / m 2 less than ×:0.8kJ / m 2 less than

[0096] [Table 9]

[0097] <Examples 19 to 24, Comparative Examples 5 to 6> According to the compounding composition (parts) in Table 10, each block polymer (X), thermoplastic resin (Y), and filler (N1) were melt-kneaded in a twin-screw extruder [product name "KZW45TW", manufactured by Technobel Co., Ltd.] at 230°C and 100 rpm to obtain each thermoplastic resin composition (Z). After pelletizing, the mixture was injection molded using an injection molding machine (product name "PS40E5ASE", manufactured by Nissei Plastics Co., Ltd.) at a nozzle temperature of 230°C and a mold temperature of 50°C to prepare test pieces, which were then evaluated according to the evaluation methods described below. The results are shown in Table 10.

[0098] (1) Bending strength The tensile strength was evaluated according to JIS K7171 (unit: MPa). (2) Impact resistance Charpy impact values ​​were measured according to ASTM D6110 (unit: J / m).

[0099] [Table 10]

[0100] From the results in Tables 1 to 10, it is seen that the block polymer (X) of the present invention imparts superior mechanical strength to the molded article of the thermoplastic resin composition (Z) compared to the comparative ones, and also imparts superior mechanical strength to the recycled polyolefin resin (YR). [Industrial Applicability]

[0101] The block polymer (X) of the present invention is useful as a modifier for the thermoplastic resin (Y) and can improve the mechanical strength (tensile strength, impact strength, etc.) of the thermoplastic resin (Y). For this reason, it is extremely useful for applications in molded articles of various thermoplastic resins.

Claims

1. A block polymer (X) having at least two polyolefin structures derived from the following polyolefin (B) as constituent units, the polyolefin structures derived from the polyolefin (B) being bonded via the following binder (γ). Polyolefin (B): contains, as a constituent monomer, an α-olefin having 3 to 8 carbon atoms, the isotacticity of the α-olefin portion being 1% or more and less than 65%, and the number average molecular weight being 1,000 to 200,000; Binder (γ): at least one selected from the group consisting of unsaturated (poly)carboxylic acid (anhydride) (C), a hydroxyl group-containing compound (F), an epoxy group-containing compound (P), an isocyanate group-containing compound (L), and an aminocarboxylic acid (H); The hydroxyl group-containing compound (F) is at least one selected from the group consisting of 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, and 2-mercaptoethanol; the epoxy group-containing compound (P) is at least one selected from the group consisting of glycidyl acrylate and glycidyl methacrylate; the isocyanate group-containing compound (L) is at least one selected from the group consisting of hexamethylene diisocyanate, diphenylmethane diisocyanate, and isophorone diisocyanate; the aminocarboxylic acid (H) is at least one selected from the group consisting of 12-aminododecanoic acid and 6-aminohexanoic acid;

2. The block polymer (X) according to claim 1, having a number average molecular weight of 3,000 to 500,000.

3. A thermoplastic resin composition (Z) comprising the block polymer (X) according to claim 1 or 2 and a thermoplastic resin (Y).

4. The thermoplastic resin composition (Z) according to claim 3, wherein the weight ratio of the block polymer (X) to the thermoplastic resin (Y) [(X) / (Y)] is 0.01 / 99.99 to 50 / 50.

5. The thermoplastic resin composition (Z) according to claim 3 or 4, further comprising a filler (N1), the weight of the filler (N1) being 3 to 50% by weight based on the weight of the thermoplastic resin composition.

6. A molded article obtained by molding the thermoplastic resin composition (Z) according to any one of claims 3 to 5.

Images