Block polymer, thermoplastic resin composition, and molded article

Abstract

A block polymer (X) having a polyolefin structure derived from the following polyolefin (A) and a polyolefin structure derived from the following polyolefin (B) as structural units. Polyolefin (A): containing an α-olefin having 3 to 8 carbon atoms as a constituent monomer, the isotactic regularity of the α-olefin moiety being 70 to 100%, the number-average molecular weight being 1,000 to 200,000, and the number of carbon-carbon double bonds per 1,000 carbon atoms being 0.01 to 8.0; Polyolefin (B): containing an α-olefin having 3 to 8 carbon atoms as a constituent monomer, the isotactic regularity of the α-olefin moiety being 1 to 65%, and the number-average molecular weight being 1,000 to 200,000.

Description

Technical Field

[0001] The present invention relates to a block polymer, a thermoplastic resin composition, and a molded article. Background Art

[0002] Polyolefin resins are excellent in moldability, rigidity, electrical insulation properties, etc., and are inexpensive, and thus are widely and commonly used as films, fibers, and molded articles of various shapes. In addition, various modifiers have been developed for polyolefin resins, and a modifier containing a low molecular weight polyolefin has been proposed for the purpose of improving pigment dispersibility and mechanical strength (for example, Patent Document 1).

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2015-117362 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] However, even with the above technology, the mechanical strength is not fully satisfactory. 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.

[0008] Means for Solving the Problems

[0009] The present inventors have conducted intensive studies to solve the above problems, and as a result, the present invention has been achieved. That is, the present invention relates to: a block polymer (X) having a polyolefin structure derived from the following polyolefin (A) and a polyolefin structure derived from the following polyolefin (B) as structural units; a thermoplastic resin composition (Z) containing the above block polymer (X) and a thermoplastic resin (Y); and a molded article obtained by molding the above thermoplastic resin composition (Z).

[0010] Polyolefin (A): contains an α-olefin having 3 to 8 carbon atoms as a constituent monomer, the isotactic regularity of the α-olefin moiety is 70 to 100%, the number average molecular weight is 1,000 to 200,000, and the number of carbon-carbon double bonds per 1000 carbon atoms is 0.01 to 8.0;

[0011] Polyolefin (B): contains an α-olefin having 3 to 8 carbon atoms as a constituent monomer, the isotactic regularity of the α-olefin moiety is 1 to 65%, and the number average molecular weight is 1,000 to 200,000.

[0012] Effects of the Invention

[0013] The block polymer (X) of the present invention exhibits the following effects.

[0014] (1) To impart excellent modification effects (improvement of mechanical strengths such as tensile strength, flexural strength, and impact strength) to the molded article of the thermoplastic resin composition (Z).

[0015] (2) To impart excellent mechanical strength to the recycled polyolefin resin (YR). Detailed implementation mode

[0016] <Polyolefin (A)>

[0017] The polyolefin (A) is a polyolefin that contains an α-olefin having 3 to 8 carbon atoms as a constituent monomer, the isotactic regularity of the α-olefin part is 70 to 100%, the number-average molecular weight is 1,000 to 200,000, and the number of carbon-carbon double bonds per 1,000 carbon atoms is 0.01 to 8.0.

[0018] It should be noted that hereinafter, the "α-olefin having 3 to 8 carbon atoms" is sometimes referred to as "α-olefin".

[0019] As the above-mentioned α-olefin, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene can be cited.

[0020] Among the above-mentioned α-olefins, propylene is preferred from the aspect of the isotactic regularity described later.

[0021] In addition, the above-mentioned polyolefin (A) and the polyolefin (B) described later can be distinguished by the isotactic regularity of the α-olefin part.

[0022] In the above-mentioned polyolefin (A), other monomers can also be used as constituent monomers. In this case, based on the weight of all monomers constituting the polyolefin (A), the weight of other monomers is preferably 20% by weight or less, more preferably 15% by weight or less, and further preferably 10% by weight or less.

[0023] As other monomers constituting the above-mentioned polyolefin (A), for example, ethylene, 2-butene, isobutene, α-olefins having 9 to 30 carbon atoms (1-decene, 1-dodecene, etc.), and C4 to 30 unsaturated monomers other than α-olefins (such as vinyl acetate) can be cited.

[0024] Among the above-mentioned other monomers, ethylene is preferred. In addition, in the polyolefin (A), a propylene / ethylene copolymer is preferred.

[0025] From the aspect of the modification effect of the block polymer (X) described later, the isotactic regularity of the α-olefin part of the polyolefin (A) is 70 to 100%, preferably 75 to 100%, and more preferably 80 to 100%.

[0026] The isotacticity of the α-olefin moiety of the above polyolefin (A) tends to be directly reflected in the isotacticity of the α-olefin moiety of the acid-modified polyolefin (AE), hydroxy-modified polyolefin (AG), aminocarboxylic acid-modified polyolefin (AJ), epoxy-group-modified polyolefin (AQ), and isocyanate-group-modified polyolefin (AM) formed by combining the polyolefin (A) with the binder (γ) described later.

[0027] The above isotacticity can be calculated using 13 C-NMR (nuclear magnetic resonance spectroscopy). It is generally known that the side-chain methyl group when the α-olefin is propylene and the side-chain methylene adjacent to the main-chain methylene when the α-olefin is 1-butene, 1-pentene, 1-hexene, 1-heptene, or 1-octene are affected by the steric configuration (meso or racemic) to the extent of the adjacent two sides (triplet, three-tuple), the adjacent two sides of this triplet (pentad, five-tuple), and further to the adjacent two sides of this pentad (septet, seven-tuple), and peaks are observed at different chemical shifts. Therefore, the evaluation of stereoregularity is usually carried out for the pentad. The isotacticity in the block polymer (X) of the present invention is also calculated based on the evaluation of the pentad.

[0028] That is, in the case where the α-olefin is propylene, for the carbon peak from the side-chain methyl group in propylene obtained by 13 C-NMR, setting the peak intensity of each pentad of the α-olefin moiety as (H) and the peak intensity of the methyl group from the isotactic polyolefin formed only by the meso structure in the pentad as (Ha), the isotacticity is calculated by the following formula (1).

[0029] Isotacticity (%) = [(Ha) / Σ(H)]×100 (1)

[0030] In addition, in the case where the α-olefin is 1-butene, 1-pentene, 1-hexene, 1-heptene, or 1-octene, for the carbon peak from the side-chain methylene adjacent to the main-chain methylene in the α-olefin obtained by 13 C-NMR, setting the peak intensity of each pentad of the α-olefin moiety as (H) and the peak intensity of the side-chain methylene adjacent to the main-chain methylene from the isotactic polyolefin formed only by the meso structure in the pentad as (Ha), the isotacticity is calculated by the above formula (1).

[0031] It should be noted that the isotacticity of the α-olefin moiety can be adjusted by changing the polymerization conditions during the polymerization of the α-olefin moiety.

[0032] The difference in the isotacticity of the α-olefin moiety between polyolefin (A) and the α-olefin moiety of polyolefin (B) is preferably 10 to 90%, more preferably 20 to 80%, and even more preferably 30 to 70%.

[0033] The measurement conditions for isotacticity in this specification are as follows.

[0034] · Apparatus: ECZ400R manufactured by JEOL Ltd.

[0035] · Measurement mode: Proton decoupling method

[0036] · Pulse width: 8 μsec

[0037] · Pulse repetition time: 4.6 sec

[0038] · Relaxation time: 3.0 sec

[0039] · Number of accumulations: 10,000 times

[0040] · Solvent: o-dichlorobenzene

[0041] · Reference substance: Tetramethylsilane

[0042] · Sample concentration: 10 mg / mL

[0043] · Measurement temperature: 120 °C

[0044] From the aspect of the modification effect of block polymer (X), the number-average molecular weight (Mn) of the above polyolefin (A) is preferably 1,000 to 200,000, more preferably 1,500 to 100,000, and particularly preferably 2,000 to 50,000.

[0045] In this specification, the number-average molecular weight (Mn) can be measured by GPC (gel permeation chromatography).

[0046] In this specification, the measurement conditions for Mn based on GPC are as described below.

[0047] · Apparatus: High-temperature gel chromatography ["Alliance GPC V2000", manufactured by Waters Corporation]

[0048] · Detection device: Refractive index detector

[0049] · Solvent: o-dichlorobenzene

[0050] · Reference substance: Polystyrene

[0051] · Sample concentration: 3 mg / mL

[0052] · Column stationary phase: Two PLgel 10 μm, MIXED-B columns connected in series [manufactured by Polymer Laboratories, Ltd.]

[0053] · Column temperature: 135 °C

[0054] From the viewpoints of the productivity of the block polymer (X) described later and the modification effect, the number of double bonds per 1,000 carbon atoms in the above polyolefin (A) [the number of carbon-carbon double bonds at the molecular terminals and / or in the molecular chain of the polyolefin (A)] is 0.01 to 8.0, preferably 0.5 to 7.0, and more preferably 1.0 to 5.0.

[0055] In this specification, the above-mentioned number of double bonds in the polyolefin (A) can be determined from the 1 1H-NMR spectrum of the polyolefin (A). That is, the peaks in the above spectrum are assigned, and the relative value of the number of double bonds in the polyolefin (A) to the number of carbon atoms in the polyolefin (A) is determined based on the integral value from the double bond at 4.5 to 6 ppm and the integral value from the polyolefin (A), and the number of double bonds at the molecular terminals and / or in the molecular chain per 1,000 carbons in the polyolefin (A) is calculated. The calculation of the number of double bonds in the examples described later follows the above method.

[0056] As a method for producing the above polyolefin (A), for example, the following methods can be mentioned.

[0057] (1) A method of thermally degrading a high molecular weight polyolefin (A0) (preferably having a Mn of 60,000 to 1,000,000, more preferably a Mn of 80,000 to 250,000)

[0058] (2) A method of polymerizing an α-olefin in the presence of a polymerization catalyst

[0059] Among the above (1) to (2), from the viewpoint of productivity, (1) is preferred.

[0060] The thermal degradation method includes: a method of heating the above high molecular weight polyolefin (A0) (1) at 300 to 450 °C for 0.1 to 10 hours in the absence of an organic peroxide; and (2) a method of heating at 180 to 300 °C for 0.5 to 10 hours in the presence of an organic peroxide [such as 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane]; etc.

[0061] Among these, from the industrial viewpoint and the viewpoint of the productivity of the block polymer (X), the method (1), which easily gives a polyolefin having more double bonds at the molecular terminals and / or in the molecular chain, is preferred.

[0062] In the above polyolefin (A), the higher the thermal degradation temperature or the longer the thermal degradation time in the thermal degradation process, the more the number of double bonds per 1,000 carbon atoms tends to increase.

[0063] In addition, the smaller the Mn of the high molecular weight polyolefin (A0), the higher the thermal degradation temperature, or the longer the thermal degradation time, the more the Mn of the polyolefin (A) tends to decrease.

[0064] In addition, the greater the isotactic regularity of the high molecular weight polyolefin (A0), the more the isotactic regularity of the polyolefin (A) tends to increase.

[0065] It should be noted that the polyolefin (A) can be used alone or in combination of two or more.

[0066] <Polyolefin (B)>

[0067] Polyolefin (B) is a polyolefin containing α-olefins having 3 to 8 carbon atoms as constituent monomers, with an isotactic regularity of the α-olefin part of 1 to 65% and a number average molecular weight of 1,000 to 200,000.

[0068] Examples of the above α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.

[0069] Among the above α-olefins, from the aspect of the modification effect of the block polymer (X) described later, propylene, 1-butene, 1-hexene, and 1-octene are preferred, propylene and 1-butene are more preferred, and propylene is particularly preferred.

[0070] In the above polyolefin (B), other monomers can also be used as constituent monomers. In this case, based on the weight of all monomers constituting the polyolefin (B), the weight of other monomers is preferably 80% by weight or less, more preferably 50% by weight or less, and further preferably 20% by weight or less.

[0071] Examples of other monomers constituting the above polyolefin (B) include ethylene, 2-butene, C9-30 α-olefins (1-decene, 1-dodecene, etc.), and C4-30 unsaturated monomers other than α-olefins (e.g., vinyl acetate).

[0072] Among the above other monomers, ethylene is preferred. In addition, in the polyolefin (B), a propylene / ethylene copolymer, a propylene / 1-butene copolymer, and an ethylene / 1-octene copolymer are preferred, and a propylene / ethylene copolymer is more preferred.

[0073] From the viewpoint of the modification effect of the block polymer (X) described below, the isotacticity of the α-olefin part of the polyolefin (B) is 1 to 65%, preferably 1 to 50%, and more preferably 1 to 35%.

[0074] The isotacticity of the α-olefin part of the above-mentioned polyolefin (B) tends to be directly reflected in the isotacticity of the α-olefin part of the acid-modified polyolefin (BE), hydroxyl-modified polyolefin (BG), aminocarboxylic acid-modified polyolefin (BJ), epoxy-modified polyolefin (BQ), and isocyanate-modified polyolefin (BM) described later.

[0075] The isotacticity of the polyolefin (B) can be used in the same manner as the isotacticity of the polyolefin (A). 13 The measurement was performed by C-NMR.

[0076] The number average molecular weight (Mn) of the polyolefin (B) is preferably 1,000 to 200,000, more preferably 1,500 to 100,000, and particularly preferably 2,000 to 50,000, from the viewpoint of the modification effect of the block polymer (X).

[0077] The Mn of the polyolefin (B) can be measured by GPC in the same manner as the Mn of the polyolefin (A).

[0078] From the perspective of productivity of the block polymer (X) described below, the number of double bonds per 1,000 carbon atoms of the polyolefin (B) [the number of carbon-carbon double bonds at the molecular ends and / or in the molecular chain of the polyolefin (B)] is preferably 0.01 to 8.0, more preferably 0.5 to 7.0, and particularly preferably 1.0 to 5.0.

[0079] The number of double bonds per 1,000 carbon atoms of the polyolefin (B) can be used in the same manner as the number of double bonds per 1,000 carbon atoms of the polyolefin (A). 1 The measurement was performed by H-NMR.

[0080] Examples of the method for producing the polyolefin (B) include a method of thermally degrading a high molecular weight (preferably Mn of 60,000 to 1,000,000, more preferably Mn of 80,000 to 800,000) polyolefin (B0).

[0081] The relationship between the polyolefin (B) and the polyolefin (B0) is the same as the relationship between the polyolefin (A) and the polyolefin (A0).

[0082] The conditions for the method for producing the polyolefin (B) from the polyolefin (B0) are the same as the conditions for the method for producing the polyolefin (A) from the polyolefin (A0).

[0083] It should be noted that one kind of polyolefin (B) can be used alone, or two or more kinds can be used in combination.

[0084] <Block polymer (X)>

[0085] The block polymer (X) of the present invention is a block polymer having a polyolefin structure derived from the above polyolefin (A) and a polyolefin structure derived from the above polyolefin (B) as structural units.

[0086] In addition, the block polymer (X) of the present invention is useful as a modifier for the thermoplastic resin (Y) described later (especially a modifier for polyolefin resins), and can improve the mechanical strength (tensile strength, flexural strength, impact strength, etc.) of the thermoplastic resin (Y).

[0087] That is, the block polymer (X) is a block polymer having the above polyolefin (A) and the above polyolefin (B) as structural units.

[0088] The block polymer (X) of the present invention can be obtained, for example, by reacting the above polyolefin (A) with the above polyolefin (B). Such a method is also a method for producing the block polymer (X) of the present invention. When reacting the above polyolefin (A) with the above polyolefin (B), a known method can be used. In addition, when reacting the above polyolefin (A) with the above polyolefin (B), the binder (γ) described later can be used.

[0089] From the aspect of the modification effect of the block polymer (X), the weight ratio [(A) / (B)] of the above polyolefin (A) to the above polyolefin (B) in the block polymer (X) is preferably 5 / 95 to 99 / 1, more preferably 10 / 90 to 90 / 10, and particularly preferably 25 / 75 to 75 / 25.

[0090] From the aspects of the modification effect and productivity of the block polymer (X), the Mn (number average molecular weight) of the block polymer (X) is preferably 3,000 to 500,000, more preferably 4,000 to 300,000, and particularly preferably 5,000 to 150,000.

[0091] In addition, the block polymer (X) can have a structure in which the polyolefin structure derived from the above polyolefin (A) and the polyolefin structure derived from the above polyolefin (B) are combined by the following binder (γ).

[0092] Binder (γ): at least one (preferably at least two) selected from the group consisting of unsaturated (poly) carboxylic acids (anhydrides) (C), hydroxyl group-containing compounds (F), epoxy group-containing compounds (P), isocyanate group-containing compounds (L), carboxyl group-containing compounds (K), and aminocarboxylic acids (H).

[0093] In the above binder (γ), a combination of an unsaturated (poly) carboxylic acid (anhydride) (C) and at least one selected from the group consisting of a hydroxyl group-containing compound (F) and an aminocarboxylic acid (H) is preferred.

[0094] The structure of the block polymer (X) is preferably any one of the following (1) to (3). Further preferably (1) and (2), and particularly preferably (2).

[0095] (1): [(A)-(B)]n type block polymer (n = 1 to 5)

[0096] (2): (A)-(B)-(A) type block polymer

[0097] (3): (B)-(A)-(B) type block polymer

[0098] The Mn of the above block polymer (X) and the structure of the block polymer (X) can be appropriately adjusted according to the Mn, weight of the polyolefin (A), Mn, weight of the polyolefin (B), type, weight of the binder (γ) described later, and reaction conditions.

[0099] As a method for producing the block polymer (X), for example, a method of reacting an acid-modified polyolefin (AE), a hydroxyl group-modified polyolefin (AG), an aminocarboxylic acid-modified polyolefin (AJ), an isocyanate group-modified polyolefin (AM), an epoxy group-modified polyolefin (AQ) described later with an acid-modified polyolefin (BE), a hydroxyl group-modified polyolefin (BG), an aminocarboxylic acid-modified polyolefin (BJ), an isocyanate group-modified polyolefin (BM), an epoxy group-modified polyolefin (BQ) under known conditions can be cited.

[0100] The acid-modified polyolefin (AE) is, for example, a reaction product of a polyolefin (A) and an unsaturated (poly) carboxylic acid (anhydride) (C) or a carboxyl group-containing compound (K).

[0101] The hydroxyl group-modified polyolefin (AG) is, for example, a reaction product of an acid-modified polyolefin (AE) and a hydroxyl group-containing compound (F), or a reaction product of a polyolefin (A) and a hydroxyl group-containing compound (F).

[0102] The aminocarboxylic acid-modified polyolefin (AJ) is, for example, a reaction product of an acid-modified polyolefin (AE) and an aminocarboxylic acid (H).

[0103] The isocyanate group-modified polyolefin (AM) is, for example, a reaction product of a hydroxyl group-modified polyolefin (AG) and an isocyanate group-containing compound (L).

[0104] The epoxy group-modified polyolefin (AQ) is, for example, a reaction product of a polyolefin (A) and an epoxy group-containing compound (P).

[0105] Similarly, the acid-modified polyolefin (BE) is, for example, a reaction product of a polyolefin (B) and an unsaturated (poly)carboxylic acid (anhydride) (C) or a carboxyl group-containing compound (K).

[0106] The hydroxyl group-modified polyolefin (BG) is, for example, a reaction product of an acid-modified polyolefin (BE) and a hydroxyl group-containing compound (F), or a reaction product of a polyolefin (B) and a hydroxyl group-containing compound (F).

[0107] The aminocarboxylic acid-modified polyolefin (BJ) is, for example, a reaction product of an acid-modified polyolefin (BE) and an aminocarboxylic acid (H).

[0108] The isocyanate group-modified polyolefin (BM) is, for example, a reaction product of a hydroxyl group-modified polyolefin (BG) and an isocyanate group-containing compound (L).

[0109] The epoxy group-modified polyolefin (BQ) is, for example, a reaction product of a polyolefin (B) and an epoxy group-containing compound (P).

[0110] That is, as combinations of the binder (γ), for example, the following can be cited:

[0111] A combination of (C) and (F);

[0112] A combination of (C), (F) and (H);

[0113] A combination of (C), (F) and (L);

[0114] A combination of (C), (F) and (P);

[0115] A combination of (C) and (H);

[0116] A combination of (C), (H) and (P);

[0117] A combination of (C), (H), (F) and (L);

[0118] A combination of (C), (H), (F) and (P);

[0119] A combination of (C) and (P);

[0120] A combination of (F) and (H);

[0121] A combination of (F) and (L);

[0122] A combination of (F) and (P);

[0123] A combination of (K) and (F);

[0124] A combination of (K), (F) and (H);

[0125] A combination of (K), (F) and (L);

[0126] (K), combination of (F) and (P).

[0127] Among the above, the combination of (C), (F) and (H) is preferred.

[0128] The block polymer (X) of the present invention can be obtained, for example, by reacting the above-mentioned polyolefin (A) with the above-mentioned polyolefin (B) by a known method. Such a method is also a method for producing the block polymer (X) of the present invention. When the above-mentioned polyolefin (A) reacts with the above-mentioned polyolefin (B), the above-mentioned binder (γ) can be used.

[0129] Specific examples of the method for producing the above-mentioned block polymer (X) are as follows.

[0130] (1) React an acid-modified polyolefin (AE) with a hydroxyl-modified polyolefin (BG). An ester bond is formed here.

[0131] (2) React an acid-modified polyolefin (BE) with a hydroxyl-modified polyolefin (AG). An ester bond is formed here.

[0132] (3) React an amino-carboxylic acid-modified polyolefin (AJ) with a hydroxyl-modified polyolefin (BG). An amide bond and / or imide bond and an ester bond are formed here.

[0133] (4) React an amino-carboxylic acid-modified polyolefin (BJ) with a hydroxyl-modified polyolefin (AG). An amide bond and / or imide bond and an ester bond are formed here.

[0134] (5) React a hydroxyl-modified polyolefin (AG) with an isocyanate-group-modified polyolefin (BM). An amide bond and / or imide bond and a urethane bond are formed here.

[0135] (6) React a hydroxyl-modified polyolefin (BG) with an isocyanate-group-modified polyolefin (AM). An amide bond and / or imide bond and a urethane bond are formed here.

[0136] (7) React an acid-modified polyolefin (AE) with an epoxy-group-modified polyolefin (BQ). An ester bond is formed here.

[0137] (8) React an acid-modified polyolefin (BE) with an epoxy-group-modified polyolefin (AQ). An ester bond is formed here.

[0138] (9) React an amino-carboxylic acid-modified polyolefin (AJ) with an epoxy-group-modified polyolefin (BQ). An amide bond and / or imide bond and an ester bond are formed here.

[0139] (10) React the amino-carboxylic acid modified polyolefin (BJ) with the epoxy group modified polyolefin (AQ). An amide bond and / or an imide bond and an ester bond are formed here.

[0140] (11) React the hydroxyl group modified polyolefin (AG) with the epoxy group modified polyolefin (BQ). An ether bond is formed here.

[0141] (12) React the hydroxyl group modified polyolefin (BG) with the epoxy group modified polyolefin (AQ). An ether bond is formed here.

[0142] <Acid modified polyolefin (AE), acid modified polyolefin (BE)>

[0143] The above-mentioned acid modified polyolefin (AE) is, for example, a reaction product of polyolefin (A) and an unsaturated (poly) carboxylic acid (anhydride) (C) or a carboxyl group-containing compound (K).

[0144] In addition, the above-mentioned acid modified polyolefin (BE) is, for example, a reaction product of polyolefin (B) and an unsaturated (poly) carboxylic acid (anhydride) (C) or a carboxyl group-containing compound (K).

[0145] In the above reactions, a radical initiator (f) such as dicumyl peroxide can be used.

[0146] The above-mentioned unsaturated (poly) carboxylic acid (anhydride) (C) is an unsaturated monocarboxylic acid, an unsaturated polycarboxylic acid and / or an unsaturated polycarboxylic acid anhydride.

[0147] The above-mentioned unsaturated (poly) carboxylic acid (anhydride) (C) is preferably a C3-24 monocarboxylic acid having one polymerizable unsaturated group, a C4-24 polycarboxylic acid having one polymerizable unsaturated group and / or a C4-24 polycarboxylic acid anhydride having one polymerizable unsaturated group.

[0148] Among the above-mentioned unsaturated (poly) carboxylic acid (anhydride) (C), as the unsaturated monocarboxylic acid, aliphatic monocarboxylic acids (C3-24, such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, isocrotonic acid) and alicyclic monocarboxylic acids (C6-24, such as cyclohexene carboxylic acid) can be mentioned; as the unsaturated poly (2-3 or more) carboxylic acid or its anhydride, unsaturated dicarboxylic acids or their anhydrides [aliphatic dicarboxylic acids or their anhydrides (C4-24, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and their anhydrides), alicyclic dicarboxylic acids or their anhydrides (C8-24, such as cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, bicycloheptene dicarboxylic acid, methyltetrahydrophthalic acid, and their anhydrides), etc.] can be mentioned. The unsaturated (poly) carboxylic acid (anhydride) (C) can be used alone or in combination of two or more.

[0149] Among the above-mentioned unsaturated (poly)carboxylic acids (anhydrides) (C), from the viewpoints of reactivity with polyolefin (A) and polyolefin (B) and mechanical strength, unsaturated dicarboxylic anhydrides are preferred, and maleic anhydride is more preferred.

[0150] As the above-mentioned carboxyl group-containing compound (K), compounds having at least one or more carboxyl groups in the molecule but not having an unsaturated group and having a functional group capable of reacting with polyolefin (A) or polyolefin (B) in addition to the carboxyl group can be cited.

[0151] As the carboxyl group-containing compound (K), for example, mercaptoacetic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, etc. can be cited.

[0152] Among the above-mentioned carboxyl group-containing compounds (K), mercaptoacetic acid is preferred.

[0153] From the viewpoint of the productivity of the block polymer (X), the acid value (mgKOH / g) of each of the acid-modified polyolefin (AE) and the acid-modified polyolefin (BE) is preferably 1 to 100 mgKOH / g, more preferably 3 to 75 mgKOH / g, and particularly preferably 5 to 50 mgKOH / g. The above acid value is a value measured according to JIS K0070 (1992).

[0154] In addition, the above acid value can be appropriately adjusted according to the number of double bonds of polyolefin (A) or polyolefin (B), the weight of polyolefin (A) or polyolefin (B), or the type and weight of the unsaturated (poly)carboxylic acid (anhydride) (C) or the carboxyl group-containing compound (K).

[0155] <Hydroxyl group-modified polyolefin (AG), hydroxyl group-modified polyolefin (BG)>

[0156] The above hydroxyl group-modified polyolefin (AG) is, for example, a reaction product of the above acid-modified polyolefin (AE) and a hydroxyl group-containing compound (F), or a reaction product of polyolefin (A) and a hydroxyl group-containing compound (F).

[0157] The above hydroxyl group-modified polyolefin (BG) is, for example, a reaction product of the above acid-modified polyolefin (BE) and a hydroxyl group-containing compound (F), or a reaction product of polyolefin (B) and a hydroxyl group-containing compound (F).

[0158] As the above hydroxyl group-containing compound (F), compounds having at least one or more hydroxyl groups in the molecule and having a functional group capable of reacting with the acid-modified polyolefin (AE), the acid-modified polyolefin (BE), polyolefin (A) or polyolefin (B) in addition to the hydroxyl group can be cited.

[0159] As the hydroxy compound (F), examples thereof include 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 2-hydroxypiperazine or 3-hydroxypiperazine, 2-aminocyclohexanol, 3-aminocyclohexanol or 4-aminocyclohexanol, 2-aminophenol, 3-aminophenol or 4-aminophenol, 2-aminop-cresol or 3-aminop-cresol, 2-aminom-cresol or 4-aminom-cresol, 3-aminool-cresol or 4-aminool-cresol, 2-mercaptoethanol, and the like.

[0160] Among the above (F), from the viewpoint of reactivity, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, and 2-mercaptoethanol are preferred, and 2-aminoethanol and 2-mercaptoethanol are more preferred.

[0161] From the viewpoint of the productivity of the block polymer (X), the hydroxyl value of each of the hydroxy-modified polyolefin (AG) and the hydroxy-modified polyolefin (BG) is preferably 1 to 100 mgKOH / g, more preferably 3 to 75 mgKOH / g, and particularly preferably 5 to 50 mgKOH / g. The above hydroxyl value is a value measured according to JIS K0070 (1992).

[0162] The above hydroxyl value can be appropriately adjusted, for example, according to the types and weights of the above acid-modified polyolefin (AE) and the above acid-modified polyolefin (BE), and the types and weights of the above hydroxy compound (F).

[0163] <Epoxy group-modified polyolefin (AQ), epoxy group-modified polyolefin (BQ)>

[0164] The above epoxy group-modified polyolefin (AQ) is, for example, a reaction product of the above polyolefin (A) and a compound containing an epoxy group (P).

[0165] In addition, the above epoxy group-modified polyolefin (BQ) is, for example, a reaction product of the above polyolefin (B) and a compound containing an epoxy group (P).

[0166] As the above compound containing an epoxy group (P), a compound having at least 1 or more epoxy groups in the molecule and having a functional group capable of reacting with the polyolefin (A) or the polyolefin (B) in addition to the epoxy group can be cited.

[0167] As the above compound containing an epoxy group, glycidyl acrylate, glycidyl methacrylate, etc. can be cited.

[0168] From the aspect of the productivity of the block polymer (X), the epoxy equivalent (g / eq) of each of the epoxy group-modified polyolefins (AQ) and (BQ) is preferably 500 to 100,000 g / eq, more preferably 650 to 50,000 g / eq, and particularly preferably 800 to 20,000 g / eq. The above epoxy equivalent is a value measured according to JIS K7236 (2001).

[0169] The above epoxy equivalent can be appropriately adjusted according to the types and weights of the above polyolefins (A) and (B) and the types and weights of the above epoxy group-containing compound (P).

[0170] <Isocyanate group-modified polyolefin (AM), isocyanate group-modified polyolefin (BM)>

[0171] The above isocyanate group-modified polyolefin (AM) is, for example, a reaction product of the above hydroxyl group-modified polyolefin (AG) and an isocyanate group-containing compound (L).

[0172] In addition, the above isocyanate group-modified polyolefin (BM) is, for example, a reaction product of the above hydroxyl group-modified polyolefin (BG) and an isocyanate group-containing compound (L).

[0173] As the above isocyanate group-containing compound (L), it is a compound having at least one or more isocyanate groups in the molecule.

[0174] Examples of the above isocyanate group-containing compound (L) include hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, etc.

[0175] From the aspect of the productivity of the block polymer (X), the isocyanate group content (wt%) of each of the isocyanate group-modified polyolefin (AM) and isocyanate group-modified polyolefin (BM) is preferably 0.04 to 8.5%, more preferably 0.08 to 6.0%, and particularly preferably 0.2 to 5.0%. The above isocyanate group content is a value measured according to JIS K1603-1 (2007).

[0176] The above isocyanate group content can be appropriately adjusted according to the types and weights of the above hydroxyl group-modified polyolefin (AG) and hydroxyl group-modified polyolefin (BG) and the types and weights of the above isocyanate group-containing compound (L).

[0177] <Amino carboxylic acid-modified polyolefin (AJ), amino carboxylic acid-modified polyolefin (BJ)>

[0178] The above amino carboxylic acid-modified polyolefin (AJ) is, for example, a reaction product of the above acid-modified polyolefin (AE) and an amino carboxylic acid (H).

[0179] In addition, the above-mentioned amino-carboxylic acid-modified polyolefin (BJ) is, for example, a reaction product of the above-mentioned acid-modified polyolefin (BE) and amino-carboxylic acid (H).

[0180] Examples of the above-mentioned amino-carboxylic acid (H) include 12-aminododecanoic acid and 6-aminohexanoic acid.

[0181] From the viewpoint of the productivity of the block polymer (X), the acid value (mgKOH / g) of each of the amino-carboxylic acid-modified polyolefin (AJ) and the amino-carboxylic acid-modified polyolefin (BJ) is preferably 1 to 100 mgKOH / g, more preferably 3 to 75 mgKOH / g, and particularly preferably 5 to 50 mgKOH / g.

[0182] The above-mentioned acid value can be appropriately adjusted according to the types and weights of the above-mentioned acid-modified polyolefin (AE) and the above-mentioned acid-modified polyolefin (BE), and the types and weights of the above-mentioned amino-carboxylic acid (H).

[0183] The block polymer (X) of the present invention imparts excellent mechanical strengths (tensile strength, flexural strength, impact strength) to molded articles of the thermoplastic resin composition (Z) described later. In addition, it imparts excellent mechanical strength to the recycled polyolefin resin (YR).

[0184] Therefore, it can be suitably used as a modifier for thermoplastic resins, particularly as a modifier for polyolefin resins.

[0185] <Thermoplastic resin composition (Z)>

[0186] The thermoplastic resin composition (Z) of the present invention contains the above-mentioned block polymer (X) and a thermoplastic resin (Y).

[0187] From the viewpoint of the modification characteristics of the block polymer (X) and the mechanical strength of the molded articles described later, 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 1 / 99 to 50 / 50, more preferably 3 / 97 to 20 / 80.

[0188] The above-mentioned thermoplastic resin (Y) includes components other than the above-mentioned (X), such as polyolefin resins [polypropylene, low-density polyethylene, high-density polyethylene], polystyrene resins, polyester resins, and nylon resins.

[0189] Among the above-mentioned thermoplastic resins (Y), a polyolefin resin is preferred.

[0190] It should be noted that as described above, recycled polyolefin resin (YR) is also suitable as the thermoplastic resin (Y). As the above (YR), it is preferably a polyolefin resin obtained by performing processes such as crushing, pulverizing, and granulating after prior molding processing.

[0191] From the aspects of the mechanical strength of the molded article and the compatibility with the above block polymer (X), the Mn of the thermoplastic resin (Y) is preferably 10,000 to 1,000,000, more preferably 20,000 to 400,000, and still more preferably 80,000 to 300,000.

[0192] The thermoplastic resin composition (Z) of the present invention may further contain one or more additives (N) selected from the group consisting of a filler (N1), a colorant (N2), a matting agent (N3), an antistatic agent (N4), a dispersant (N5), a flame retardant (N6), a foaming agent (N7), an antioxidant (N8), an ultraviolet absorber (N9), and a plasticizer (N10) as needed within a range that does not impair the effects of the present invention.

[0193] Examples of the above filler (N1) include organic fillers (such as wood powder and cellulose) and inorganic fillers (such as calcium carbonate, talc, glass fiber, and carbon fiber).

[0194] Among these fillers (N1), from the aspect of mechanical strength, inorganic fillers are preferred, and calcium carbonate is more preferred. Based on the total weight of the thermoplastic resin composition (Z), the amount of the filler (N1) is preferably 3 to 70% by weight, more preferably 3 to 50% by weight, and still more preferably 5 to 40% by weight.

[0195] The total amount of the additives (N2) to (N10) in the thermoplastic resin composition (Z) of the present invention is preferably 30% by weight or less based on the total weight of the block polymer (X), and more preferably 0.1 to 20% by weight from the aspects of the functional performance of the additive (N) and industriality.

[0196] Regarding the preferred amounts of the respective additives (N) other than the filler (N1), based on the total weight of the thermoplastic resin composition (Z), the colorant (N2) is, for example, 10% by weight or less, more preferably 0.1 to 5% by weight; the matting agent (N3) is, for example, 20% by weight or less, more preferably 0.1 to 10% by weight; the antistatic agent (N4) is, for example, 10% by weight or less, more preferably 0.1 to 5% by weight; the dispersant (N5) is, for example, 20% by weight or less, more preferably 0 to 15% by weight, further preferably 0 to 10% by weight; the flame retardant (N6) is, for example, 15% by weight or less, more preferably 3 to 10% by weight; the foaming agent (N7) is, for example, 1 to 20% by weight or less, more preferably 5 to 15% by weight; the antioxidant (N8) is, for example, 3% by weight or less, more preferably 0.01 to 1% by weight; the ultraviolet absorber (N9) is, for example, 3% by weight or less, more preferably 0.01 to 1% by weight; the plasticizer (N10) is, for example, 20% by weight or less, more preferably 5 to 15% by weight.

[0197] It should be noted that in the case where the additives are the same and repeated among the additives (N1) to (N10), the amounts of the respective additives that can exhibit the corresponding additive effects are not used regardless of the effects of other additives. It is also necessary to consider that the effects of other additives are also obtained simultaneously, and the amounts are adjusted according to the purpose of use.

[0198] As a method for producing the thermoplastic resin composition (Z) of the present invention, the following methods can be mentioned:

[0199] (1) A method (one-step method) of mixing the total amounts of the thermoplastic resin (Y) and the block polymer (X) and, if necessary, the additive (N) at one time to form a resin composition;

[0200] (2) A method (masterbatch method) of mixing a part of the thermoplastic resin (Y), the total amount of the block polymer (X), and a part or the total amount of the additive (N) if necessary to first prepare a masterbatch resin composition containing a high concentration of the block polymer (X), and then adding the remaining thermoplastic resin (Y) and the remaining amount of the additive (N) if necessary and mixing them to form a resin composition.

[0201] From the aspect of the mixing efficiency of the block polymer (X), the method (2) is preferred.

[0202] <Molded article>

[0203] The molded article of the present invention is a molded product of the above-mentioned thermoplastic resin composition (Z). That is, the molded article of the present invention is formed by molding the thermoplastic resin composition (Z) of the present invention.

[0204] As the molding method, injection molding, compression molding, calendering molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) can be cited, and molding can be performed by any method that also employs means such as single-layer molding, multi-layer molding, or foaming molding according to the purpose. As the form of the molded product, plate-like, sheet-like, film, fiber (including non-woven fabric, etc.) can be cited.

[0205] Examples

[0206] The present invention will be further described below by way of examples, but the present invention is not limited to these examples. Parts in the examples represent parts by weight. In the examples, the number average molecular weight (Mn), the number 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 methods.

[0207] <Production Example 1>

[0208] 100 parts of high molecular weight polyolefin (A0-1) [trade name "SunAllomer PZA20A", manufactured by SunAllomer Co., Ltd.] were put into a reaction vessel, heated and melted with a heating jacket while introducing nitrogen into the liquid phase, and thermally degraded under stirring at 350 °C for 15 minutes to obtain polyolefin (A-1).

[0209] It should be noted that the Mn of polyolefin (A-1) is 30,000, the number of double bonds at the molecular end and / or in the molecular chain per 1,000 carbons is 0.5, and the isotacticity is 95%.

[0210] <Production Examples 2 to 5>

[0211] Except for changing the high molecular weight polyolefin (A0) and the thermal degradation conditions (temperature, time) according to Table 1, thermal degradation was carried out in the same manner as in Production Example 1 to obtain each of the polyolefins (A-2) to (A-5). The results are shown in Table 1.

[0212] <Production Example 6>

[0213] 100 parts of high molecular weight polyolefin (B0-1) [trade name "Vistamaxx 6102", manufactured by ExxonMobil Corporation] were put into a reaction vessel, heated and melted with a heating jacket while introducing nitrogen into the liquid phase, and thermally degraded under stirring at 350 °C for 10 minutes to obtain polyolefin (B-1).

[0214] It should be noted that the Mn of polyolefin (B-1) is 30,000, the number of double bonds at the molecular end and / or in the molecular chain per 1,000 carbons is 0.5, and the isotacticity is 28%.

[0215] <Production Examples 7 to 12>

[0216] Except for changing the high molecular weight polyolefin (B0) and the thermal degradation conditions (temperature, time) according to Table 1, thermal degradation was carried out in the same manner as in Production Example 6 to obtain each polyolefin (B-2) to (B-7). The results are shown in Table 1.

[0217]

[0218] <Production Example 13>

[0219] 100 parts of polyolefin (A-1) and 1 part of maleic anhydride (C-1) were put into a reaction vessel, and the temperature was raised to 200 °C under nitrogen ventilation and stirred continuously for 10 hours. After that, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (AE-1).

[0220] It should be noted that the acid value of the acid-modified polyolefin (AE-1) is 2.0 mgKOH / g and the Mn is 30,100.

[0221] <Production Examples 14 to 21>

[0222] Except for changing the polyolefin, unsaturated (poly) carboxylic acid (anhydride) (C), and free radical initiator (f) according to Table 2, the reaction was carried out in the same manner as in Production Example 13 to obtain each acid-modified polyolefin (AE-2) to (AE-4), (BE-1) to (BE-5). The results are shown in Table 2.

[0223] <Production Example 22>

[0224] 100 parts of polyolefin (A-5) and 1 part of mercaptoacetic acid (K-1) were put into a reaction vessel, 200 parts of xylene was added, the temperature was raised to 160 °C under nitrogen ventilation, 1 part of dicumyl peroxide (f-1) was added, and the mixture was stirred continuously for 10 hours. After that, xylene and unreacted mercaptoacetic acid were distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin (AE-15).

[0225] It should be noted that the acid value of the acid-modified polyolefin (AE-15) is 0.3 mgKOH / g and the Mn is 180,100.

[0226] <Production Examples 23 to 24>

[0227] Except for changing the polyolefin and free radical initiator (f) according to Table 2, the reaction was carried out in the same manner as in Production Example 22 to obtain each acid-modified polyolefin (BE-16) to (BE-17). The results are shown in Table 2.

[0228]

[0229] <Production Example 25>

[0230] 100 parts of polyolefin (A-3) and 7 parts of glycidyl methacrylate (P-1) were charged into a reaction vessel, and the temperature was raised to 200 °C under nitrogen ventilation, followed by continuous stirring for 10 hours. Thereafter, unreacted glycidyl methacrylate (P-1) was distilled off under reduced pressure (1.5 kPa) to obtain epoxy group-modified polyolefin (AQ-3).

[0231] It should be noted that the epoxy equivalent of the epoxy group-modified polyolefin (AQ-3) is 2200 g / eq and the Mn is 3,200.

[0232] <Production Example 26>

[0233] The reaction was carried out in the same manner as in Production Example 25 except that the polyolefin and the radical initiator (f) were changed according to Table 3 to obtain epoxy group-modified polyolefin (BQ-3). The results are shown in Table 3.

[0234] [Table 3]

[0235]

[0236] <Production Example 27>

[0237] 100 parts of acid-modified polyolefin (AE-1) and 1 part of 2-aminoethanol (F-1) were charged into a reaction vessel, and the temperature was raised to 180 °C under nitrogen ventilation, followed by continuous stirring for 10 hours. Thereafter, stirring was continued for 10 hours under reduced pressure (1.5 kPa) to obtain hydroxy group-modified polyolefin (AG-1).

[0238] It should be noted that the hydroxyl value of the hydroxy group-modified polyolefin (AG-1) is 2.0 mgKOH / g and the Mn is 30,000.

[0239] <Production Examples 28 to 32>

[0240] The reaction was carried out in the same manner as in Production Example 27 except that the acid-modified polyolefin (AE) and the acid-modified polyolefin (BE) were changed according to Table 4 to obtain each hydroxy group-modified polyolefin (AG-2), (BG-1) to (BG-2), (BG-16) to (BG-17). The results are shown in Table 4.

[0241] <Production Example 33>

[0242] 100 parts of acid-modified polyolefin (AE-3) and 10 parts of 12-aminododecanoic acid (H-1) were charged into a reaction vessel, and the temperature was raised to 180 °C under nitrogen ventilation, followed by continuous stirring for 10 hours. Thereafter, stirring was continued for 10 hours under reduced pressure (1.5 kPa) to obtain amino carboxylic acid-modified polyolefin (AJ-3).

[0243] Note that the acid value of the amino carboxylic acid-modified polyolefin (AJ-3) is 26.2 mgKOH / g and the Mn is 3,500.

[0244] <Production Examples 34 to 37>

[0245] Except for changing the acid-modified polyolefin (AE), acid-modified polyolefin (BE), and amino carboxylic acid (H) according to Table 4, the reaction was carried out in the same manner as in Production Example 33 to obtain each amino carboxylic acid-modified polyolefin (AJ-4), (BJ-3) to (BJ-5).

[0246] The results are shown in Table 4.

[0247]

[0248] <Production Example 38>

[0249] 100 parts of polyolefin (A-1), 2 parts of 2-mercaptoethanol (F-2), and 200 parts of xylene were put into a reaction vessel, heated to 160 °C under nitrogen ventilation, and 1 part of dicumyl peroxide (f-1) was added, followed by continuous stirring for 10 hours. Then, xylene and unreacted 2-mercaptoethanol (F-2) were distilled off under reduced pressure (1.5 kPa) to obtain hydroxy-modified polyolefin (AG-11).

[0250] Note that the hydroxyl value of the hydroxy-modified polyolefin (AG-11) is 2.0 mgKOH / g and the Mn is 30,100.

[0251] <Production Example 39>

[0252] Except for changing the polyolefin and free radical initiator (f) according to Table 5, the reaction was carried out in the same manner as in Production Example 38 to obtain hydroxy-modified polyolefin (BG-11). The results are shown in Table 5.

[0253] [Table 5]

[0254]

[0255] <Production Example 40>

[0256] 100 parts of hydroxy-modified polyolefin (AG-2), 8 parts of hexamethylene diisocyanate (L-1), and 200 parts of xylene were put into a reaction vessel, heated to 150 °C under nitrogen ventilation, and continuously stirred for 10 hours. Then, xylene and unreacted hexamethylene diisocyanate (L-1) were distilled off under reduced pressure (1.5 kPa) to obtain isocyanate group-modified polyolefin (AM-2).

[0257] Note that the isocyanate group content of the isocyanate group-modified polyolefin (AM-2) is 0.78% and the Mn is 10,600.

[0258] <Production Example 41>

[0259] Except for changing the hydroxy-modified polyolefin and the isocyanate group-containing compound (L) according to Table 6, the reaction was carried out in the same manner as in Production Example 38 to obtain an isocyanate group-modified polyolefin (BM-3). The results are shown in Table 6.

[0260] [Table 6]

[0261]

[0262] <Example 1>

[0263] 8 parts of an amino carboxylic acid-modified polyolefin (AJ-3), 100 parts of a hydroxy-modified polyolefin (BG-1), and 0.1 part of dibutyltin as an esterification catalyst were charged into a reaction vessel. After purging with nitrogen, the temperature was raised to 200 °C under nitrogen flow to dissolve them. Stirring was continued at 200 °C for 3 hours. Then, after reacting under reduced pressure (1.5 kPa) for 5 hours, the product was taken out from the reaction vessel to obtain a block polymer (X-1).

[0264] It should be noted that the Mn of the block polymer (X-1) is 62,000, the weight ratio [(A) / (B)] is 7 / 93, and the acid value is 0.01 mgKOH / g.

[0265] <Examples 2 to 5>

[0266] Except for changing the amino carboxylic acid-modified polyolefin and the hydroxy-modified polyolefin according to Table 7, the reaction was carried out in the same manner as in Example 1 to obtain the block polymers (X-2) to (X-5). The results are shown in Table 7.

[0267] <Example 6>

[0268] 20 parts of an isocyanate group-modified polyolefin (AM-2), 100 parts of a hydroxy-modified polyolefin (BG-11), 200 parts of xylene, and 0.1 part of bismuth tris(2-ethylhexanoate) as a urethanization catalyst were charged into a reaction vessel. After purging with nitrogen, the temperature was raised to 150 °C under nitrogen flow to dissolve them. Stirring was continued at 150 °C for 3 hours. Then, after distilling off xylene under reduced pressure (1.5 kPa), the product was taken out from the reaction vessel to obtain a block polymer (X-6).

[0269] It should be noted that the Mn of the block polymer (X-6) is 63,000, the weight ratio [(A) / (B)] is 16 / 84, and the hydroxyl value is 0.02 mgKOH / g.

[0270] <Example 7>

[0271] Except for changing the isocyanate group-modified polyolefin and hydroxyl group-modified polyolefin according to Table 7, the reaction was carried out in the same manner as in Example 6 to obtain a block polymer (X-7). The results are shown in Table 7.

[0272] <Example 8>

[0273] 100 parts of amino carboxylic acid-modified polyolefin (BJ-3), 80 parts of epoxy group-modified polyolefin (AQ-3), and 0.1 part of the epoxidation catalyst diazabicycloundecene were put into a reaction vessel. After nitrogen replacement, the temperature was raised to 150 °C under nitrogen ventilation for dissolution. After continuously stirring at 150 °C for 3 hours, it was taken out from the reaction vessel to obtain a block polymer (X-8).

[0274] It should be noted that the Mn of the block polymer (X-8) is 11,000, the weight ratio [(A) / (B)] is 46 / 54, and the acid value is 0.01 mgKOH / g.

[0275] <Example 9>

[0276] Except for changing the amino carboxylic acid-modified polyolefin and epoxy group-modified polyolefin according to Table 7, the reaction was carried out in the same manner as in Example 8 to obtain a block polymer (X-9). The results are shown in Table 7.

[0277] <Example 10>

[0278] 100 parts of acid-modified polyolefin (AE-15) and 130 parts of hydroxyl group-modified polyolefin (BG-16) were put into a reaction vessel. The temperature was raised to 180 °C under nitrogen ventilation and continuously stirred for 10 hours. Then, it was continuously stirred under reduced pressure (1.5 kPa, the same below) for 10 hours to obtain a block polymer (X-10).

[0279] It should be noted that the Mn of the block polymer (X-10) is 355,000 and the weight ratio [(A) / (B)] is 43 / 57.

[0280] <Example 11>

[0281] Except for changing the hydroxyl group-modified polyolefin according to Table 7, the reaction was carried out in the same manner as in Example 10 to obtain a block polymer (X-11). The results are shown in Table 7.

[0282]

[0283] <Examples 21 to 31, Comparative Examples 21 to 24>

[0284] The respective block polymers (X) and thermoplastic resins (Y) were melt-kneaded using a twin-screw extruder [trade name "KZW45TW", manufactured by Technovel Corporation] under the conditions of 230°C and 100 rpm according to the blending composition (parts) shown in Table 8 to obtain the respective thermoplastic resin compositions (Z-1) to (Z-11).

[0285] In Comparative Examples 21 to 24, for comparison, polyolefin (A-1) was used in place of the block polymer (X) to obtain the thermoplastic resin compositions (CZ-1) to (CZ-4).

[0286] The respective thermoplastic resin compositions (Z-1) to (Z-11), (CZ-1) to (CZ-4) were injection-molded using an injection molding machine [trade name "PS40E5ASE", manufactured by Nissei Plastic Industrial 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.

[0287] <Evaluation Method>

[0288] (1) Tensile strength

[0289] The measurement was carried out in accordance with JIS K7161-2 (2014) to evaluate the tensile strength.

[0290] <Evaluation Criteria> (Examples 21 to 28, Comparative Example 21)

[0291] ◎: 30 MPa or more

[0292] ○: 25 MPa or more and less than 30 MPa

[0293] △: 20 MPa or more and less than 25 MPa

[0294] ×: Less than 20 MPa

[0295] <Evaluation Criteria> (Examples 29 to 30, Comparative Examples 22 to 23)

[0296] ◎: 25 MPa or more

[0297] ○: 20 MPa or more and less than 25 MPa

[0298] △: 15 MPa or more and less than 20 MPa

[0299] ×: Less than 15 MPa

[0300] <Evaluation Criteria> (Example 31, Comparative Example 24)

[0301] ◎: 20 MPa or more

[0302] ○: 15 MPa or more and less than 20 MPa

[0303] △: 10 MPa or more and less than 15 MPa

[0304] ×: less than 10 MPa

[0305] (2) Impact resistance

[0306] The Izod impact strength was measured in accordance with JIS K7110 (1999). <Evaluation criteria> (Examples 21 to 28, Comparative Example 21)

[0307] ◎: 3.0 kJ / m 2 or more

[0308] ○: 1.5 kJ / m 2 or more and less than 3.0 kJ / m 2

[0309] △: 1.0 kJ / m 2 or more and less than 1.5 kJ / m 2

[0310] ×: less than 1.0 kJ / m 2

[0311] <Evaluation criteria> (Examples 29 to 30, Comparative Examples 22 to 23) ◎: 10.0 kJ / m 2 or more

[0312] ○: 5.0 kJ / m 2 or more and less than 10.0 kJ / m 2

[0313] △: 1.0 kJ / m 2 or more and less than 5.0 kJ / m 2

[0314] ×: less than 1.0 kJ / m 2

[0315] <Evaluation criteria> (Example 31, Comparative Example 24)

[0316] ◎: 2.0 kJ / m 2 or more

[0317] ○: 1.5 kJ / m 2 or more and less than 2.0 kJ / m 2

[0318] △: 1.0 kJ / m 2 or more and less than 1.5 kJ / m 2

[0319] ×: less than 1.0 kJ / m2

[0320]

[0321] <Examples 41 to 51, Comparative Example 41>

[0322] Each block polymer (X) and thermoplastic resin (YR-1) [recycled polyolefin resin, trade name "PP Shreds", manufactured by Miki Resin Industry Co., Ltd.] were melt-kneaded using a twin-screw extruder [trade name "KZW45TW", manufactured by Technovel Corporation] under the conditions of 230 °C and 100 rpm according to the blending composition (parts) in Table 9 to obtain each thermoplastic resin composition (Z-21) to (Z-31).

[0323] In Comparative Example 41, for comparison, a polyolefin (A-1) was used instead of the block polymer (X) to obtain a thermoplastic resin composition (CZ-21).

[0324] Furthermore, after pelletization, injection molding was carried out using an injection molding machine [trade name "PS40E5ASE", manufactured by Nissei Plastic Industrial Co., Ltd.] at a nozzle temperature of 230 °C and a mold temperature of 50 °C to produce test pieces, which were evaluated according to the evaluation method described below. The results are shown in Table 9.

[0325] (1) Tensile strength

[0326] The evaluation of tensile strength was carried out in accordance with JIS K7161-2 (2014).

[0327] <Evaluation criteria>

[0328] ◎: 25 MPa or more

[0329] ○: 20 MPa or more and less than 25 MPa

[0330] △: 15 MPa or more and less than 20 MPa

[0331] ×: Less than 15 MPa

[0332] (2) Impact resistance

[0333] The Izod impact strength was measured in accordance with JIS K7110 (1999).

[0334] <Evaluation criteria>

[0335] ◎: 2.5 kJ / m 2 or more

[0336] ○: 1.2 kJ / m 2 or more and less than 2.5 kJ / m 2

[0337] △: 0.8 kJ / m 2 equal to or greater than the above and less than 1.2 kJ / m 2

[0338] ×: less than 0.8 kJ / m 2

[0339]

[0340] <Examples 61 to 71, Comparative Example 61>

[0341] Using a twin-screw extruder [trade name "KZW45TW", manufactured by Technovel Corporation], each block polymer (X), thermoplastic resin (Y), and filler (N1) were melt-kneaded under the conditions of 230°C and 100 rpm according to the blending composition (parts) in Table 10 to obtain each thermoplastic resin composition (Z-41) to (Z-51).

[0342] In Comparative Example 61, for comparison, a polyolefin (A-1) was used instead of the block polymer (X) to obtain a thermoplastic resin composition (CZ-41).

[0343] Furthermore, after pelletizing, injection molding was performed using an injection molding machine [trade name "PS40E5ASE", manufactured by Nissei Plastic Industrial Co., Ltd.] at a nozzle temperature of 230°C and a mold temperature of 50°C to produce test pieces, which were evaluated according to the evaluation method described below. The results are shown in Table 10.

[0344] (1) Flexural strength

[0345] Evaluated for flexural strength (unit: MPa) according to JIS K7171 (2016).

[0346] (2) Impact resistance

[0347] The Charpy impact value (unit: J / m) was measured according to ASTM D6110.

[0348]

[0349] From the results in Tables 8 to 10, it can be seen that compared with each comparative example, the block polymer (X) in each example can impart excellent mechanical strength to the molded products of the thermoplastic resin composition (Z). In addition, it can be seen that excellent mechanical strength can be imparted to the recycled polyolefin resin (YR).

[0350] Industrial applicability

[0351] The block polymer (X) of the present invention is useful as a modifier for a thermoplastic resin (Y) and can improve the mechanical strength (tensile strength, flexural strength, impact strength, etc.) of the thermoplastic resin (Y). Therefore, it is very useful in the applications of molded articles of various thermoplastic resins.

Claims

1. A block polymer (X) having a polyolefin structure derived from the following polyolefin (A) and a polyolefin structure derived from the following polyolefin (B) as structural units, and having a number average molecular weight of 11,000 to 355,000, Polyolefin (A): comprising, as a constituent monomer, an α-olefin having 3 to 8 carbon atoms, the isotacticity of the α-olefin portion being 70% to 100%, the number average molecular weight being 1,000 to 200,000, and the number of carbon-carbon double bonds per 1,000 carbon atoms being 0.01 to 8.0; Polyolefin (B): contains an α-olefin having 3 to 8 carbon atoms as a constituent monomer, the isotacticity of the α-olefin portion is 1% to 65%, and the number average molecular weight is 1,000 to 200,000.

2. The block polymer (X) according to claim 1, in, The weight ratio (A) / (B) of the polyolefin (A) to the polyolefin (B) is 5 / 95 to 99 / 1.

3. The block polymer (X) according to claim 1 or 2, in, The block polymer (X) is a structure in which a polyolefin structure derived from the polyolefin (A) and a polyolefin structure derived from the polyolefin (B) are bonded via the following binder (γ), Binder (γ): at least one selected from the group consisting of unsaturated monocarboxylic acids, unsaturated polycarboxylic acids and / or unsaturated polycarboxylic acid anhydrides (C), hydroxyl-containing compounds (F), epoxy-containing compounds (P), isocyanate-containing compounds (L), carboxyl-containing compounds (K) and aminocarboxylic acids (H), wherein the carboxyl-containing compound (K) does not include carboxyl-containing compounds and aminocarboxylic acids having unsaturated groups. 4 . A thermoplastic resin composition (Z) comprising the block polymer (X) according to claim 1 and a thermoplastic resin (Y).

5. The thermoplastic resin composition (Z) according to claim 4, in, The weight ratio (X) / (Y) of the block polymer (X) to the thermoplastic resin (Y) is 1 / 99 to 50 / 50.

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

7. A molded article obtained by molding the thermoplastic resin composition (Z) according to any one of claims 4 to 6.

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