JP2022131155A - block polymer - Google Patents

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

The present invention relates to block polymers.

Polyolefin resins are excellent in moldability, rigidity, electrical insulation, etc., and are inexpensive, so that they are widely used as molded articles of various shapes such as films, fibers, and the like. In addition, various modifiers have been developed for polyolefin resins, and modifiers containing low molecular weight polyolefin have been proposed for the purpose of improving pigment dispersibility and mechanical strength (for example, patent Reference 1).

JP 2015-117362 A

However, even with the above technique, the mechanical strength was not sufficiently satisfactory. An object of the present invention is to provide a block polymer that imparts excellent mechanical strength to thermoplastic resins, particularly polyolefin resins.

The present inventors arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides a block polymer having at least two polyolefin structures derived from the following polyolefin (B) as structural units, and having a structure in which the polyolefin structures derived from the polyolefin (B) are bonded via the following binder (γ). (X).
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% or more and less than 65%, and the number average molecular weight is 1,000 ~200,000;
Binder (γ): 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) At least one selected from the group consisting of;

The block polymer (X) of the present invention has the following effects.
(1) It imparts excellent mechanical strength (tensile strength, impact strength, etc.) to molded articles of the thermoplastic resin composition (Z).
(2) It imparts excellent mechanical strength to recycled polyolefin resin (YR).

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

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

The above polyolefin (B) may contain monomers other than the α-olefin as constituent monomers. In that case, the weight of the other monomers is preferably 70% by weight or less, more preferably 30% by weight or less, and still more preferably 10% by weight, based on the weight of all monomers constituting the polyolefin (B). It is below.

Other monomers constituting the polyolefin (B) include, for example, ethylene, 2-butene, isobutene, α-olefins (1-decene , 1-dodecene, etc.), and C4-30 unsaturated monomers other than α-olefins (eg, vinyl acetate).
Among the above other monomers, ethylene is preferred. Among (B), a propylene/ethylene copolymer is preferred.

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%, particularly preferably 1 to 35, from the viewpoint of mechanical strength. %.
The isotacticity of the α-olefin portion of the polyolefin (B) is determined by acid-modified polyolefin (BE), hydroxyl group-modified polyolefin (BG), aminocarboxylic acid-modified It tends to be directly reflected in the isotacticity of the α-olefin portion of polyolefin (BJ), epoxy group-modified polyolefin (BQ), and isocyanate group-modified polyolefin (BM).

The isotacticity can be calculated using ¹³ C-NMR (nuclear magnetic resonance spectroscopy). In general, if the α-olefin is propylene, the side chain methyl group, and if 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 A group has a configuration (meso or racemo) to the extent of both neighbors (triad, triad), both sides of the triad (quintuplet, pentad), and both sides of the quintuplet (septad, heptad). It is known that peaks are observed at different chemical shifts. Therefore, stereoregularity is generally evaluated for pentads, and isotacticity in the present invention is also calculated based on pentad evaluation.

That is, when the α-olefin is propylene, the carbon peak derived from the side-chain methyl group in propylene obtained by ¹³ C-NMR shows that the α-olefin is 1-butene, 1-pentene, 1-hexene, 1-heptene, In the case of 1-octene, for the carbon peak derived from the side chain methylene group next to the main chain methine group in the α-olefin obtained by ¹³ C-NMR, the pentad peak intensity of the α-olefin portion of polyolefin (B) is calculated as ( H), a methyl group when the α-olefin in the isotactic polyolefin in which the pentad is formed only by the meso structure is propylene, the α-olefin is 1-butene, 1-pentene, 1-hexene, 1-heptene, 1 -In the case of octene, when the peak intensity derived from the side chain methylene group next to the main chain methine group in the α-olefin obtained by ¹³ C-NMR is (Ha), the isotacticity is calculated by the following formula. be.

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

The conditions for measuring isotacticity in the present invention are as follows.
・Equipment: ECZ400R manufactured by JEOL Ltd.
・Measurement mode: proton decoupling method ・Pulse width: 8 μsec
・Pulse repetition time: 4.6 sec
・Relaxation time: 3.0 sec
・Number of accumulations: 10,000 times ・Solvent: ortho-dichlorobenzene ・Reference material: tetramethylsilane ・Sample concentration: 10 mg/mL
・Measurement temperature: 120°C

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

In the present invention, the number average molecular weight (Mn) and weight average molecular weight (Mw) can be measured by GPC (gel permeation chromatography).
The conditions for measuring Mn by GPC in the present invention are as follows.
・Equipment: high temperature gel permeation chromatography
["Alliance GPCV2000", manufactured by Waters Co., Ltd.]
・Detection device: refractive index detector ・Solvent: ortho-dichlorobenzene ・Reference material: polystyrene ・Sample concentration: 3 mg/ml
・Column stationary phase: PLgel 10 μm, MIXED-B 2 in series
[Manufactured by Polymer Laboratories Co., Ltd.]
・Column temperature: 135°C

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

Examples of the method for producing the polyolefin (B) in the present invention include the following.
(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.

Of the above (1) to (2), (1) is preferable from the viewpoint of productivity.

The thermal degradation method includes (1) heating the high molecular weight polyolefin (B0) in the absence of an organic peroxide, for example, at 300 to 450° C. for 0.5 to 10 hours, and (2) organic peroxide in the presence of a compound [eg, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane], for example, a method of heating at 180 to 300° C. for 0.5 to 10 hours.
Of these, the method (1) is preferable from the industrial point of view and the productivity of the block polymer (X) because it is easy to obtain a polymer having a larger number of double bonds at the molecular terminal and/or in the molecular chain.

In the above polyolefin (B), the higher the thermal degradation temperature or the longer the thermal degradation time in the thermal degradation step, the greater the number of double bonds per 1,000 carbon atoms.
Furthermore, the Mn of the polyolefin (B) tends to decrease as the Mn of the high-molecular-weight polyolefin (B0) is smaller, the thermal degradation temperature is higher, or the thermal degradation time is longer.
Also, there is a tendency that the higher the isotacticity of the high-molecular-weight polyolefin (B0), the higher the isotacticity of the polyolefin (B).
In addition, the polyolefin (B) may be used singly or in combination of two or more.

<Block polymer (X)>
The block polymer (X) of the present invention has at least two polyolefin structures derived from the following polyolefin (B) as structural units, and the polyolefin structures derived from the polyolefin (B) are bonded via the following binder (γ). Structure.
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% or more and less than 65%, and the number average molecular weight is 1,000 ~200,000;
Binder (γ): 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) at least one (preferably at least two) selected from the group consisting of;

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 resin), and the mechanical strength of the thermoplastic resin (Y) ( tensile strength, impact strength, etc.) can be improved.
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).

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

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): 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) at least one (preferably at least two) selected from the group consisting of;
Among the above binders (γ), preferred are unsaturated (poly)carboxylic acid (anhydride) (C) [sometimes referred to as unsaturated carboxylic acid (anhydride) (C)] and hydroxyl group-containing It is a combination with at least one selected from the group consisting of compound (F) and aminocarboxylic acid (H).

The structure of the block polymer (X) is preferably any one of the following (1) to (3). (1) and (2) are more preferred, and (1) is particularly preferred.
(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 (1) to (3) above, n is preferably 1 to 2, more preferably n=1.

The Mn of the block polymer (X) and the structure of the block polymer (X) can be appropriately adjusted depending on the Mn and weight of (B), the type and weight of the binder (γ) described later, and the reaction conditions.

Examples of the method for producing the block polymer (X) include the following.
Acid-modified polyolefin (BE), hydroxyl group-modified polyolefin (BG), aminocarboxylic acid-modified polyolefin (BJ), isocyanate group-modified polyolefin (BM), and epoxy-modified polyolefin (BQ) described below are reacted under known conditions.

For example, acid-modified polyolefin (BE) is a reaction product of polyolefin (B) and unsaturated (poly)carboxylic acid (anhydride) (C), and hydroxyl group-modified polyolefin (BG) is 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), wherein the aminocarboxylic acid-modified polyolefin (BJ) is an acid-modified polyolefin (BE) and an aminocarboxylic acid ( H), the isocyanate group-modified polyolefin (BM) is a reaction product of the hydroxyl group-modified polyolefin (BG) and the isocyanate group-containing compound (L), and the epoxy group-modified polyolefin (BQ) is It is a reaction product of a polyolefin (B) and an epoxy group-containing compound (P).

That is, as a combination of binders (γ), for example,
a combination of (C) and (F);
a combination of (C) and (F) and (H);
a combination of (C) and (F) and (L);
a combination of (C) and (F) and (P);
a combination of (C) and (H);
a combination of (C) and (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);
Combination of (F) and (P).
Among the above, the combination of (C), (F) and (H) is preferable.

Examples of the method for producing the block polymer (X) are as follows.
(1) Acid-modified polyolefin (BE) and hydroxyl-modified polyolefin (BG) are reacted. An ester bond is formed here.
(2) Aminocarboxylic acid-modified polyolefin (BE) and hydroxyl group-modified polyolefin (BG) are reacted. Here, an amide bond and/or an imide bond and an ester bond are formed.

(3) Hydroxyl group-modified polyolefin (BG) and isocyanate group-modified polyolefin (BM) are reacted. Here, an amide bond and/or an imide bond and a urethane bond are formed.
(4) Acid-modified polyolefin (BE) and epoxy group-modified polyolefin (BQ) are reacted. An ester bond is formed here.

(5) Aminocarboxylic acid-modified polyolefin (BE) and epoxy group-modified polyolefin (BQ) are reacted. Here, an amide bond and/or an imide bond and an ester bond are formed.
(6) Hydroxyl-modified polyolefin (BE) and epoxy-modified polyolefin (BQ) are reacted. An ether bond is formed here.

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

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

Among the unsaturated (poly)carboxylic acids (anhydrides) (C), unsaturated monocarboxylic acids include aliphatic monocarboxylic acids (C3-24, such as acrylic acid, methacrylic acid, α-ethylacrylic acid, croton acid, isocrotonic acid), alicyclic-containing monocarboxylic acids (C6-24, such as cyclohexenecarboxylic acid); Acid anhydrides [aliphatic dicarboxylic acids or their acid anhydrides (C4-24, such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and their acid anhydrides), alicyclic-containing dicarboxylic acids or their acids anhydrides (C8-24, such as cyclohexenedicarboxylic acid, cycloheptenedicarboxylic acid, bicycloheptenedicarboxylic acid, methyltetrahydrophthalic acid, and acid anhydrides thereof) and the like]. The unsaturated carboxylic acid (anhydride) (C) may be used alone or in combination of two or more.

Of the (poly)unsaturated carboxylic acids (anhydrides) (C), from the viewpoint of reactivity with the polyolefin (B) and mechanical strength, unsaturated dicarboxylic acid anhydrides are preferred, and maleic anhydride is more preferred. is an acid.

The acid value (mgKOH/g) of the acid-modified polyolefin (BE) is preferably 1 to 100 mgKOH/g (only numerical values are shown below), more preferably 3 to 75, particularly Preferably it is 5-50. The acid value here is a value measured according to JIS K0070.
Moreover, the acid value can be appropriately adjusted by the amount of double bonds possessed by the polyolefin (B), the weight of the polyolefin (B), and the type and weight of the unsaturated carboxylic acid (anhydride) (C).

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

The hydroxyl group-containing compound (F) has at least one hydroxyl group in the molecule and has a functional group capable of reacting with the acid-modified polyolefin (BE) or the polyolefin (B) in addition to the hydroxyl group.
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, 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. .

From the viewpoint of the productivity of (X), the hydroxyl value of the hydroxyl-modified polyolefin (BG) is preferably 1 to 100 mgKOH/g (only numerical values are shown below), more preferably 3 to 75, and particularly preferably 5 to 50. is. The hydroxyl value here is a value measured according to 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).

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

The epoxy group-containing compound (P) has at least one or more epoxy groups in the molecule and has a functional group capable of reacting with the polyolefin (B) in addition to the epoxy group.

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

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

<Isocyanate group-modified polyolefin (BM)>
The isocyanate group-modified polyolefin (BM) is, for example, a reaction product of the hydroxyl group-modified polyolefin (BG) and the isocyanate group-containing compound (L).

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.

The isocyanate group content (% by weight) of the isocyanate group-modified polyolefin (BM) is preferably 0.04 to 8.5% (only numerical values are shown below) from the viewpoint of productivity of (M), more preferably 0.08 to 6.0, particularly preferably 0.2 to 5.0. The isocyanate group content here is a value measured according to JIS K1603.
The isocyanate group content rate can be appropriately adjusted depending on the type and weight of the hydroxyl group-modified polyolefin (BG) and the type and weight of the isocyanate group-containing compound (L).

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

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

The acid value (mgKOH/g) of the aminocarboxylic acid-modified polyolefin (BJ) is preferably 1 to 100 mgKOH/g (only numerical values are shown below), more preferably 3 to 75, from the viewpoint of the productivity of (X). , particularly preferably 5 to 50.
The above acid value can be appropriately adjusted depending on the type and weight of the acid-modified polyolefin (BE) and the type and weight of the aminocarboxylic acid (H).

The block polymer of the present invention imparts excellent mechanical strength (tensile strength, impact strength) to molded articles of the thermoplastic resin composition (Z) described below. Furthermore, it imparts excellent mechanical strength to the recycled polyolefin resin (YR).
Therefore, it can be suitably used as a modifier for thermoplastic resins, especially as a modifier for polyolefin resins.

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

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

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.
Among the thermoplastic resins (Y), polyolefin resins are preferable.

As described above, a recycled polyolefin resin (YR) is also suitable as the thermoplastic resin (Y). The (YR) is a polyolefin resin that has been subjected to crushing, pulverization, pelletization, etc. after being subjected to a molding process.

Mn of the thermoplastic resin (Y) is preferably 10,000 to 500,000, more preferably 20,000 to 400,000 from the viewpoint of mechanical strength of the molded product and compatibility with the block polymer (X). , more preferably 80,000 to 300,000.

The thermoplastic resin composition (Z) of the present invention may further contain a filler (N1), a coloring agent (N2), a matting agent (N3), and an antistatic agent (N4) as long as the effects of the present invention are not impaired. , Dispersant (N5), Flame Retardant (N6), Foaming Agent (N7), Antioxidant (N8), UV Absorber (N9) and Plasticizer (N10) One or more selected from the group consisting of of additive (N) can be contained.

Examples of the filler (N1) include organic fillers (eg, wood flour, cellulose) and inorganic fillers (eg, 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, more preferably 5 to 40% by weight.

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 from an industrial point of view, it is preferably 1 to 20% by weight.

Based on the total weight of the thermoplastic resin composition (Z), the amount of each additive (N) other than (N1) used, (N2) 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, 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, preferably 5% by weight. (N8) is, for example, 3% or less, preferably 0.01 to 1% by weight; (N9) is, for example, 3% or less, preferably 0.01 to 1% by weight; (N10) is, for example, 20% by weight or less, preferably 5 to 15% by weight.

In addition, when the additives are the same and overlap between (N1) to (N10), the amount of each additive that produces the corresponding additive effect is used regardless of the effect of the other additives. Considering that the effects of other additives can also be obtained at the same time, the amount used should be adjusted according to the purpose of use.

As a method for producing the thermoplastic resin composition (Z) of the present invention,
(1) A method of collectively mixing the total amount of the thermoplastic resin (Y) and the block polymer (X) and, if necessary, (N) to form a resin composition (collective method);
(2) A master containing a block polymer (X) at a high concentration by mixing 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). A method (masterbatch method) of once preparing a batch resin composition and then adding and mixing the rest of the thermoplastic resin (Y) and, if necessary, the remainder of the additive (N) to obtain a resin composition (masterbatch method).
The method (2) is preferable from the viewpoint of mixing efficiency of the block polymer (X).

<Molded product>
The molded article of the present invention is a molded article of the thermoplastic resin composition (Z). That is, the molded article of the present invention is obtained by molding the thermoplastic resin composition (Z).
Molding methods include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (cast method, tenter method, inflation method, etc.). It can be molded by any method including molding, multi-layer molding or foam molding. Examples of the form of the molded article include plate-like, sheet-like, film, fiber (including non-woven fabric and the like), and the like.

The present invention will be further described with reference to the following examples, but the present invention is not limited to these. Parts in the examples represent parts by weight. In the examples, the number average molecular weight (Mn), polyolefin double bond content, isotacticity, acid value, hydroxyl value, epoxy equivalent, and isocyanate group content were measured by the methods described above.

<Production Example 1>
A high molecular weight polyolefin (B0-1) [trade name “Vistamaxx6102” manufactured by ExxonMobil, the same applies hereinafter. ], heated and melted with a mantle heater while passing nitrogen through the liquid phase, and thermally degraded at 350° C. for 10 minutes with stirring to obtain polyolefin (B-1).
The Mn of the polyolefin (B-1) was 30,000, the number of double bonds in the molecular terminal and/or the molecular chain per 1,000 carbon atoms was 0.5, and the isotacticity was 28%. .

<Production Examples 2 to 5>
Thermal degradation was carried out 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 to obtain each polyolefin (B). Table 1 shows the results.

<Production Example 6>
A reaction vessel was charged with 100 parts of polyolefin (B-1) and 1 part of maleic anhydride (C-1), and the mixture was heated to 200° C. under nitrogen ventilation and stirred for 10 hours. Thereafter, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa, hereinafter the same) to obtain acid-modified polyolefin (BE-1).
The acid-modified polyolefin (BE-1) had an acid value of 2.0, an Mn of 30,100, and an isotacticity of 28%.

<Production Examples 7 to 10>
According to Table 2, except that the polyolefin (B), the unsaturated carboxylic acid (anhydride) (C), and the radical initiator (f) were changed, the reaction was carried out in the same manner as in Production Example 6 to obtain each acid-modified polyolefin (BE). Obtained. Table 2 shows the results.

<Production Example 11>
Into a reaction vessel, 100 parts of polyolefin (B-3), 6 parts of glycidyl methacrylate (P-1), heated to 200° C. under nitrogen ventilation, and charged with 1 part of dicumyl peroxide (f-1), Stirring was continued for 10 hours. Thereafter, unreacted glycidyl methacrylate was distilled off under reduced pressure (1.5 kPa, hereinafter the same) to obtain epoxy group-modified polyolefin (BQ-1).
The epoxy group-modified polyolefin (BQ-1) had an epoxy equivalent of 2,500, an Mn of 3,200, and an isotacticity of 50%.

<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, heated to 180° C. under nitrogen ventilation, and stirred for 10 hours. Thereafter, stirring was continued for 10 hours under reduced pressure (1.5 kPa, hereinafter the same) to obtain a hydroxyl-modified polyolefin (BG-1).
The hydroxyl modified polyolefin (BG-1) had a hydroxyl value of 2.0, an Mn of 30,500 and an isotacticity of 28%.

<Production Example 13>
According to Table 4, the reaction was carried out in the same manner as in Production Example 12 except that the acid-modified polyolefin (BE) was changed to obtain each hydroxyl group-modified polyolefin (BG). Table 4 shows the results.

<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, heated to 180° C. under nitrogen ventilation, and stirred for 10 hours. Thereafter, stirring was continued for 10 hours under reduced pressure (1.5 kPa, hereinafter the same) to obtain an aminocarboxylic acid-modified polyolefin (BJ-1).
The aminocarboxylic acid-modified polyolefin (BJ-1) had an acid value of 22.2, an Mn of 3,400, and an isotacticity of 50%.

<Production Examples 15-16>
Except for changing the acid-modified polyolefin (BE) and aminocarboxylic acid (H) according to Table 4, the reaction was carried out in the same manner as in Production Example 14 to obtain each aminocarboxylic acid-modified polyolefin (BJ). Table 4 shows the results.

<Production Example 17>
100 parts of polyolefin (B-1), 1 part of 2-mercaptoethanol (F-2), and 200 parts of xylene are charged in a reaction vessel, heated to 160° C. under nitrogen ventilation, and 1,1′-azobis (Cyclohexane-1-carbonitrile) (f-1) (1 part) 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, hereinafter the same) to obtain a hydroxyl group-modified polyolefin (BG-3).
The hydroxyl modified polyolefin (BG-3) had a hydroxyl value of 2.0, an Mn of 30,100 and an isotacticity of 28%.

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

<Example 1>
10 parts of (BJ-1), 100 parts of (BG-1), and 0.1 part of dibutyltin as an esterification catalyst were placed in a reaction vessel, and after purging with nitrogen, the mixture was heated to 200° C. under a stream of nitrogen and dissolved. rice field. Stirring was continued at 200° C. for 3 hours. Thereafter, the mixture was reacted for 5 hours under reduced pressure (1.5 kPa, hereinafter the same), and then removed from the reactor to obtain block polymer (X-1).
(X-1) had an Mn of 42,000 and an acid value of 0.01.

<Examples 2-3>
In Example 1, each block polymer (X) was obtained by performing the same reaction as in Example 1 except that each starting material was used according to Table 7. Table 7 shows the results.

<Example 4>
25 parts of (BM-1), 100 parts of (BG-3), 200 parts of xylene, and 0.1 part of bismath tris (2-ethylhexaate) as a urethanization catalyst are charged in a reaction vessel, and after purging with nitrogen, under nitrogen ventilation. was heated up to 150° C. and dissolved. Stirring was continued at 150° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure (1.5 kPa, hereinafter the same), and the reaction vessel was taken out to obtain a block polymer (X-4).
Incidentally, (X-4) had an Mn of 62,000 and a hydroxyl value of 0.02.

<Example 5>
In Example 4, each block polymer (X) was obtained by performing the same reaction as in Example 4, except that each starting material was used according to Table 7. Table 7 shows the results.

<Example 6>
100 parts of (BJ-2), 100 parts of (BQ-1), and 0.1 part of the epoxidation catalyst diazabicycloundecene were charged into a reaction vessel, and after purging with nitrogen, the temperature was raised to 150° C. under nitrogen ventilation. Dissolved. After continuing stirring at 150° C. for 3 hours, the mixture was taken out from the reaction vessel to obtain (X-6).
(X-6) had an Mn of 9,500 and an acid value of 0.01.

Table 7 shows the results for each block polymer (X). Polyolefin (B-1) was used as a block polymer for comparison.

<Examples 7-12, Comparative Examples 1-2>
According to the composition (parts) of Table 8, each block polymer (X) and thermoplastic resin (Y) were melted at 230° C. and 100 rpm with a twin-screw extruder [trade name “KZW45TW” manufactured by Technobell Co., Ltd.]. The mixture was kneaded to obtain each thermoplastic resin composition (Z).
Each thermoplastic resin composition (Z) was injection molded with 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 later. . Table 8 shows the results.

<Evaluation method>
(1) Tensile strength Measured according to JIS K7171 to evaluate tensile strength.
<Evaluation Criteria>
◎: 30 MPa or more ○: 25 MPa or more and less than 30 MPa △: 20 MPa or more and less than 25 MPa ×: less than 20 MPa

(2) Impact resistance The Izod impact value was measured according to JIS K7110.
<Evaluation Criteria>
◎: 3.0 kJ/m ² or more ○: 1.5 kJ/m ² or more and less than 3.0 kJ/m ² △: 1.0 kJ/m ² or more and less than 1.5 kJ/m ² ×: less than 1.0 kJ/m ²

<Examples 13-18, Comparative Examples 3-4>
According to the formulation (parts) in Table 9, each block polymer (X) and thermoplastic resin (YR-1) [recycled polyolefin resin, trade name “PP crushed”, manufactured by Miki Jushi Kogyo Co., Ltd.] were subjected to biaxial extrusion. The mixture was melt-kneaded at 230° C. and 100 rpm using a machine [trade name “KZW45TW” manufactured by Technobell Co., Ltd.] to obtain each thermoplastic resin composition (Z).
Furthermore, after pelletizing, injection molding was performed at a nozzle temperature of 230 ° C. and a mold temperature of 50 ° C. with an injection molding machine [trade name “PS40E5ASE”, manufactured by Nissei Plastics Co., Ltd.] to prepare a test piece according to the evaluation method described later. evaluated. Table 9 shows the results.

(1) Tensile strength Measured according to JIS K7171 to evaluate tensile strength.
<Evaluation Criteria>
A: 25 MPa or more B: 20 MPa or more and less than 25 MPa C: 15 MPa or more and less than 20 MPa C: Less than 15 MPa (2) Impact resistance The Izod impact value was measured according to JIS K7110.
<Evaluation Criteria>
◎: 2.5 kJ/m ² or more ○: 1.2 kJ/m ² or more and less than 2.5 kJ/m ² △: 0.8 kJ/m ² or more and less than 1.2 kJ/m ² ×: less than 0.8 kJ/m ²

<Examples 19 to 24, Comparative Examples 5 to 6>
Each block polymer (X), thermoplastic resin (Y), and filler (N1) were extruded at 230° C. using a twin-screw extruder [trade name “KZW45TW” manufactured by Technobell Co., Ltd.] according to the composition (parts) shown in Table 10. , and 100 rpm to obtain each thermoplastic resin composition (Z).
Furthermore, after pelletizing, injection molding was performed at a nozzle temperature of 230 ° C. and a mold temperature of 50 ° C. with an injection molding machine [trade name “PS40E5ASE”, manufactured by Nissei Plastics Co., Ltd.] to prepare a test piece according to the evaluation method described later. evaluated. Table 10 shows the results.

(1) Bending strength Measured according to JIS K7171 to evaluate tensile strength. (Unit: MPa)
(2) Impact resistance The Charpy impact value was measured according to ASTM D6110. (Unit: J/m)

From the results in Tables 1 to 10, it can be seen that the block polymer (X) of the present invention imparts superior mechanical strength to molded articles of the thermoplastic resin composition (Z) compared to the comparative ones. It also imparts excellent mechanical strength to recycled polyolefin resin (YR).

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 molded articles of various thermoplastic resins.

Claims (6)

A block polymer (X) having at least two polyolefin structures derived from the following polyolefin (B) as constituent units, and having 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, the isotacticity of the α-olefin portion is 1% or more and less than 65%, and the number average molecular weight is 1,000 ~200,000;
Binder (γ): 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) At least one selected from the group consisting of; 3. The block polymer according to claim 1, which has a number average molecular weight of 3,000 to 500,000. A thermoplastic resin composition (Z) comprising the block polymer (X) according to claim 1 or 2 and a thermoplastic resin (Y). The thermoplastic resin according to claim 3, wherein the weight ratio [(X)/(Y)] between the block polymer (X) and the thermoplastic resin (Y) is 0.01/99.99 to 50/50. Composition. The thermoplastic resin composition according to claim 3 or 4, further comprising a filler (N1), wherein the weight of the filler (N1) is 3 to 50% by weight based on the weight of the thermoplastic resin composition. . A molded article obtained by molding the thermoplastic resin composition (Z) according to any one of claims 3 to 5.