JP6839029B2 - Resin composition - Google Patents

Description

The present invention relates to resin compositions.

Vinyl aromatic and / or conjugated diene-based block (co) polymers exhibit various properties depending on the proportion and arrangement of blocks, the degree of hydrogenation, etc., but modified groups are used for the purpose of imparting further performance. Modified block copolymers containing them have been proposed.
For example, Patent Document 1 proposes an amino group-modified block copolymer produced by reacting a block copolymer terminal with an amino group-containing compound.

Modified block copolymers are used for modifying polar resins because they have excellent compatibility with polar resins based on the reactivity of modifying groups and intermolecular interactions such as hydrogen bonds. One of the polar resins to be modified is thermoplastic polyurethane (hereinafter, may be referred to as "TPU"). For example, Patent Document 2 proposes modification of a polar resin with a modified block copolymer.

Further, the modified block copolymer is being studied for use as a compatibilizer for polymer alloying a polar resin and a non-polar resin. For example, Patent Document 3 proposes a polymer alloy of polyamide and polyolefin using a modified block copolymer as a compatibility agent.

Japanese Unexamined Patent Publication No. 2004-59817 Japanese Unexamined Patent Publication No. 2009-242463 Japanese Unexamined Patent Publication No. 2016-222932

Alloying of TPU with polyolefin is being studied for the main purpose of cost reduction and weight reduction.
In this alloy of TPU and polyolefin, it is required to realize cost reduction and weight reduction while maintaining the tear strength and abrasion resistance characteristic of polyurethane.
However, the prior art has a problem that the compatibility between TPU and polyolefin is not sufficiently examined.

Therefore, in the present invention, in view of the above-mentioned problems of the prior art, a resin composition containing TPU and polyolefin having excellent tear strength and abrasion resistance is provided by using a modified block copolymer as a compatibilizer. That is.

As a result of diligent studies to solve the above-mentioned problems of the prior art, the present inventors have found the resin in a resin composition containing TPU and polyolefin using a modified block copolymer as a compatibilizer. When the composition is a molded product, it has been found that a product having a specific sea-island structure in the cross section of the molded product can solve the above problems, and the present invention has been completed.

That is, the present invention is as follows.
[1]
A resin composition comprising a modified block copolymer (a), a thermoplastic polyurethane (b), and a polyolefin (c).
The modified block copolymer (a) is a polymer block (A) mainly composed of a vinyl aromatic compound, a polymer block (B) mainly composed of a conjugated diene compound, and an atomic group (C) having a functional group. ) And, including
In the cross section of the molded product of the resin composition, the thermoplastic polyurethane (b) has a sea-island structure, and the modified block copolymer (a) and / or the polyolefin (c) forms an island phase.
Heat having a major axis of 3 μm or less in the island phase formed by the modified block copolymer (a) and / or the polyolefin (c) surrounded by the sea phase formed by the thermoplastic polyurethane (b). There is an island phase of thermoplastic polyurethane (b),
The ratio of the intensity obtained by singular value decomposition of the absorption spectrum obtained by scanning transmission electron X-ray microscope measurement between the island phase of (b) and the sea phase of (b) (intensity in the island phase of (b)). / (Strength in the sea phase of (b)) is 0.5 or more.
Resin composition.
[2]
When the resin composition is 100% by mass, the modified block copolymer (a) is 1 to 98% by mass, the thermoplastic polyurethane (b) is 1 to 98% by mass, and the polyolefin (c) is 1. The resin composition according to [1], which comprises ~ 98% by mass.
[3]
The resin composition according to [1] or [2], wherein the functional group is NHx (x = 0 to 2).

According to the present invention, a composition containing TPU and polyolefin using a modified block copolymer as a compatibilizer can have a specific sea-island structure because the molded product of the resin composition has a specific sea-island structure. It is possible to provide a composition having improved tear strength and abrasion resistance as compared with a resin composition having no resin composition.

It is a figure which shows the schematic diagram of the cross section of the molded body of the resin composition of this embodiment. In the schematic diagram, the A phase represents the sea phase formed of the thermoplastic polyurethane (b), and the B phase represents the island phase formed of the modified block copolymer (a) and / or the polyolefin (c). , C phase represents the island phase of the thermoplastic polyurethane (b) having a major axis of 3 μm or less, which is contained in the island phase formed by the modified block copolymer (a) and / or the polyolefin (c). It is a figure which shows the image obtained by observing the cross section of the molded article of the resin composition of Example 1 using a scanning transmission electron X-ray microscope. In the image, the circled portion is a thermoplastic polyurethane (b) having a major axis of 3 μm or less contained in the island phase formed by the modified block copolymer (a) and / or the polyolefin (c). Island fauna. It is a figure which shows the image obtained by observing the cross section of the molded article of the resin composition of Example 3 using a scanning transmission X-ray microscope. In the image, the circled portion is a thermoplastic polyurethane (b) having a major axis of 3 μm or less contained in the island phase formed by the modified block copolymer (a) and / or the polyolefin (c). Island fauna. It is a figure which shows the image obtained by observing the cross section of the molded article of the resin composition of Comparative Example 1 using a scanning transmission electron X-ray microscope. FIG. 5 is a color diagram showing an image obtained by observing a cross section of a molded product of the resin composition of Example 1 using a scanning transmission electron X-ray microscope. FIG. 5 is a color diagram showing an image obtained by observing a cross section of a molded product of the resin composition of Example 3 using a scanning transmission electron X-ray microscope. FIG. 5 is a color diagram showing an image obtained by observing a cross section of a molded product of the resin composition of Comparative Example 1 using a scanning transmission electron X-ray microscope.

Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

The resin composition of the present embodiment contains a modified block copolymer (a), a thermoplastic polyurethane (b), and a polyolefin (c).
The modified block copolymer (a) is a polymer block (A) mainly composed of a vinyl aromatic compound, a polymer block (B) mainly composed of a conjugated diene compound, and an atomic group (C) having a functional group. including.
In the cross section of the molded product of the resin composition of the present embodiment, the thermoplastic polyurethane (b) forms a sea phase, and the modified block copolymer (a) and / or the polyolefin (c) form an island phase, and have a sea-island structure. And
Heat having a major axis of 3 μm or less in the island phase formed by the modified block copolymer (a) and / or the polyolefin (c) surrounded by the sea phase formed by the thermoplastic polyurethane (b). There is an island phase of thermoplastic polyurethane (b),
The ratio of the intensity obtained by singular value decomposition of the absorption spectrum obtained by scanning transmission electron X-ray microscope measurement between the island phase of (b) and the sea phase of (b) (intensity in the island phase of (b)). / (Strength in the sea phase of (b)) is 0.5 or more.

[Modified block copolymer (a)]
The modified block copolymer (a) in the present embodiment includes a polymer block (A) mainly composed of a vinyl aromatic compound, a polymer block (B) mainly composed of a conjugated diene compound, and an atom having a functional group. Includes group (C) and.

Here, "mainly" means that the target monomer unit is contained in the target polymer block in an amount of 60% by mass or more.
From the viewpoint of compatibility and strength between the modified block copolymer (a) and the polyolefin, the content of the conjugated diene compound monomer unit in the polymer block (B) mainly composed of the conjugated diene compound is preferably 70. It is 0% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.
Further, from the viewpoint of the strength of the molded product of the composition of the modified block copolymer (a) and TPU, the inclusion of the vinyl aromatic compound monomer unit in the polymer block (A) mainly composed of the vinyl aromatic compound. The amount is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more.

In the modified block copolymer (a) contained in the resin composition of the present embodiment, the content of the polymer block (A) mainly composed of a vinyl aromatic compound is compatible with polyolefin and molding of the TPU composition. From the viewpoint of the mechanical strength of the body, it is preferably 1 to 70% by mass.
The content of the polymer block (A) mainly composed of a vinyl aromatic compound is more preferably 3 to 50% by mass, and further preferably 5 to 35% by mass.

The content of the polymer block (A) mainly composed of a vinyl aromatic compound can be measured by using a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, by the method described in Examples described later. Can be calculated.
The content of the polymer block (A) mainly composed of a vinyl aromatic compound can be controlled by adjusting the type and the amount of the monomer added in the polymerization step of the modified block copolymer.

In the modified block copolymer (a) contained in the resin composition of the present embodiment, the amount of vinyl bond of the polymer block (B) mainly composed of the conjugated diene compound before hydrogenation is the phase of fluidity and polyolefin. From the viewpoint of tolerability, it is preferably 20 to 100 mL.
"Amount of vinyl bond before hydrogenation" means 1,4-bond (cis and trans) and 1,2-bond (however, 3,) due to the conjugated diene compound incorporated in the polymer before hydrogenation. When incorporated into a polymer with 4-bonds, it refers to the total amount of 1,2-bonds and 3,4-bonds) with respect to the amount of 1,2-bonds (mol%).
The amount of vinyl bond before hydrogenation of the polymer block (B) mainly composed of the conjugated diene compound is more preferably 30 to 90 mL, still more preferably 35 to 80 mL.
The amount of vinyl bonds in the modified block copolymer can be measured using a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, can be measured by the method described in Examples described later.
The vinyl bond amount can be controlled within the above numerical range by using a Lewis base, for example, a compound such as ether or amine as a vinyl bond amount adjusting agent (hereinafter, referred to as a vinylizing agent).

In the modified block copolymer (a) contained in the resin composition of the present embodiment, the hydrogenation rate of the polymer block (B) mainly composed of the conjugated diene compound is 0 to 100 mL, and the phase with the polyolefin is From the viewpoint of tolerability, the polymer block (B) is preferably a hydrogenated product, and the hydrogenation rate is preferably 40 to 100 mL, more preferably 70 to 100 mL, and even more preferably. Is 80 to 100 mL, and even more preferably 90 to 100 mL.
The hydrogenation rate of the modified block copolymer can be measured using a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, it can be measured by the method described in Examples described later.
Further, the hydrogenation rate can be controlled within the above numerical range by adjusting the amount of hydrogen at the time of hydrogenation, for example.

In the modified block copolymer (a) contained in the resin composition of the present embodiment, the amount of butylene and / or the amount of propylene is compatible with fluidity and polyolefin with respect to a total of 100 mol% of the conjugated diene compound units. From the viewpoint of, it is preferably 25 to 100 mol%. The amount of butylene and / or the amount of propylene is more preferably 29 to 99 mL, and even more preferably 31 to 98 mL, based on 100 mol% of the total amount of the conjugated diene compound unit.
The amount of butylene and / or the amount of propylene can be measured using a nuclear magnetic resonance apparatus (NMR) or the like, and specifically, can be measured by the method described in Examples described later.
The amount of butylene and / or the amount of propylene with respect to the total 100 mL% of the conjugated diene compound units can be controlled by adjusting the vinyl bond amount and the hydrogenation rate of the block copolymer.

In the modified block copolymer (a) contained in the resin composition of the present embodiment, the aromatic vinyl compound contained in the polymer block (A) mainly composed of a vinyl aromatic compound is limited to the following. Not, for example, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethyl Examples include vinyl aromatic compounds such as styrene.
Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferably mentioned, and styrene is more preferable, from the viewpoint of availability and productivity.
The polymer block (A) mainly composed of a vinyl aromatic compound may be composed of one type of aromatic vinyl compound unit, or may be composed of two or more types.

In the modified block copolymer (a) contained in the resin composition of the present embodiment, the conjugated diene compound contained in the polymer block (B) mainly composed of the conjugated diene compound has a pair of conjugated double bonds. It is a diolefin. The diolefin is not limited to the following, and is, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3. -Pentaniene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, farnesene and the like can be mentioned.
Among these, 1,3-butadiene and isoprene are preferably mentioned from the viewpoint of availability and productivity.
The polymer block (B) mainly composed of a conjugated diene compound may be composed of one kind of conjugated diene compound unit, or may be composed of two or more kinds.

In the modified block copolymer (a) contained in the resin composition of the present embodiment, in addition to the conjugated diene monomer and vinyl aromatic monomer, the conjugated diene monomer and vinyl aromatic monomer are used together. Other polymerizable monomers can also be used.

The melt flow rate (MFR; 230 ° C., load 2.16 kg, conforming to ISO 1133) of the modified block copolymer (a) is 0.1 to 50 g / g from the viewpoint of processability of the obtained TPU resin composition. The range of 10 minutes is preferable, the range of 0.5 to 30 g / 10 minutes is more preferable, and the range of 1.0 to 25 g / 10 minutes is further preferable.

The modified block copolymer (a) is not particularly limited as long as it satisfies the conditions in the present embodiment, and any structure can be used.
For example, examples of the basic structure of the modified block copolymer (a) include those having a structure represented by the following general formula.
In the following general formula, the block (A) and the block (B) are used to represent the basic structure, and the description of the atomic group (C) is omitted.
A- (BA) _n
B- (AB) _n
(AB) _n
(AB _{) m-} ^{X 1}
(BA _{) m-} ^{X 1}

In the above general formula, A is a polymer block (A) mainly composed of a vinyl aromatic compound, and when a plurality of them are present, they may be different or the same.
B is a polymer block (B) mainly composed of a conjugated diene compound, and when a plurality of them are present, they may be different or the same.
n is 1 or more, preferably an integer of 1 to 3.
m indicates 2 or more, and is preferably an integer of 2 to 6.
X ¹ indicates a coupling agent residue or a polyfunctional initiator residue.
The basic structure of the modified block copolymer (a) is particularly preferably a polymer represented by the structural formulas ABA and ABAB.

The functional group of the atomic group (C) having a functional group in the modified block copolymer (a) is preferably NHx (x = 0 to 2).
That is, in the above general formula, it is preferable that the atomic group (C) having NHx (x = 0 to 2) is added to the blocks A and / or B.

The weight average molecular weight (Mw) (hereinafter, also referred to as “Mw”) of the modified block copolymer is 3 × 10 ⁴ to 30 × 10 ^{4 from the viewpoints of mechanical strength, fluidity, wear resistance, and compatibility.} It is preferably 4 × 10 ^{4 to} 27 × 10 ⁴ , and even more preferably 5 × 10 ^{4 to} 25 × 10 ⁴ .

The weight average molecular weight (Mw) of the modified block copolymer is prepared by measuring the peak molecular weight of the chromatogram obtained by GPC measurement using a calibration line obtained from the measurement of commercially available standard polystyrene (using the peak molecular weight of standard polystyrene). ) Is the weight average molecular weight (Mw) obtained. The molecular weight distribution of the block copolymer before modification can also be obtained from the measurement by GPC, and the molecular weight distribution is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

The molecular weight distribution of a single peak measured by gel permeation chromatography (hereinafter, also referred to as “GPC”) of the modified block copolymer is preferably 5.0 or less, more preferably 4.0 or less. Yes, more preferably 3.0 or less, and even more preferably 2.5 or less.

In the present embodiment, the "atomic group (C) having a functional group" is an atomic group other than the monomer unit constituting the main chain of the modified block copolymer. As the functional group, an amino group, a carbonyl group and a hydroxyl group are preferable, and an amino group and a carbonyl group are preferable. The functional group has polarity by containing N, O, P, etc., and the portion having this polarity interacts with the polar portion such as the urethane bond in the TPU to improve the compatibility of the resin composition. It is estimated to be. Therefore, the functional group contained in the atomic group (C) is preferably one having a polarity that easily interacts with a polar portion such as a urethane bond.

Examples of the method for obtaining a modified block copolymer include a polymerization initiator having a functional group, a method of polymerizing using an unsaturated monomer having a functional group, and a modifying agent forming or containing a functional group at the living end. Examples thereof include a method of addition reaction.

Examples of the modifier that forms or contains a functional group include tetraglycidyl methoxylylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, 1,3-dimethyl-2-imidazolidinone, 1, Examples thereof include 3-diethyl-2-imidazolidinone, N, N'-dimethylpropylene urea, and N-methylpyrrolidone.

As another method for obtaining a modified block copolymer, a modifier having a functional group in the polymer to which the organic alkali metal is added by reacting the copolymer with an organic alkali metal compound such as an organic lithium compound (metallation reaction). Examples thereof include a method of causing an addition reaction.

As another method for obtaining the modified block copolymer, a method of grafting an atomic group (C) having a functional group on the unmodified block copolymer can be mentioned, and NHx (x = 0 to 2) is preferable. It is a method of grafting an atomic group (C) having.

In the present embodiment, the "atomic group (C) having NHx (x = 0 to 2)" is an atomic group other than the monomer unit constituting the main chain of the modified block copolymer, and is at least one. It refers to an atomic group having NHx (x = 0 to 2). The atomic group may have a functional group such as an imide group in addition to at least one NHx (x = 0 to 2). The atomic group (C) having NHx (x = 0 to 2) may be contained in the modified block copolymer in any way, and preferably the polymer block (A) mainly composed of a vinyl aromatic compound. And / or a polymer block (B) mainly composed of a conjugated diene compound is contained by forming a chemical bond.

The atomic group (C) having NHx (x = 0 to 2) may be contained at any position of the modified block copolymer.
When NHx (x = 0 to 2) reacts with a polar part such as a urethane bond in the TPU, the copolymer produced by the reaction becomes a compatibilizer for the TPU and the modified block copolymer, or the TPU and the polyolefin. It acts as a compatibilizer and improves the compatibility of the resin composition. Alternatively, intermolecular interactions such as hydrogen bonds act between NHx (x = 0 to 2) and polar parts such as urethane bonds in the TPU, so that the compatibility between the TPU and the modified block copolymer or the TPU. And polyolefin compatibility is improved.

The atomic group (C) having NHx (x = 0 to 2) has the following structure.
When x = 2, it is X ^2- R _{1 −} NH ₂ .
When x = 1, it is X ^2- R ₁ −NHR ₂ .
When x = 0, it is X ^2- R ₁ −NR ₃ R ₄ .
In a preferred embodiment, X ² is a structure in which a vinyl or a derivative of α, β-unsaturated carboxylic acid forms a chemical bond with the polymer block (A) and / or the polymer block (B) by graft modification.

X ² is, for example, an imidized, amidated or esterified structure of α, β-unsaturated carboxylic acid, specifically, N-substituted maleimide, maleic acid amide, maleic acid ester, acrylic acid amide, Acrylic acid ester, methacrylic acid amide, methacrylic acid ester, endo-cis-bicyclo [2,2,1] -5-hepten-2,3-dicarboxylic acid amide, endo-cis-bicyclo [2,2,1]- It is a structure in which 5-heptene-2,3-dicarboxylic acid ester forms a chemical bond with the polymer block (A) and / or the polymer block (B) by graft modification.
X ² preferably has an imidized structure or an amidated structure, and more preferably N-substituted maleimide or maleic acid amide is chemically bonded to the polymer block (A) and / or the polymer block (B) by graft modification. It is a structure that formed.
R ₁ is a hydrocarbon group of C1 to C22, preferably an alkylene group of C1 to C12, for example ethylene, propylene, butylene, or an aromatic group of C6 to C10, for example phenylene. R ₁ may further contain a heteroatom.
R ₂ is a hydrocarbon group of C1 to C13, preferably an alkyl group of C1 to C6, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl and This structural isomer, hexyl and this structural isomer, are cycloalkyls of C6 to C12, such as cyclohexyl, aromatics of C6 to C13, such as phenyl, benzyl, and more preferably R ₂ is cyclohexyl or benzyl. .. R ₂ may further contain a heteroatom.
R ₁ and R ₂ may be bonded to form a ring structure, and the ring structure is preferably an N-alkylpiperazine structure.

R ₃ and R ₄ may be different or the same, each of which is a hydrocarbon group of C1 to C13, preferably an alkyl group of C1 to C6, for example methyl, ethyl, propyl, etc. Examples thereof include isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, pentyl and structural isomers thereof, hexyl and structural isomers thereof. Further, R ₃ and R ₄ are cycloalkyls of C6 to C12, for example, cyclohexyl, aromatics of C6 to C13, for example, phenyl and benzyl, and more preferably, R ₃ and R ₄ are cyclohexyl or benzyl, respectively. ..
R ₃ and R ₄ may each further contain a heteroatom.
R ₃ and R ₄ may be contained in the same _{ring structure, and −NR 3} R ₄ is, for example, piperidinyl or pyridinyl.

The NHx of the atomic group (C) having NHx (x = 0 to 2) is preferably a secondary amino group or an amide group having x = 1, and more preferably the reaction rate constants are -NH ₂ and -NH-CH. It is a secondary amino group that is less than _3.

“The reaction rate constant is _{less than −NH 2} and −NH-CH ₃ ” means that the secondary reaction rate constant k with the electrophilic reactive compound is less than R ₁ −NH ₂ and R ₁ −NH −CH ₃ . , R ₁ − NH − R ₂ .
The method for measuring the secondary reaction rate constant k is not particularly limited, but is a method using phenylglycidyl ether described in Toshio Kakurai et al., Synthetic Organic Chemistry, Vol. 18, No. 7, 485 (1960) as an electrophilic reactive compound. Then, a method of calculating from the following formula can be mentioned.
k = lоg ((ax) b / (bx) a) / (0.4343 (ab) t)
k: Secondary reaction rate constant (L / mol / min)
a: Initial concentration of phenylglycidyl ether (mоl / L)
b: Initial _{concentration of R 1-} NH-R ₂ (mоl / L)
x: Decrease in phenylglycidyl ether concentration or R _1- NH-R ₂ concentration after t minutes (mоl / L)
t: Reaction time (min)

The amino group having a reaction rate constant of _{less than R 1} −NH ₂ and R ₁ −NH −CH ₃ is not limited to the following, but for example, _{R 2} of R ₁ −NH − _{R 2} is linear. Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their structural isomers, or cyclohexyl, phenyl, benzyl, or R ₁ and R ₂ form the same ring structure. Cases include pyridinyl and piperazinyl.

The method for producing the modified block copolymer of the present embodiment is not particularly limited, but the atomic group (C) having NHx (x = 0 to 2) is used as the polymer block (A) mainly composed of a vinyl aromatic compound and the polymer block (A). / Or a method of introducing into the side chain of the polymer block (B) mainly composed of a conjugated diene compound can be mentioned.
As a method of introducing the atomic group (C) into the side chain of the polymer block (A) and / or the polymer block (B), for example, a graft of the atomic group (C) having NHx (x = 0 to 2) is used. A production method for directly grafting a precursor having an unsaturated group that contributes to the reaction, a polymer block (A) mainly composed of a vinyl aromatic compound, and / or a polymer block (B) mainly composed of a conjugated diene compound. An α, β-unsaturated carboxylic acid or a derivative thereof is introduced into the side chain by a graft reaction so that the compound having NHx (x = 0 to 2) reacts with the α, β-unsaturated carboxylic acid or a derivative thereof. The manufacturing method to be carried out can be mentioned.

A polymer block (A) mainly composed of a vinyl aromatic compound by directly grafting a precursor having an unsaturated radical that contributes to the graft reaction of the atomic group (C) having NHx (x = 0 to 2) and / or In the case of a production method in which an atomic group (C) having NHx (x = 0 to 2) is introduced into the side chain of a polymer block (B) mainly composed of a conjugated diene compound, for example, in the presence of a radical initiator. A block copolymer containing a polymer block (A) mainly composed of a vinyl aromatic compound and a polymer block (B) mainly composed of a conjugated diene compound, and an atomic group (C) having NHx (x = 0 to 2). ), A production method in which a precursor having an unsaturated group that contributes to the graft reaction of) is radically added can be mentioned.

Α, β-unsaturated carboxylic acid or a derivative thereof is introduced into the side chain of the polymer block (A) mainly composed of a vinyl aromatic compound and / or the polymer block (B) mainly composed of a conjugated diene compound by a graft reaction. In the case of a production method in which the compound having NHx (x = 0 to 2) reacts with the α, β-unsaturated carboxylic acid or a derivative thereof, the α, β-unsaturated carboxylic acid or a derivative thereof may be used. , But not limited to, for example, maleic acid, maleic halide, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo [2,2,1]-. Examples thereof include 5-heptene-2,3-dicarboxylic acid and the like, anhydrides of these dicarboxylic acids, acrylic acid, methacrylic acid, crotonic acid and the like and esters of these monocarboxylic acids, for example, methyl methacrylate and glycidyl methacrylate. Anhydrous is preferable, and among these, maleic anhydride is preferable from the viewpoint of reactivity.

The compound having NHx (x = 0 to 2) has, in addition to NHx (x = 0 to 2), at least one functional group that reacts with the α, β-unsaturated carboxylic acid, its induction, or the like. It is preferable that the functional group is typically a nucleophilic functional group such as a primary amino group, a secondary amino group or a hydroxyl group. When the nucleophilic reactivity of these functional groups to the carbonyl group is equal to or higher than NHx (x = 0 to 2), the functional group reacts with α, β-unsaturated carboxylic acid or a derivative thereof, and imide, amide, or the like. An ester can be formed and NHx (x = 0 to 2) can be introduced into the block copolymer. Therefore, as the functional group, it is preferable that the nucleophilic reactivity with respect to the carbonyl group is equal to or higher than that of NHx (x = 0 to 2). When the functional group is an amino group, steric hindrance of the amino group and NHx (x = 0 to 2) is a factor that determines the nucleophilic reactivity of the amino group and NHx (x = 0 to 2) to the carbonyl group. In general, it is more difficult to add a nucleophilic addition to a bulky substituent.

Examples of the compound having NHx (x = 0 to 2) include the compounds exemplified below, and all of these compounds exert an effect based on this principle.

Ethan-1,2-diamine, propane-1,3-diamine, butane-1,4-diamine, pentane-1,5-diamine, hexane-1,6-diamine, heptane-1,7-diamine, octane- 1,8-Diamine, Nonan-1,9-Diamine, Decane-1,10-Diamine, Undecane-1,11-Diamine, Dodecane-1,12-Diamine, benzene-1,4-Diamine, benzene-1, 3-diamine, benzene-1,2-diamine, cyclohexane-1,4-diamine, cyclohexane-1,3-diamine, cyclohexane-1,2-diamine, 1,4-phenylenedimethaneamine, 1,3-pheni Range methaneamine, 1,2-phenylenedi methaneamine,

N-Methylethane-1,2-diamine, N-methylpropane-1,3-diamine, N-methylbutane-1,4-diamine, N-methylpentane-1,5-diamine, N-methylhexane-1,6 -Diamine, N-methylheptane-1,7-diamine, N-methyloctane-1,8-diamine, N-methylnonan-1,9-diamine, N-methyldecane-1,10-diamine, N-methylundecane- 1,11-diamine, N-methyldodecane-1,12-diamine, N-methylbenzene-1,4-diamine, N-methylbenzene-1,3-diamine, N-methylbenzene-1,2-diamine, N-methylcyclohexane-1,4-diamine, N-methylcyclohexane-1,3-diamine, N-methylcyclohexane-1,2-diamine, 1-((4-aminomethyl) phenyl) -N-methylmethaneamine , 1-((3-aminomethyl) phenyl) -N-methylmethaneamine, 1-((2-aminomethyl) phenyl) -N-methylmethaneamine,

N-Ethylethane-1,2-diamine, N-ethylpropane-1,3-diamine, N-ethylbutane-1,4-diamine, N-ethylpentane-1,5-diamine, N-ethylhexane-1,6 -Diamine, N-ethylheptane-1,7-diamine, N-ethyloctane-1,8-diamine, N-ethylnonan-1,9-diamine, N-ethyldecane-1,10-diamine, N-ethylundecane- 1,11-diamine, N-ethyldodecane-1,12-diamine, N-ethylbenzene-1,4-diamine, N-ethylbenzene-1,3-diamine, N-ethylbenzene-1,2-diamine, N-ethyl Cyclohexane-1,4-diamine, N-ethylcyclohexane-1,3-diamine, N-ethylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) ethaneamine, N-((3-amino) Methyl) benzyl) ethaneamine, N-((2-aminomethyl) benzyl) ethaneamine,

N-Propylethane-1,2-diamine, N-propylpropane-1,3-diamine, N-propylbutane-1,4-diamine, N-propylpentane-1,5-diamine, N-propylhexane-1 , 6-Diamine, N-Propylheptan-1,7-Diamine, N-Propyloctane-1,8-Diamine, N-Propylnonan-1,9-Diamine, N-Propyldecane-1,10-Diamine, N -Propylundecane-1,11-diamine, N-propyldodecane-1,12-diamine, N-propylbenzene-1,4-diamine, N-propylbenzene-1,3-diamine, N-propylbenzene-1, 2-Diamine, N-propylcyclohexane-1,4-diamine, N-propylcyclohexane-1,3-diamine, N-propylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) propane- 1-amine, N-((3-aminomethyl) benzyl) propan-1-amine, N-((2-aminomethyl) benzyl) propan-1-amine,

N-isopropylethane-1,2-diamine, N-isopropylpropane-1,3-diamine, N-isopropylbutane-1,4-diamine, N-isopropylpentane-1,5-diamine, N-isopropylhexane-1 , 6-Diamine, N-Isopropylheptan-1,7-Diamine, N-Isopropyloctane-1,8-Diamine, N-Isopropylnonan-1,9-Diamine, N-Isopropyldecane-1,10-Diamine, N -Isopropylundecane-1,11-diamine, N-isopropyldodecane-1,12-diamine, N-isopropylbenzene-1,4-diamine, N-isopropylbenzene-1,3-diamine, N-isopropylbenzene-1, 2-diamine, N-isopropylcyclohexane-1,4-diamine, N-isopropylcyclohexane-1,3-diamine, N-isopropylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) propane- 2-amine, N-((3-aminomethyl) benzyl) propan-2-amine, N-((2-aminomethyl) benzyl) propan-2-amine,

N-Butylethane-1,2-diamine, N-butylpropane-1,3-diamine, N-butylbutane-1,4-diamine, N-butylpentane-1,5-diamine, N-butylhexane-1,6 -Diamine, N-butylheptane-1,7-diamine, N-butyloctane-1,8-diamine, N-butylnonan-1,9-diamine, N-butyldecane-1,10-diamine, N-butylundecane- 1,11-diamine, N-butyldodecane-1,12-diamine, N-butylbenzene-1,4-diamine, N-butylbenzene-1,3-diamine, N-butylbenzene-1,2-diamine, N-Butylcyclohexane-1,4-diamine, N-butylcyclohexane-1,3-diamine, N-butylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) butane-1-amine, N-((3-aminomethyl) benzyl) butane-1-amine, N-((2-aminomethyl) benzyl) butane-1-amine,

N- (sec-butyl) ethane-1,2-diamine, N- (sec-butyl) propane-1,3-diamine, N- (sec-butyl) butane-1,4-diamine, N- (sec-) Butyl) pentane-1,5-diamine, N- (sec-butyl) hexane-1,6-diamine, N- (sec-butyl) heptane-1,7-diamine, N- (sec-butyl) octane-1 , 8-Diamine, N- (sec-Butyl) Nonan-1,9-Diamine, N- (sec-Butyl) Decane-1,10-Diamine, N- (sec-Butyl) Undecane-1,11-Diamine, N- (sec-butyl) dodecane-1,12-diamine, N- (sec-butyl) benzene-1,4-diamine, N- (sec-butyl) benzene-1,3-diamine, N- (sec-) Butyl) benzene-1,2-diamine, N-butyl (sec-butyl) cyclohexane-1,4-diamine, N- (sec-butyl) cyclohexane-1,3-diamine, N- (sec-butyl) cyclohexane- 1,2-diamine, N-((4-aminomethyl) benzyl) butane-2-amine, N-((3-aminomethyl) benzyl) butane-2-amine, N-((2-aminomethyl) benzyl) ) Butyl-2-amine,

N-isobutylethane-1,2-diamine, N-isobutylpropane-1,3-diamine, N-isobutylbutane-1,4-diamine, N-isobutylpentane-1,5-diamine, N-isobutylhexane-1 , 6-Diamine, N-isobutylheptane-1,7-diamine, N-isobutyloctane-1,8-diamine, N-isobutylnonane-1,9-diamine, N-isobutyldecane-1,10-diamine, N -Isobutylundecane-1,11-diamine, N-isobutyldodecane-1,12-diamine, N-isobutylbenzene-1,4-diamine, N-isobutylbenzene-1,3-diamine, N-isobutylbenzene-1, 2-Diamine, N-isobutylcyclohexane-1,4-diamine, N-isobutylcyclohexane-1,3-diamine, N-isobutylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -2 -Methylpropan-1-amine, N-((3-aminomethyl) benzyl) -2-methylpropane-1-amine, N-((2-aminomethyl) benzyl) -2-methylpropan-1-amine,

N- (tert-butyl) ethane-1,2-diamine, N- (tert-butyl) propane-1,3-diamine, N- (tert-butyl) butane-1,4-diamine, N- (tert- Butyl) pentane-1,5-diamine, N- (tert-butyl) hexane-1,6-diamine, N- (tert-butyl) heptane-1,7-diamine, N- (tert-butyl) octane-1 , 8-diamine, N- (tert-butyl) nonane-1,9-diamine, N- (tert-butyl) decane-1,10-diamine, N- (tert-butyl) undecane-1,11-diamine, N- (tert-butyl) dodecane-1,12-diamine, N- (tert-butyl) benzene-1,4-diamine, N- (tert-butyl) benzene-1,3-diamine, N- (tert- Butyl) benzene-1,2-diamine, N- (tert-butyl) cyclohexane-1,4-diamine, N- (tert-butyl) cyclohexane-1,3-diamine, N- (tert-butyl) cyclohexane-1 , 2-Diamine, N-((4-Aminomethyl) benzyl) -2-methylpropan-2-amine, N-((3-Aminomethyl) benzyl) -2-methylpropan-2-amine, N-( (2-Aminomethyl) benzyl) -2-methylpropan-2-amine,

N-pentylethane-1,2-diamine, N-pentylpropane-1,3-diamine, N-pentylbutane-1,4-diamine, N-pentylpentane-1,5-diamine, N-pentylhexane-1 , 6-Diamine, N-Pentylheptane-1,7-Diamine, N-Pentyloctane-1,8-Diamine, N-Pentylnonan-1,9-Diamine, N-Pentyldecane-1,10-Diamine, N- Pentylundecane-1,11-diamine, N-pentyldodecane-1,12-diamine, N-pentylbenzene-1,4-diamine, N-pentylbenzene-1,3-diamine, N-pentylbenzene-1,2 -Diamine, N-pentylcyclohexane-1,4-diamine, N-pentylcyclohexane-1,3-diamine, N-pentylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) pentane-1 -Amine, N-((3-aminomethyl) benzyl) pentane-1-amine, N-((2-aminomethyl) benzyl) pentane-1-amine,

N- (pentane-2-yl) ethane-1,2-diamine, N- (pentane-2-yl) propan-1,3-diamine, N- (pentane-2-yl) butane-1,4-diamine , N- (pentane-2-yl) pentane-1,5-diamine, N- (pentane-2-yl) hexane-1,6-diamine, N- (pentane-2-yl) heptane-1,7- Diamine, N- (pentane-2-yl) octane-1,8-diamine, N- (pentane-2-yl) nonane-1,9-diamine, N- (pentane-2-yl) decan-1,10 -Diamine, N- (pentane-2-yl) undecane-1,11-diamine, N- (pentane-2-yl) dodecane-1,12-diamine, N- (pentane-2-yl) benzene-1, 4-Diamine, N- (pentane-2-yl) benzene-1,3-diamine, N- (pentane-2-yl) benzene-1,2-diamine, N- (pentane-2-yl) cyclohexane-1 , 4-Diamine, N- (pentane-2-yl) cyclohexane-1,3-diamine, N- (pentane-2-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) Pentane-2-amine, N-((3-aminomethyl) benzyl) pentane-2-amine, N-((2-aminomethyl) benzyl) pentane-2-amine,

N- (pentane-3-yl) ethane-1,2-diamine, N- (pentane-3-yl) propan-1,3-diamine, N- (pentane-3-yl) butane-1,4-diamine , N- (pentane-3-yl) pentane-1,5-diamine, N- (pentane-3-yl) hexane-1,6-diamine, N- (pentane-3-yl) heptane-1,7- Diamine, N- (pentane-3-yl) octane-1,8-diamine, N- (pentane-3-yl) nonane-1,9-diamine, N- (pentane-3-yl) decan-1,10 -Diamine, N- (pentane-3-yl) undecane-1,11-diamine, N- (pentane-3-yl) dodecane-1,12-diamine, N- (pentane-3-yl) benzene-1, 4-Diamine, N- (pentane-3-yl) benzene-1,3-diamine, N- (pentane-3-yl) benzene-1,2-diamine, N- (pentane-3-yl) cyclohexane-1 , 4-Diamine, N- (pentane-3-yl) cyclohexane-1,3-diamine, N- (pentane-3-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) Pentane-3-amine, N-((3-aminomethyl) benzyl) pentane-3-amine, N-((2-aminomethyl) benzyl) pentane-3-amine,

N-Isopentylethane-1,2-diamine, N-Isopentylpropan-1,3-diamine, N-Isopentylbutane-1,4-diamine, N-Isopentylpentane-1,5-diamine, N- Isopentylhexane-1,6-diamine, N-isopentylheptan-1,7-diamine, N-isopentyloctane-1,8-diamine, N-isopentylnonan-1,9-diamine, N-isopentyl Decane-1,10-Diamine, N-Isopentylundecane-1,11-Diamine, N-Isopentyldodecane-1,12-Diamine, N-Isopentylbenzene-1,4-Diamine, N-Isopentylbenzene- 1,3-Diamine, N-Isopentylbenzene-1,2-Diamine, N-Isopentylcyclohexane-1,4-Diamine, N-Isopentylcyclohexane-1,3-Diamine, N-Isopentylcyclohexane-1, 2-diamine, N-((4-aminomethyl) benzyl) -3-methylbutane-1-amine, N-((3-aminomethyl) benzyl) -3-methylbutane-1-amine, N-((2-2-aminomethyl) benzyl) Aminomethyl) benzyl) -3-methylbutane-1-amine,

N- (3-Methylbutane-2-yl) ethane-1,2-diamine, N- (3-methylbutane-2-yl) propan-1,3-diamine, N- (3-methylbutane-2-yl) butane -1,4-diamine, N- (3-methylbutane-2-yl) pentane-1,5-diamine, N- (3-methylbutane-2-yl) hexane-1,6-diamine, N- (3-) Methylbutane-2-yl) heptane-1,7-diamine, N- (3-methylbutane-2-yl) octane-1,8-diamine, N- (3-methylbutane-2-yl) nonane-1,9- Diamine, N- (3-methylbutane-2-yl) decane-1,10-diamine, N- (3-methylbutane-2-yl) undecane-1,11-diamine, N- (3-methylbutane-2-yl) ) Dodecane-1,12-diamine, N- (3-methylbutane-2-yl) benzene-1,4-diamine, N- (3-methylbutane-2-yl) benzene-1,3-diamine, N- ( 3-Methylbutane-2-yl) benzene-1,2-diamine, N- (3-methylbutane-2-yl) cyclohexane-1,4-diamine, N- (3-methylbutane-2-yl) cyclohexane-1, 3-diamine, N- (3-methylbutane-2-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -3-methylbutane-2-amine, N-((3-amino) Methyl) benzyl) -3-methylbutane-2-amine, N-((2-aminomethyl) benzyl) -3-methylbutane-2-amine,

N- (tert-pentyl) ethane-1,2-diamine, N- (tert-pentyl) propane-1,3-diamine, N- (tert-pentyl) butane-1,4-diamine, N- (tert- Pentyl) Pentan-1,5-diamine, N- (tert-pentyl) hexane-1,6-diamine, N- (tert-pentyl) heptane-1,7-diamine, N- (tert-pentyl) octane-1 , 8-Diamine, N- (tert-Pentyl) Nonan-1,9-Diamine, N- (tert-Pentyl) Decane-1,10-Diamine, N- (tert-Pentyl) Undecane-1,11-Diamine, N- (tert-pentyl) dodecane-1,12-diamine, N- (tert-pentyl) benzene-1,4-diamine, N- (tert-pentyl) benzene-1,3-diamine, N- (tert- Pentyl) benzene-1,2-diamine, N- (tert-pentyl) cyclohexane-1,4-diamine, N- (tert-pentyl) cyclohexane-1,3-diamine, N- (tert-pentyl) cyclohexane-1 , 2-Diamine, N-((4-aminomethyl) benzyl) -2-methylbutane-2-amine, N-((3-aminomethyl) benzyl) -2-methylbutane-2-amine, N-((2) -Aminomethyl) benzyl) -2-methylbutane-2-amine,

N- (2-methylbutyl) ethane-1,2-diamine, N- (2-methylbutyl) propane-1,3-diamine, N- (2-methylbutyl) butane-1,4-diamine, N- (2-) Methylbutyl) pentane-1,5-diamine, N- (2-methylbutyl) hexane-1,6-diamine, N- (2-methylbutyl) heptane-1,7-diamine, N- (2-methylbutyl) octane-1 , 8-diamine, N- (2-methylbutyl) nonane-1,9-diamine, N- (2-methylbutyl) decane-1,10-diamine, N- (2-methylbutyl) undecane-1,11-diamine, N- (2-methylbutyl) dodecane-1,12-diamine, N- (2-methylbutyl) benzene-1,4-diamine, N- (2-methylbutyl) benzene-1,3-diamine, N- (2-) Methylbutyl) benzene-1,2-diamine, N- (2-methylbutyl) cyclohexane-1,4-diamine, N- (2-methylbutyl) cyclohexane-1,3-diamine, N- (2-methylbutyl) cyclohexane-1 , 2-Diamine, N-((4-aminomethyl) benzyl) -2-methylbutane-1-amine, N-((3-aminomethyl) benzyl) -2-methylbutane-1-amine, N-((2) -Aminomethyl) benzyl) -2-methylbutane-1-amine,

N-neopentylethane-1,2-diamine, N-neopentylpropane-1,3-diamine, N-neopentylbutane-1,4-diamine, N-neopentylpentane-1,5-diamine, N- Neopentyl hexane-1,6-diamine, N-neopentyl heptane-1,7-diamine, N-neopentyl octane-1,8-diamine, N-neopentyl nonane-1,9-diamine, N-neopentyl Decane-1,10-diamine, N-neopentylundecane-1,11-diamine, N-neopentyldodecane-1,12-diamine, N-neopentylbenzene-1,4-diamine, N-neopentylbenzene- 1,3-Diamine, N-neopentylbenzene-1,2-diamine, N-neopentylcyclohexane-1,4-diamine, N-neopentylcyclohexane-1,3-diamine, N-neopentylcyclohexane-1, 2-diamine, N-((4-aminomethyl) benzyl) -2,2-dimethylpropane-1-amine, N-((3-aminomethyl) benzyl) -2,2-dimethylpropane-1-amine, N-((2-Aminomethyl) benzyl) -2,2-dimethylpropan-1-amine,

N-hexylethane-1,2-diamine, N-hexylpropane-1,3-diamine, N-hexylbutane-1,4-diamine, N-hexylpentane-1,5-diamine, N-hexylhexane-1 , 6-Diamine, N-Hexylheptane-1,7-Diamine, N-Hexyloctane-1,8-Diamine, N-Hexylnonan-1,9-Diamine, N-Hexyldecane-1,10-Diamine, N-Hexil Undecane-1,11-diamine, N-hexyldodecane-1,12-diamine, N-hexylbenzene-1,4-diamine, N-hexylbenzene-1,3-diamine, N-hexylbenzene-1,2- Diamine, N-hexylcyclohexane-1,4-diamine, N-hexylcyclohexane-1,3-diamine, N-hexylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) hexane-1- Amin, N-((3-aminomethyl) benzyl) hexane-1-amine, N-((2-aminomethyl) benzyl) hexane-1-amine,

N- (Hexane-2-yl) ethane-1,2-diamine, N- (hexane-2-yl) propane-1,3-diamine, N- (hexane-2-yl) butane-1,4-diamine , N- (Hexane-2-yl) Pentan-1,5-diamine, N- (Hexane-2-yl) Hexane-1,6-diamine, N- (Hexane-2-yl) Heptane-1,7- Diamine, N- (Hexane-2-yl) Octane-1,8-Diamine, N- (Hexane-2-yl) Nonan-1,9-Diamine, N- (Hexane-2-yl) Decane-1,10 -Diamine, N- (Hexane-2-yl) undecane-1,11-diamine, N- (Hexane-2-yl) dodecane-1,12-diamine, N- (Hexane-2-yl) benzene-1, 4-Diamine, N- (Hexane-2-yl) benzene-1,3-diamine, N- (Hexane-2-yl) benzene-1,2-diamine, N- (Hexane-2-yl) cyclohexane-1 , 4-Diamine, N- (Hexane-2-yl) Cyclohexane-1,3-Diamine, N- (Hexane-2-yl) Cyclohexane-1,2-Diamine, N-((4-Aminomethyl) benzyl) Hexane-2-amine, N-((3-aminomethyl) benzyl) hexane-2-amine, N-((2-aminomethyl) benzyl) hexane-2-amine,

N- (Hexane-3-yl) ethane-1,2-diamine, N- (hexane-3-yl) propane-1,3-diamine, N- (hexane-3-yl) butane-1,4-diamine , N- (Hexane-3-yl) Pentan-1,5-diamine, N- (Hexane-3-yl) Hexane-1,6-diamine, N- (Hexane-3-yl) Heptane-1,7- Diamine, N- (Hexane-3-yl) Octane-1,8-Diamine, N- (Hexane-3-yl) Nonan-1,9-Diamine, N- (Hexane-3-yl) Decane-1,10 -Diamine, N- (Hexane-3-yl) undecane-1,11-diamine, N- (Hexane-3-yl) dodecane-1,12-diamine, N- (Hexane-3-yl) benzene-1, 4-Diamine, N- (Hexane-3-yl) benzene-1,3-Diamine, N- (Hexane-3-yl) benzene-1,2-diamine, N- (Hexane-3-yl) Cyclohexane-1 , 4-Diamine, N- (Hexane-3-yl) Cyclohexane-1,3-Diamine, N- (Hexane-3-yl) Cyclohexane-1,2-Diamine, N-((4-Aminomethyl) benzyl) Hexane-3-amine, N-((3-aminomethyl) benzyl) hexane-3-amine, N-((2-aminomethyl) benzyl) hexane-3-amine,

N- (4-methylpentyl) ethane-1,2-diamine, N- (4-methylpentyl) propan-1,3-diamine, N- (4-methylpentyl) butane-1,4-diamine, N- (4-Methylpentyl) pentane-1,5-diamine, N- (4-methylpentyl) hexane-1,6-diamine, N- (4-methylpentyl) heptane-1,7-diamine, N- (4) -Methylpentyl) octane-1,8-diamine, N- (4-methylpentyl) nonane-1,9-diamine, N- (4-methylpentyl) decane-1,10-diamine, N- (4-methyl) Pentyl) undecane-1,11-diamine, N- (4-methylpentyl) dodecane-1,12-diamine, N- (4-methylpentyl) benzene-1,4-diamine, N- (4-methylpentyl) Benzene-1,3-diamine, N-((4-methylpentyl) benzene-1,2-diamine, N- (4-methylpentyl) cyclohexane-1,4-diamine, N- (4-methylpentyl) cyclohexane -1,3-diamine, N- (4-methylpentyl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -4-methylpentane-1-amine, N-((3-aminomethyl) benzyl) Aminomethyl) benzyl) -4-methylpentane-1-amine, N-((2-aminomethyl) benzyl) -4-methylpentane-1-amine,

N- (4-methylpentane-2-yl) ethane-1,2-diamine, N- (4-methylpentan-2-yl) propan-1,3-diamine, N- (4-methylpentane-2-yl) Il) Butane-1,4-diamine, N- (4-methylpentane-2-yl) pentane-1,5-diamine, N- (4-methylpentane-2-yl) hexane-1,6-diamine, N- (4-methylpentane-2-yl) heptane-1,7-diamine, N- (4-methylpentane-2-yl) octane-1,8-diamine, N- (4-methylpentane-2-yl) Il) Nonan-1,9-diamine, N- (4-methylpentane-2-yl) decane-1,10-diamine, N- (4-methylpentane-2-yl) undecane-1,11-diamine, N- (4-methylpentane-2-yl) dodecane-1,12-diamine, N- (4-methylpentan-2-yl) benzene-1,4-diamine, N- (4-methylpentane-2-yl) Il) benzene-1,3-diamine, N- (4-methylpentane-2-yl) benzene-1,2-diamine, N- (4-methylpentane-2-yl) cyclohexane-1,4-diamine, N- (4-methylpentane-2-yl) cyclohexane-1,3-diamine, N- (4-methylpentan-2-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl ) -4-Methylpentane-2-amine, N-((3-aminomethyl) benzyl) -4-methylpentane-2-amine, N-((2-aminomethyl) benzyl) -4-methylpentane-2 -Amin,

N- (2-Methylpentane-3-yl) ethane-1,2-diamine, N- (2-methylpentane-3-yl) propan-1,3-diamine, N- (2-methylpentane-3-yl) Il) Butane-1,4-diamine, N- (2-methylpentane-3-yl) pentane-1,5-diamine, N- (2-methylpentane-3-yl) hexane-1,6-diamine, N- (2-Methylpentane-3-yl) heptane-1,7-diamine, N- (2-methylpentane-3-yl) octane-1,8-diamine, N- (2-methylpentane-3-yl) Il) Nonan-1,9-diamine, N- (2-methylpentane-3-yl) decane-1,10-diamine, N- (2-methylpentane-3-yl) undecane-1,11-diamine, N- (2-Methylpentane-3-yl) dodecane-1,12-diamine, N- (2-methylpentane-3-yl) benzene-1,4-diamine, N- (2-methylpentane-3-yl) Il) benzene-1,3-diamine, N- (2-methylpentane-3-yl) benzene-1,2-diamine, N- (2-methylpentane-3-yl) cyclohexane-1,4-diamine, N- (2-Methylpentane-3-yl) cyclohexane-1,3-diamine, N- (2-methylpentane-3-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl ) -2-Methylpentane-3-amine, N-((3-aminomethyl) benzyl) -2-methylpentane-3-amine, N-((2-aminomethyl) benzyl) -2-methylpentane-3 -Amin,

N- (2-Methylpentane-2-yl) ethane-1,2-diamine, N- (2-methylpentane-2-yl) propan-1,3-diamine, N- (2-methylpentane-2-yl) Il) Butane-1,4-diamine, N- (2-methylpentane-2-yl) pentane-1,5-diamine, N- (2-methylpentane-2-yl) hexane-1,6-diamine, N- (2-Methylpentane-2-yl) heptane-1,7-diamine, N- (2-methylpentane-2-yl) octane-1,8-diamine, N- (2-methylpentane-2-yl) Il) Nonan-1,9-diamine, N- (2-methylpentane-2-yl) decane-1,10-diamine, N- (2-methylpentane-2-yl) undecane-1,11-diamine, N- (2-Methylpentane-2-yl) dodecane-1,12-diamine, N- (2-methylpentane-2-yl) benzene-1,4-diamine, N- (2-methylpentane-2-yl) Il) benzene-1,3-diamine, N- (2-methylpentane-2-yl) benzene-1,2-diamine, N- (2-methylpentane-2-yl) cyclohexane-1,4-diamine, N- (2-Methylpentane-2-yl) cyclohexane-1,3-diamine, N- (2-methylpentane-2-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl ) -2-Methylpentane-2-amine, N-((3-aminomethyl) benzyl) -2-methylpentane-2-amine, N-((2-aminomethyl) benzyl) -2-methylpentane-2 -Amin,

N- (2-Methylpentane-2-yl) ethane-1,2-diamine, N- (2-methylpentane-2-yl) propan-1,3-diamine, N- (2-methylpentane-2-yl) Il) Butane-1,4-diamine, N- (2-methylpentane-2-yl) pentane-1,5-diamine, N- (2-methylpentane-2-yl) hexane-1,6-diamine, N- (2-Methylpentane-2-yl) heptane-1,7-diamine, N- (2-methylpentane-2-yl) octane-1,8-diamine, N- (2-methylpentane-2-yl) Il) Nonan-1,9-diamine, N- (2-methylpentane-2-yl) decane-1,10-diamine, N- (2-methylpentane-2-yl) undecane-1,11-diamine, N- (2-Methylpentane-2-yl) dodecane-1,12-diamine, N- (2-methylpentane-2-yl) benzene-1,4-diamine, N- (2-methylpentane-2-yl) Il) benzene-1,3-diamine, N- (2-methylpentane-2-yl) benzene-1,2-diamine, N- (2-methylpentane-2-yl) cyclohexane-1,4-diamine, N- (2-Methylpentane-2-yl) cyclohexane-1,3-diamine, N- (2-methylpentane-2-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl ) -2-Methylpentane-2-amine, N-((3-aminomethyl) benzyl) -2-methylpentane-2-amine, N-((2-aminomethyl) benzyl) -2-methylpentane-2 -Amin,

N- (2-methylpentyl) ethane-1,2-diamine, N- (2-methylpentyl) propan-1,3-diamine, N- (2-methylpentyl) butane-1,4-diamine, N- (2-Methylpentyl) pentane-1,5-diamine, N- (2-methylpentyl) hexane-1,6-diamine, N- (2-methylpentyl) heptane-1,7-diamine, N- (2) -Methylpentyl) octane-1,8-diamine, N- (2-methylpentyl) nonane-1,9-diamine, N- (2-methylpentyl) decane-1,10-diamine, N- (2-methyl) Pentyl) undecane-1,11-diamine, N- (2-methylpentyl) dodecane-1,12-diamine, N- (2-methylpentyl) benzene-1,4-diamine, N- (2-methylpentyl) Benzene-1,3-diamine, N- (2-methylpentyl) benzene-1,2-diamine, N- (2-methylpentyl) cyclohexane-1,4-diamine, N- (2-methylpentyl) cyclohexane- 1,3-Diamine, N- (2-methylpentyl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -2-methylpentane-1-amine, N-((3-amino) Methyl) benzyl) -2-methylpentane-1-amine, N-((2-aminomethyl) benzyl) -2-methylpentane-1-amine,

N- (3-Methylpentyl) ethane-1,2-diamine, N- (3-methylpentyl) propan-1,3-diamine, N- (3-methylpentyl) butane-1,4-diamine, N- (3-Methylpentyl) pentane-1,5-diamine, N- (3-methylpentyl) hexane-1,6-diamine, N- (3-methylpentyl) heptane-1,7-diamine, N- (3) -Methylpentyl) octane-1,8-diamine, N- (3-methylpentyl) nonane-1,9-diamine, N- (3-methylpentyl) decane-1,10-diamine, N- (3-methyl) Pentyl) undecane-1,11-diamine, N- (3-methylpentyl) dodecane-1,12-diamine, N- (3-methylpentyl) benzene-1,4-diamine, N- (3-methylpentyl) Benzene-1,3-diamine, N- (3-methylpentyl) benzene-1,2-diamine, N- (3-methylpentyl) cyclohexane-1,4-diamine, N- (3-methylpentyl) cyclohexane- 1,3-Diamine, N- (3-methylpentyl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -3-methylpentane-1-amine, N-((3-amino) Methyl) benzyl) -3-methylpentane-1-amine, N-((2-aminomethyl) benzyl) -3-methylpentane-1-amine,

N- (3-Methylpentane-2-yl) ethane-1,2-diamine, N- (3-methylpentane-2-yl) propan-1,3-diamine, N- (3-methylpentane-2-yl) Il) Butane-1,4-diamine, N- (3-methylpentane-2-yl) pentane-1,5-diamine, N- (3-methylpentane-2-yl) hexane-1,6-diamine, N- (3-Methylpentane-2-yl) heptane-1,7-diamine, N- (3-methylpentane-2-yl) octane-1,8-diamine, N- (3-methylpentane-2-yl) Il) Nonan-1,9-diamine, N- (3-methylpentane-2-yl) decane-1,10-diamine, N- (3-methylpentane-2-yl) undecane-1,11-diamine, N- (3-Methylpentane-2-yl) dodecane-1,12-diamine, N- (3-methylpentane-2-yl) benzene-1,4-diamine, N- (3-methylpentane-2-yl) Il) benzene-1,3-diamine, N- (3-methylpentane-2-yl) benzene-1,2-diamine, N- (3-methylpentane-2-yl) cyclohexane-1,4-diamine, N- (3-Methylpentane-2-yl) cyclohexane-1,3-diamine, N- (3 (3-methylpentane-2-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) ) Benzyl) -3-methylpentane-2-amine, N-((3-aminomethyl) benzyl) -3-methylpentane-2-amine, N-((2-aminomethyl) benzyl) -3-methylpentane -2-Amin,

N- (3-Methylpentane-3-yl) ethane-1,2-diamine, N- (3-methylpentane-3-yl) propan-1,3-diamine, N- (3-methylpentane-3-yl) Il) Butane-1,4-diamine, N- (3-methylpentane-3-yl) pentane-1,5-diamine, N- (3-methylpentane-3-yl) hexane-1,6-diamine, N- (3-Methylpentane-3-yl) heptane-1,7-diamine, N- (3-methylpentane-3-yl) octane-1,8-diamine, N- (3-methylpentane-3-yl) Il) Nonan-1,9-diamine, N- (3-methylpentane-3-yl) decane-1,10-diamine, N- (3-methylpentane-3-yl) undecane-1,11-diamine, N- (3-Methylpentane-3-yl) dodecane-1,12-diamine, N- (3-methylpentane-3-yl) benzene-1,4-diamine, N- (3-methylpentane-3-yl) Il) benzene-1,3-diamine, N- (3-methylpentane-3-yl) benzene-1,2-diamine, N- (3-methylpentane-3-yl) cyclohexane-1,4-diamine, N- (3-Methylpentane-3-yl) cyclohexane-1,3-diamine, N- (3 (3-methylpentane-3-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) ) Benzyl) -3-methylpentane-3-amine, N-((3-aminomethyl) benzyl) -3-methylpentane-3-amine, N-((2-aminomethyl) benzyl) -3-methylpentane -3-amine,

N- (2-ethylbutyl) ethane-1,2-diamine, N- (2-ethylbutyl) propane-1,3-diamine, N- (2-ethylbutyl) butane-1,4-diamine, N- (2-) Ethylbutyl) pentane-1,5-diamine, N- (2-ethylbutyl) hexane-1,6-diamine, N- (2-ethylbutyl) heptane-1,7-diamine, N-((2-ethylbutyl) octane- 1,8-Diamine, N- (2-ethylbutyl) nonane-1,9-diamine, N- (2-ethylbutyl) decane-1,10-diamine, N- (2-ethylbutyl) undecane-1,11-diamine , N- (2-ethylbutyl) dodecane-1,12-diamine, N- (2-ethylbutyl) benzene-1,4-diamine, N- (2-ethylbutyl) benzene-1,3-diamine, N- (2) -Ethylbutyl) benzene-1,2-diamine, N- (2-ethylbutyl) cyclohexane-1,4-diamine, N- (2-ethylbutyl) cyclohexane-1,3-diamine, N- (2-ethylbutyl) cyclohexane- 1,2-diamine, N-((4-aminomethyl) benzyl) -2-ethylbutane-1-amine, N-((3-aminomethyl) benzyl) -2-ethylbutane-1-amine, N-(( 2-Aminomethyl) benzyl) -2-ethylbutane-1-amine,

N- (2,3-dimethylbutyl) ethane-1,2-diamine, N- (2,3-dimethylbutyl) propane-1,3-diamine, N- (2,3-dimethylbutyl) butane-1, 4-diamine, N- (2,3-dimethylbutyl) pentane-1,5-diamine, N- (2,3-dimethylbutyl) hexane-1,6-diamine, N- (2,3-dimethylbutyl) Heptane-1,7-diamine, N- (2,3-dimethylbutyl) octane-1,8-diamine, N- (2,3-dimethylbutyl) nonane-1,9-diamine, N- (2,3) -Dimethylbutyl) decane-1,10-diamine, N- (2,3-dimethylbutyl) undecane-1,11-diamine, N- (2-ethylbutyl) (2,3-dimethylbutyl) dodecane-1,12 -Diamine, N- (2,3-dimethylbutyl) benzene-1,4-diamine, N- (2,3-dimethylbutyl) benzene-1,3-diamine, N- (2,3-dimethylbutyl) benzene -1,2-diamine, N- (2,3-dimethylbutyl) cyclohexane-1,4-diamine, N- (2,3-dimethylbutyl) cyclohexane-1,3-diamine, N- (2,3-diamine) Dimethylbutyl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -2,3-dimethylbutane-1-amine, N-((3-aminomethyl) benzyl) -2,3- Dimethylbutane-1-amine, N-((2-aminomethyl) benzyl) -2,3-dimethylbutane-1-amine,

N- (2,3-Dimethylbutane-2-yl) ethane-1,2-diamine, N- (2,3-dimethylbutane-2-yl) propane-1,3-diamine, N- (2,3) -Dimethylbutane-2-yl) butane-1,4-diamine, N- (2,3-dimethylbutane-2-yl) pentane-1,5-diamine, N- (2,3-dimethylbutane-2-) Ile) Hexane-1,6-diamine, N- (2,3-dimethylbutane-2-yl) heptane-1,7-diamine, N- (2,3-dimethylbutane-2-yl) octane-1, 8-diamine, N- (2,3-dimethylbutane-2-yl) nonane-1,9-diamine, N- (2,3-dimethylbutane-2-yl) decane-1,10-diamine, N- (2,3-Dimethylbutane-2-yl) undecane-1,11-diamine, N- (2-ethylbutyl) (2,3-dimethylbutane-2-yl) dodecane-1,12-diamine, N-( 2,3-Dimethylbutane-2-yl) benzene-1,4-diamine, N- (2,3-dimethylbutane-2-yl) benzene-1,3-diamine, N- (2,3-dimethylbutane) -2-yl) benzene-1,2-diamine, N- (2,3-dimethylbutane-2-yl) cyclohexane-1,4-diamine, N- (2,3-dimethylbutane-2-yl) cyclohexane -1,3-diamine, N- (2,3-dimethylbutane-2-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -2,3-dimethylbutane-2- Amine, N-((3-aminomethyl) benzyl) -2,3-dimethylbutane-2-amine, N-((2-aminomethyl) benzyl) -2,3-dimethylbutane-2-amine,

N- (2,2-dimethylbutyl) ethane-1,2-diamine, N- (2,2-dimethylbutyl) propane-1,3-diamine, N- (2,2-dimethylbutyl) butane-1, 4-diamine, N- (2,2-dimethylbutyl) pentane-1,5-diamine, N- (2,2-dimethylbutyl) hexane-1,6-diamine, N- (2,2-dimethylbutyl) Heptane-1,7-diamine, N- (2,2-dimethylbutyl) octane-1,8-diamine, N- (2,2-dimethylbutyl) nonane-1,9-diamine, N- (2,2) -Dimethylbutyl) decane-1,10-diamine, N- (2,2-dimethylbutyl) undecane-1,11-diamine, N- (2-ethylbutyl) (2,2-dimethylbutyl) dodecane-1,12 -Diamine, N- (2,2-dimethylbutyl) benzene-1,4-diamine, N- (2,2-dimethylbutyl) benzene-1,3-diamine, N- (2,2-dimethylbutyl) benzene -1,2-diamine, N- (2,2-dimethylbutyl) cyclohexane-1,4-diamine, N- (2,2-dimethylbutyl) cyclohexane-1,3-diamine, N- (2,2-diamine) Dimethylbutyl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -2,2-dimethylbutane-1-amine, N-((3-aminomethyl) benzyl) -2,2- Dimethylbutane-1-amine, N-((2-aminomethyl) benzyl) -2,2-dimethylbutane-1-amine,
N- (3,3-dimethylbutane-2-yl) ethane-1,2-diamine, N- (3,3-dimethylbutan-2-yl) propan-1,3-diamine, N- (3,3) -Dimethylbutane-2-yl) butane-1,4-diamine, N- (3,3-dimethylbutane-2-yl) pentane-1,5-diamine, N- (3,3-dimethylbutane-2-yl) Il) Hexane-1,6-diamine, N- (3,3-dimethylbutane-2-yl) heptane-1,7-diamine, N- (3,3-dimethylbutan-2-yl) octane-1, 8-diamine, N- (3,3-dimethylbutane-2-yl) nonane-1,9-diamine, N- (3,3-dimethylbutan-2-yl) decane-1,10-diamine, N- (3,3-Dimethylbutane-2-yl) undecane-1,11-diamine, N- (2-ethylbutyl) (3,3-dimethylbutan-2-yl) dodecane-1,12-diamine, N-( 3,3-Dimethylbutane-2-yl) benzene-1,4-diamine, N- (3,3-dimethylbutane-2-yl) benzene-1,3-diamine, N- (3,3-dimethylbutane) -2-yl) benzene-1,2-diamine, N- (3,3-dimethylbutane-2-yl) cyclohexane-1,4-diamine, N- (3,3-dimethylbutane-2-yl) cyclohexane -1,3-diamine, N- (3,3-dimethylbutane-2-yl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -3,3-dimethylbutane-2- Amin, N-((3-aminomethyl) benzyl) -3,3-dimethylbutane-2-amine, N-((2-aminomethyl) benzyl) -3,3-dimethylbutane-2-amine,

N- (3,3-dimethylbutyl) ethane-1,2-diamine, N- (3,3-dimethylbutyl) propane-1,3-diamine, N- (3,3-dimethylbutyl) butane-1, 4-diamine, N- (3,3-dimethylbutyl) pentane-1,5-diamine, N- (3,3-dimethylbutyl) hexane-1,6-diamine, N- (3,3-dimethylbutyl) Heptane-1,7-diamine, N- (3,3-dimethylbutyl) octane-1,8-diamine, N- (3,3-dimethylbutyl) nonane-1,9-diamine, N- (3,3) -Dimethylbutyl) decane-1,10-diamine, N- (3,3-dimethylbutyl) undecane-1,11-diamine, N- (2-ethylbutyl) (3,3-dimethylbutyl) dodecane-1,12 -Diamine, N- (3,3-dimethylbutyl) benzene-1,4-diamine, N- (3,3-dimethylbutyl) benzene-1,3-diamine, N- (3,3-dimethylbutyl) benzene -1,2-diamine, N- (3,3-dimethylbutyl) cyclohexane-1,4-diamine, N- (3,3-dimethylbutyl) cyclohexane-1,3-diamine, N- (3,3-diamine) Dimethylbutyl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -3,3-dimethylbutane-1-amine, N-((3-aminomethyl) benzyl) -3,3- Dimethylbutane-1-amine, N-((2-aminomethyl) benzyl) -3,3-dimethylbutane-1-amine,

N-Cyclohexylethane-1,2-diamine, N-cyclohexylpropane-1,3-diamine, N-cyclohexylbutane-1,4-diamine, N-cyclohexylpentane-1,5-diamine, N-cyclohexylhexane-1 , 6-Diamine, N-Cyclohexylheptan-1,7-Diamine, N-Cyclohexyloctane-1,8-Diamine, N-Cyclohexylnonan-1,9-Diamine, N-Cyclohexyldecane-1,10-diamine, N -Cyclohexylundecane-1,11-diamine, N-cyclohexylhydrate-1,12-diamine, N-cyclohexylbenzene-1,4-diamine, N-cyclohexylbenzene-1,3-diamine, N-cyclohexylbenzene-1, 2-Diamine, N-cyclohexylcyclohexane-1,4-diamine, N-cyclohexylcyclohexane-1,3-diamine, N-cyclohexylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) cyclohexaneamine , N-((3-aminomethyl) benzyl) cyclohexaneamine, N-((2-aminomethyl) benzyl) cyclohexaneamine,

N- (cyclohexylmethyl) ethane-1,2-diamine, N- (cyclohexylmethyl) propan-1,3-diamine, N- (cyclohexylmethyl) butane-1,4-diamine, N- (cyclohexylmethyl) pentane- 1,5-diamine, N- (cyclohexylmethyl) hexane-1,6-diamine, N- (cyclohexylmethyl) heptane-1,7-diamine, N- (cyclohexylmethyl) octane-1,8-diamine, N- (Cyclohexylmethyl) nonane-1,9-diamine, N- (cyclohexylmethyl) decane-1,10-diamine, N- (cyclohexylmethyl) undecane-1,11-diamine, N- (cyclohexylmethyl) dodecane-1, 12-Diamine, N- (cyclohexylmethyl) benzene-1,4-diamine, N- (cyclohexylmethyl) benzene-1,3-diamine, N- (cyclohexylmethyl) benzene-1,2-diamine, N- (cyclohexyl) Methyl) cyclohexane-1,4-diamine, N- (cyclohexylmethyl) cyclohexane-1,3-diamine, N- (cyclohexylmethyl) cyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl)- 1-Cyclohexylmethaneamine, N-((3-aminomethyl) benzyl) -1-cyclohexylmethaneamine, N-((2-aminomethyl) benzyl) -1-cyclohexylmethaneamine,
N-phenylethane-1,2-diamine, N-phenylpropane-1,3-diamine, N-phenylbutane-1,4-diamine, N-phenylpentane-1,5-diamine, N-phenylhexane-1 , 6-Diamine, N-phenylheptane-1,7-diamine, N-phenyloctane-1,8-diamine, N-phenylnonan-1,9-diamine, N-phenyldecane-1,10-diamine, N -Phenylundecane-1,11-diamine, N-phenyldodecane-1,12-diamine, N-phenylbenzene-1,4-diamine, N-phenylbenzene-1,3-diamine, N-phenylbenzene-1, 2-Diamine, N-phenylcyclohexane-1,4-diamine, N-phenylcyclohexane-1,3-diamine, N-phenylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) aniline, N-((3-aminomethyl) benzyl) aniline, N-((2-aminomethyl) benzyl) aniline,

N-Benzylethane-1,2-diamine, N-benzylpropane-1,3-diamine, N-benzylbutane-1,4-diamine, N-benzylpentane-1,5-diamine, N-benzylhexane-1 , 6-Diamine, N-benzylheptane-1,7-diamine, N-benzyloctane-1,8-diamine, N-benzylnonan-1,9-diamine, N-benzyldecane-1,10-diamine, N -Benzylundecane-1,11-diamine, N-benzyldodecane-1,12-diamine, N-benzylbenzene-1,4-diamine, N-benzylbenzene-1,3-diamine, N-benzylbenzene-1, 2-Diamine, N-benzylcyclohexane-1,4-diamine, N-benzylcyclohexane-1,3-diamine, N-benzylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) -1 -Phenylmethaneamine, N-((3-aminomethyl) benzyl) -1-phenylmethaneamine, N-((2-aminomethyl) benzyl) -1-phenylmethaneamine,

2- (Piperazine-1-yl) ethane-1-amine, 3- (piperazine-1-yl) propan-1-amine, 4- (piperazine-1-yl) butane-1-amine, 5- (piperazin-) 1-yl) pentane-1-amine, 6- (piperazin-1-yl) hexane-1-amine, 7- (piperazin-1-yl) heptane-1-amine, 8- (piperazin-1-yl) octane -1-Amine, 9- (piperazin-1-yl) nonane-1-amine, 10- (piperazin-1-yl) decane-1-amine, 11- (piperazin-1-yl) undecane-1-amine, 12- (piperazin-1-yl) dodecane-1-amine, 4- (piperazin-1-yl) aniline, 3- (piperazin-1-yl) aniline, 2- (piperazin-1-yl) aniline, 4- (Piperazine-1-yl) cyclohexane-1-amine, 3- (piperazine-1-yl) cyclohexane-1-amine, 2- (piperazine-1-yl) cyclohexane-1-amine, (4- (piperazine-1) -Ilmethyl) phenyl) methaneamine, (3- (piperazine-1-ylmethyl) phenyl) methaneamine, (2- (piperazine-1-ylmethyl) phenyl) methaneamine,

2- (Piperidin-1-yl) ethane-1-amine, 3- (piperidin-1-yl) propan-1-amine, 4- (piperidin-1-yl) butane-1-amine, 5- (piperidin-) 1-yl) pentane-1-amine, 6- (piperidin-1-yl) hexane-1-amine, 7- (piperidin-1-yl) heptane-1-amine, 8- (piperidin-1-yl) octane -1-Amine, 9- (piperidin-1-yl) nonane-1-amine, 10- (piperidin-1-yl) decane-1-amine, 11- (piperidin-1-yl) undecane-1-amine, 12- (piperidin-1-yl) dodecane-1-amine, 4- (piperidin-1-yl) aniline, 3- (piperidin-1-yl) aniline, 2- (piperidin-1-yl) aniline, 4- (Piperidin-1-yl) cyclohexane-1-amine, 3- (piperidin-1-yl) cyclohexane-1-amine, 2- (piperidin-1-yl) cyclohexane-1-amine, (4- (piperidin-1) -Ilmethyl) phenyl) methaneamine, (3- (piperidine-1-ylmethyl) phenyl) methaneamine, (2- (piperidine-1-ylmethyl) phenyl) methaneamine,

2- (Piperidin-4-yl) ethane-1-amine, 3- (piperidin-4-yl) propan-1-amine, 4- (piperidin-4-yl) butane-1-amine, 5- (piperidin-) 4-yl) pentane-1-amine, 6- (piperidin-4-yl) hexane-1-amine, 7- (piperidin-4-yl) heptane-1-amine, 8- (piperidin-4-yl) octane -1-amine, 9- (piperidin-4-yl) nonane-1-amine, 10- (piperidin-4-yl) decane-1-amine, 11- (piperidin-4-yl) undecane-1-amine, 12- (piperidin-4-yl) dodecane-1-amine, 4- (piperidin-4-yl) aniline, 3- (piperidin-4-yl) aniline, 2- (piperidin-4-yl) aniline, 4- (Piperidin-4-yl) cyclohexane-1-amine, 3- (piperidin-4-yl) cyclohexane-1-amine, 2- (piperidin-4-yl) cyclohexane-1-amine, (4- (piperidin-4) -Ilmethyl) phenyl) methaneamine, (3- (piperidine-4-ylmethyl) phenyl) methaneamine, (2- (piperidine-4-ylmethyl) phenyl) methaneamine,

N-heptylethane-1,2-diamine, N-heptylpropane-1,3-diamine, N-heptylbutane-1,4-diamine, N-heptylpentane-1,5-diamine, N-heptyl Hexyl-1,6-diamine, N-heptylheptan-1,7-diamine, N-heptyloctane-1,8-diamine, N-heptylnonan-1,9-diamine, N-heptyldecane-1,10 -Diamine, N-heptylundecane-1,11-diamine, N-heptyldodecane-1,12-diamine, N-heptylbenzene-1,4-diamine, N-heptylbenzene-1,3-diamine, N-Heptylbenzene-1,2-diamine, N-Heptylcyclohexane-1,4-diamine, N-Heptylcyclohexane-1,3-diamine, N-Heptylcyclohexane-1,2-diamine, N- ((4-Aminomethyl) benzyl) heptane-1-amine, N-((3-aminomethyl) benzyl) heptane-1-amine, N-((2-aminomethyl) benzyl) heptane-1-amine,

N-octylethane-1,2-diamine, N-octylpropane-1,3-diamine, N-octylbutane-1,4-diamine, N-octylpentane-1,5-diamine, N-octylhexane-1 , 6-Diamine, N-octylheptan-1,7-diamine, N-octyloctane-1,8-diamine, N-octylnonan-1,9-diamine, N-octyldecane-1,10-diamine, N -Octylundecane-1,11-diamine, N-octyldodecane-1,12-diamine, N-octylbenzene-1,4-diamine, N-octylbenzene-1,3-diamine, N-octylbenzene-1, 2-Diamine, N-octylcyclohexane-1,4-diamine, N-octylcyclohexane-1,3-diamine, N-octylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) octane- 1-amine, N-((3-aminomethyl) benzyl) octane-1-amine, N-((2-aminomethyl) benzyl) octane-1-amine,

N-nonylethane-1,2-diamine, N-nonylpropane-1,3-diamine, N-nonylbutane-1,4-diamine, N-nonylpentane-1,5-diamine, N-nonylhexane-1,6 -Diamine, N-nonylheptan-1,7-diamine, N-nonyloctane-1,8-diamine, N-nonylnonan-1,9-diamine, N-nonyldecane-1,10-diamine, N-nonylundecane- 1,11-diamine, N-nonyldodecane-1,12-diamine, N-nonylbenzene-1,4-diamine, N-nonylbenzene-1,3-diamine, N-nonylbenzene-1,2-diamine, N -Nonylcyclohexane-1,4-diamine, N-nonylcyclohexane-1,3-diamine, N-nonylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) nonane-1-amine, N -((3-Aminomethyl) benzyl) nonane-1-amine, N-((2-aminomethyl) benzyl) nonan-1-amine,

N-decylethane-1,2-diamine, N-decylpropane-1,3-diamine, N-decylbutane-1,4-diamine, N-decylpentane-1,5-diamine, N-decylhexane-1,6 -Diamine, N-decylheptan-1,7-diamine, N-decyloctane-1,8-diamine, N-decylnonan-1,9-diamine, N-decyldecane-1,10-diamine, N-decylundecane- 1,11-Diamine, N-decyldodecane-1,12-diamine, N-decylbenzene-1,4-diamine, N-decylbenzene-1,3-diamine, N-decylbenzene-1,2-diamine, N -Decilcyclohexane-1,4-diamine, N-decylcyclohexane-1,3-diamine, N-decylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) decane-1-amine, N -((3-Aminomethyl) benzyl) diamine-1-amine, N-((2-aminomethyl) benzyl) diamine-1-amine,

N-Undecylethane-1,2-diamine, N-Undecylpropane-1,3-diamine, N-Undecylbutane-1,4-diamine, N-Undecylpentane-1,5-diamine, N- Undecylhexane-1,6-diamine, N-Undecylheptane-1,7-diamine, N-Undecyloctane-1,8-diamine, N-Undecylnonan-1,9-diamine, N-Undecyldecane-1, 10-Diamine, N-Undecyl Undecane-1,11-Diamine, N-Undecyldodecane-1,12-Diamine, N-Undecylbenzene-1,4-Diamine, N-Undecylbenzene-1,3- Diamine, N-Undecylbenzene-1,2-Diamine, N-Undecylcyclohexane-1,4-Diamine, N-Undecylcyclohexane-1,3-Diamine, N-Undecylcyclohexane-1,2-Diamine, N-((4-aminomethyl) benzyl) undecane-1-amine, N-((3-aminomethyl) benzyl) undecane-1-amine, N-((2-aminomethyl) benzyl) undecane-1-amine ,

N-dodecylethane-1,2-diamine, N-dodecylpropane-1,3-diamine, N-dodecylbutane-1,4-diamine, N-dodecylpentane-1,5-diamine, N-dodecylhexane-1 , 6-Diamine, N-Dodecylheptane-1,7-Diamine, N-Dodecyloctane-1,8-Diamine, N-Dodecylnonane-1,9-Diamine, N-Dodecyldecane-1,10-Diamine, N -Dodecylundecane-1,11-diamine, N-dodecyldodecane-1,12-diamine, N-dodecylbenzene-1,4-diamine, N-dodecylbenzene-1,3-diamine, N-dodecylbenzene-1, 2-Diamine, N-dodecylcyclohexane-1,4-diamine, N-dodecylcyclohexane-1,3-diamine, N-dodecylcyclohexane-1,2-diamine, N-((4-aminomethyl) benzyl) dodecane- 1-amine, N-((3-aminomethyl) benzyl) dodecane-1-amine, N-((2-aminomethyl) benzyl) dodecane-1-amine,

N, N'-dimethylethane-1,2-diamine, N, N'-dimethylpropane-1,3-diamine, N, N'-dimethylbutane-1,4-diamine, N, N'-dimethylpentane- 1,5-diamine, N, N'-dimethylhexane-1,6-diamine, N, N'-dimethylheptane-1,7-diamine, N, N'-dimethyloctane-1,8-diamine, N, N'-dimethylnonan-1,9-diamine, N, N'-dimethyldecane-1,10-diamine, N, N'-dimethylundecane-1,11-diamine, N, N'-dimethyldodecane-1, 12-diamine, N, N'-dimethylbenzene-1,4-diamine, N, N'-dimethylbenzene-1,3-diamine, N, N'-dimethylbenzene-1,2-diamine, N, N' -Dimethylcyclohexane-1,4-diamine, N, N'-dimethylcyclohexane-1,3-diamine, N, N'-dimethylcyclohexane-1,2-diamine, 1,1'-(1,4-phenylene) Bis (N-methylmethaneamine), 1,1'-(1,3-phenylene) bis (N-methylmethaneamine), 1,1'-(1,2-phenylene) bis (N-methylmethaneamine)

The above-mentioned "compound having NHx (x = 0 to 2)" is preferably a secondary amino group in which NHx is x = 1, and at least one of the α, β-unsaturated carboxylic acids or an induction thereof or the like. It is a structure having a primary amino group that reacts with. Further, the bulkier the substituent of the secondary amino group of x = 1, the more difficult it is for the secondary amino group to undergo nucleophilic addition to the carbonyl group, and the primary amino group reacts preferentially to the secondary amino group side. It will be possible to introduce it into the chain.

[Method for producing modified block copolymer]
The modified block copolymer (a) contained in the resin composition of the present embodiment is not limited to the following, but for example, a vinyl aromatic compound and a conjugated diene in an organic solvent using an organic alkali metal compound as a polymerization initiator. It can be produced by carrying out polymerization using a compound to obtain a block copolymer, and then carrying out a modification reaction.
The modified block copolymer (a) can be preferably produced by carrying out a hydrogenation reaction and a modification reaction of the block copolymer. The hydrogenation reaction and the denaturation reaction are not limited to this order and may be reversed. The polymerization mode may be batch polymerization, continuous polymerization, or a combination thereof.
From the viewpoint of obtaining a block copolymer having a narrow molecular weight distribution and high strength, the batch polymerization method is preferable.

The polymerization temperature is generally 0 to 180 ° C., preferably 20 to 160 ° C., more preferably 30 to 150 ° C.
The polymerization time varies depending on the target polymer, but is usually within 48 hours, preferably 0.1 to 10 hours. From the viewpoint of obtaining a block copolymer having a narrow molecular weight distribution and high strength, the polymerization time is more preferably 0.5 to 5 hours.
The atmosphere of the polymerization system is not particularly limited as long as it is in a pressure range sufficient to maintain the nitrogen and the solvent in the liquid phase. It is preferable that the polymerization system is free of impurities such as water, oxygen, carbon dioxide, etc. that inactivate the polymerization initiator and the living polymer.

Examples of organic solvents include, but are not limited to, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane; cyclohexane, cycloheptan, Aliphatic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, xylene, toluene and ethylbenzene; and the like.

As the organic alkali metal compound as the polymerization initiator, an organic lithium compound is preferable.
Examples of the organic lithium compound include an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound.
Specific examples of the organic lithium compound include, but are not limited to, ethyl lithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, n-pentyllithium, and n-. Examples thereof include hexyllithium, benzyllithium, phenyllithium, hexamethylenedilithium, butazienyllithium, isopropenyldilithium, lithium piperidide and the like.
By using an organolithium initiator containing N, such as lithium piperidide, a polymer having an atomic group with X = 0 in NHx can be obtained.
Only one of these may be used alone, or two or more thereof may be used in combination. Among these, n-butyllithium, sec-butyllithium, and lithium piperidide are preferable from the viewpoint of polymerization activity.

The amount of the organic alkali metal compound used as the polymerization initiator depends on the molecular weight of the target block copolymer, but is generally 0.01 to 0.5 fm (parts by mass with respect to 100 parts by mass of the monomer). It is preferably in the range, more preferably in the range of 0.03 to 0.3 fm, and even more preferably in the range of 0.05 to 0.2 fm.

The vinyl bond amount of the modified block copolymer (a) can be adjusted by using a Lewis base, for example, a compound such as ether or amine as a vinyl bond amount adjusting agent (hereinafter, referred to as a vinylizing agent).
Further, the amount of the vinylizing agent used can be adjusted according to the target amount of vinyl bonding.

Examples of the vinylizing agent include, but are not limited to, ether compounds, tertiary amine compounds, and the like.

Examples of the ether compound include a linear ether compound and a cyclic ether compound.
The linear ether compound is not limited to the following, and is, for example, ethylene glycol dialkyl ether compounds such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether; Dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether; and the like.
The cyclic ether compound is not limited to the following, but is, for example, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis. Examples thereof include (2-oxolanyl) propane and alkyl ethers of furfuryl alcohol.

The tertiary amine compound is not limited to the following, but is not limited to, for example, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidin, N, N, N. ', N'-Tetramethylethylenediamine, N, N, N', N'-Tetraethylethylenediamine, 1,2-dipiperidinoethane, Trimethylaminoethylpiperazin, N, N, N', N'', N' Examples thereof include'-pentamethylethylenetriamine, N, N'-dioctyl-p-phenylenediamine, pyridine, tetramethylpropanediamine, bis [2- (N, N-dimethylamino) ethyl] ether and the like.
These may be used alone or in combination of two or more.
As the tertiary amine compound, a compound having two amines is preferable. Further, among them, those having a structure showing intramolecular symmetry are more preferable, and N, N, N', N'-tetramethylethylenediamine and bis [2- (N, N-dimethylamino) ethyl] ether are preferable. And 1,2-dipiperidinoethane are more preferred.

In the step of producing the modified block copolymer (a), the block copolymer may be copolymerized in the coexistence of the vinylizing agent, the organic lithium compound, and the alkali metal alkoxide described above.
Here, the alkali metal alkoxide is a compound represented by the general formula MOR (in the formula, M is an alkali metal and R is an alkyl group).

The alkali metal of the alkali metal alkoxide is preferably sodium or potassium from the viewpoint of high vinyl bond amount, narrow molecular weight distribution, high polymerization rate, and high blocking rate.
The alkali metal alkoxide is not limited to the following, but is preferably sodium alkoxide, lithium alkoxide, or potassium alkoxide having an alkyl group having 2 to 12 carbon atoms, and more preferably 3 to 6 carbon atoms. Sodium alkoxides and potassium alkoxides having an alkyl group, more preferably sodium-t-butoxide, sodium-t-pentoxide, potassium-t-butoxide, potassium-t-pentoxide.
Among these, sodium-t-butoxide and sodium-t-pentoxide, which are sodium alkoxides, are even more preferable.

The modified block copolymer may be hydrogenated, and the method of hydrogenation is not particularly limited. For example, hydrogen is added to the block copolymer obtained above in the presence of a hydrogenation catalyst. By supplying and hydrogenating, a hydrogenated block copolymer in which the double-bonded residue of the conjugated diene compound unit is hydrogenated can be obtained.
The hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, and the hydrogenation rate can be controlled by, for example, the amount of catalyst at the time of hydrogenation, the amount of hydrogen feed, pressure, temperature, and the like.

In the method for producing the modified block copolymer (a), the atomic group (C) having NHx (x = 0 to 2) is used as the polymer block (A) mainly composed of a vinyl aromatic compound and / or the conjugated diene compound. As a means for introducing into the side chain of the polymer block (B) mainly composed of, a production method for directly grafting an atomic group (C) having NHx (x = 0 to 2), or NHx (x = 0 to 0). When the atomic group (C) having 2) is obtained as a reaction product of α, β-unsaturated carboxylic acid or a derivative thereof and a compound having NHx (x = 0 to 2), it is mainly composed of a vinyl aromatic compound. Α, β-unsaturated carboxylic acid or a derivative thereof is introduced into the side chain of the polymer block (A) and / or the polymer block (B) mainly composed of a conjugated diene compound, and NHx (x = 0 to 2). Examples thereof include a production method in which the compound having is reacted with the α, β-unsaturated carboxylic acid or a derivative thereof.

A polymer block (A) mainly composed of a vinyl aromatic compound and / or a polymer block (B) mainly composed of a conjugated diene compound by directly grafting an atomic group (C) having NHx (x = 0 to 2). In the case of the production method of introducing an atomic group (C) having NHx (x = 0 to 2) in the side chain of, for example, in the presence of a radical initiator, a polymer block (A) mainly composed of a vinyl aromatic compound. ) And a block copolymer containing a polymer block (B) mainly composed of a conjugated diene compound, and a production method in which an atomic group (C) having NHx (x = 0 to 2) is radically added.

The atomic group (C) having NHx (x = 0 to 2) is obtained as a reaction product of α, β-unsaturated carboxylic acid or a derivative thereof and a compound having NHx (x = 0 to 2), and has a vinyl fragrance. An α, β-unsaturated carboxylic acid or a derivative thereof is introduced into the side chain of the polymer block (A) mainly composed of a group compound and / or the polymer block (B) mainly composed of a conjugated diene compound, and NHx (x) (x) is introduced. In the case of a production method in which a compound having = 0 to 2) reacts with the α, β-unsaturated carboxylic acid or a derivative thereof, the molecular unit containing the α, β-unsaturated carboxylic acid or a derivative thereof may be used. For example, maleic acid, maleic halide, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid, etc. And anhydrides of these dicarboxylic acids, acrylic acid, methacrylic acid, crotonic acid and the like, and esters of these monocarboxylic acids, for example, methyl methacrylate, glycidyl methacrylate and the like, which are preferably anhydrides. Of these, maleic anhydride is more preferable from the viewpoint of reactivity.

The amount of the molecular unit added containing α, β-unsaturated carboxylic acid or a derivative thereof is preferably 0.1 to 20 parts by mass, more preferably 0, with respect to 100 parts by mass of the block copolymer. It is 1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass. From the viewpoint of compatibility of the polar resin composition, the added amount is preferably 0.1 part by mass or more. On the other hand, from the viewpoint of the fluidity of the modified block copolymer, the added amount is preferably 20 parts by mass or less.

The method for producing an acid-modified block copolymer in which α, β-unsaturated carboxylic acid or a derivative thereof is bonded to the polymer block (A) and / or the polymer block (B) is not particularly limited, but for example, a radical. It is obtained by dry-blending a compound containing an initiator, a block copolymer, and an α, β-unsaturated carboxylic acid group or a derivative group thereof, and then melt-kneading with an extruder.

The reaction method for reacting the acid-modified block copolymer obtained as described above with the compound having NHx (x = 0 to 2) is not particularly limited, and a known method can be used. ..
As the above reaction method, for example, after dry-blending an acid-modified block copolymer and a compound having NHx (x = 0 to 2), a Banbury mixer, a single-screw screw extruder, a twin-screw screw extruder, Conida, etc. Examples thereof include a method of melt-kneading each component using a general mixer such as a multi-screw screw extruder, a method of dissolving or dispersing and mixing each component, and then heating and removing the solvent.
In the present embodiment, the melt kneading method using an extruder is preferable from the viewpoint of productivity and good kneading property.
The shape of the obtained modified block copolymer (a) is not particularly limited, and examples thereof include pellet shape, sheet shape, strand shape, and chip shape. Further, after melt-kneading, it can be directly molded.

The compounding ratio of the acid-modified block copolymer and the compound having an amino group is such that the compound having NHx (x = 0 to 2) is acidized from the viewpoint of quantitative reaction, economy, and removal of unreacted substances. It is preferable to blend 0.3 mL or more and 2.0 mL or less of the carboxylic acid group or its derivative group in the modified block copolymer. The compounding ratio is more preferably 0.3 mol equivalent or more and 1.8 mol equivalent or less, still more preferably 0.4 mol equivalent or more and 1.5 mol equivalent or less, and even more preferably 0.5 mol equivalent or more and 1.3 mol equivalent or less.

By pelletizing the modified block copolymer (a), pellets of the modified block copolymer (a) can be produced.
As a method of pelletizing, for example, a modified block copolymer is extruded into a strand shape from a uniaxial or biaxial extruder and cut in water by a rotary blade installed in front of the die portion; uniaxial or biaxial extrusion. A method in which a modified block copolymer is extruded into a strand shape from a machine, water-cooled or air-cooled, and then cut with a strand cutter; after melting and mixing with an open roll and a Banbury mixer, the sheet is further molded into a sheet shape with a roll. Examples thereof include a method of cutting into strips and then cutting into cubic pellets with a pelletizer.
The size and shape of the pellet molded product of the hydrogenated block copolymer are not particularly limited.

If necessary, the modified block copolymer (a) can be blended with a pellet blocking inhibitor for the purpose of preventing pellet blocking.
Examples of the pellet blocking inhibitor include, but are not limited to, calcium stearate, magnesium stearate, zinc stearate, polyethylene, polypropylene, ethylene bisstearylamide, talc, and amorphous silica.
From the viewpoint of the transparency of the resin composition obtained from the modified block copolymer (a) and the tube-shaped molded product or sheet-shaped molded product containing the resin composition, calcium stearate, polyethylene, and polypropylene are preferable as the pellet blocking inhibitor.
The preferred amount of the pellet blocking inhibitor is 500 to 6000 ppm with respect to the modified block copolymer. A more preferable amount of the pellet blocking inhibitor is 1000 to 5000 ppm with respect to the modified block copolymer. The pellet blocking inhibitor is preferably blended in a state of being adhered to the pellet surface, but may be contained in the pellet to some extent.

[Resin composition]
The resin composition of the present embodiment is a resin composition containing a modified block copolymer (a), a thermoplastic polyurethane (b), and a polyolefin (c).
The modified block copolymer (a) is a polymer block (A) mainly composed of a vinyl aromatic compound, a polymer block (B) mainly composed of a conjugated diene compound, and an atomic group (C) having a functional group. And, including
In the cross section of the molded product of the resin composition, the thermoplastic polyurethane (b) has a sea-island structure, and the modified block copolymer (a) and / or the polyolefin (c) forms an island phase.
Heat having a major axis of 3 μm or less in the island phase formed by the modified block copolymer (a) and / or the polyolefin (c) surrounded by the sea phase formed by the thermoplastic polyurethane (b). It is a resin composition in which the island phase of the plastic polyurethane (b) is present.

The thermoplastic polyurethane (b) contained in the resin composition of the present embodiment is composed of a diisocyanate, a long-chain polyol and a chain extender (short-chain diol), and has a urethane bond (-NH-COO-) in the molecule. It is a resin. In the thermoplastic polyurethane, the hard segment is composed of diisocyanate and a chain extender, and the soft segment is composed of a long chain polyol, and has rubber elasticity.

The thermoplastic polyurethane (b) is preferably a resin obtained by reacting a polymer polyol having a number average molecular weight of 500 to 10,000, an organic diisocyanate, and a chain extender.
The long-chain polyol having a number average molecular weight of 500 to 10000 is not limited to the following, and examples thereof include polyester diols, polyether diols, polyester ether diols, polycarbonate diols, and polyester carbonate diols.
Examples of the organic diisocyanate include, but are not limited to, aromatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates.
Examples of the chain extender include, but are not limited to, aromatic diols and alicyclic diols.

Here, the number average molecular weight of the high molecular weight polyol is measured by gel permeation chromatography (GPC), and the calibration curve (peak of standard polystyrene) obtained from the measurement of commercially available standard polystyrene from the molecular weight of the peak of the chromatogram. Can be determined using (created using molecular weight).

The polyolefin (c) is not particularly limited, but a polypropylene resin or a polyethylene resin is preferable from the viewpoint of mechanical strength.

The polypropylene-based resin used is not particularly limited, and examples thereof include a crystalline propylene homopolymer, a crystalline ethylene-propylene copolymer, and a crystalline propylene-α-olefin copolymer.
These may be used alone or in combination of two or more.

The crystalline ethylene-propylene copolymer is not particularly limited, and examples thereof include a crystalline ethylene-propylene block copolymer composed of a propylene homopolymer moiety and an ethylene-propylene random copolymer moiety.

The α-olefin used in the crystalline propylene-α-olefin copolymer is not particularly limited, but is, for example, an α-olefin having 4 or more carbon atoms, preferably an α-olefin having 4 to 20 carbon atoms. It is more preferably an α-olefin having 4 to 12 carbon atoms.
Examples of such α-olefins include, but are not limited to, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and the like. The crystalline propylene-α-olefin copolymer is not particularly limited, and examples thereof include a crystalline propylene-1-butene copolymer and a crystalline propylene-1-hexene copolymer.

Of these, crystalline propylene homopolymers, crystalline ethylene-propylene block copolymers, or mixtures thereof are preferable.

Examples of the polyethylene-based resin include low-density polyethylene, linear low-density polyethylene, high-density polyethylene, and a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms. In the case of a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, the α-olefin may be, for example, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl1-pentene, etc. 1-octene and the like can be mentioned. In this case, the proportion of α-olefin in the copolymer is preferably 30% by mass or less.

When the resin composition of the present embodiment is 100% by mass, the modified block copolymer (a) 1 to 98% by mass, the thermoplastic polyurethane (b) 1 to 98% by mass, and the polyolefin ( c) It is preferable to contain 1 to 98% by mass.
From the viewpoint of abrasion resistance and mechanical strength, the resin composition of the present embodiment is more preferably heat-modified block copolymer (a) 3 to 85% by mass when the resin composition is 100% by mass. It contains 10 to 92% by mass of the plastic polyurethane (b) and 5 to 87% by mass (c) of the polyolefin, and more preferably 4 to 53% by mass of the modified block copolymer (a) and the thermoplastic polyurethane (b). It contains 40 to 89% by mass and 7 to 56% by mass of the polyolefin (c), and more preferably 5 to 35% by mass of the modified block copolymer (a) and 55 to 85% by mass of the thermoplastic polyurethane (b). %, And 10 to 40% by mass of the polyolefin (c).

As shown in FIG. 1, the resin composition of the present embodiment has an island phase (B) composed of (a) and / or (c) surrounded by the sea phase (A phase) of (b) in the resin composition. In the phase), there is an island (C phase) of (b) having a major axis of 3 μm or less, and the C phase is preferably 2 μm or less in the major axis, and more preferably 1 μm or less in the major axis. Is.
The presence of the island (C phase) of (b) whose major axis is 3 μm or less increases the interface between the TPU and other components, and each component may be finely dispersed to the extent that the C phase exists. It is presumed that the tear strength and wear resistance tend to improve.
The minimum value of the long axis of the C phase is not particularly limited as long as it is larger than 0 μm, but is preferably 0.005 μm or more, and more preferably 0.1 μm or more.
Examples of the method for setting the major axis of the C phase to 3 μm or less include a method using the above-mentioned modified block copolymer (a).

The ratio of the intensity obtained by singular value decomposition of the absorption spectrum obtained by scanning transmission electron X-ray microscope measurement between the island phase of (b) and the sea phase of (b) (in the island phase of (b)). Strength / strength in the sea phase of (b) above) is 0.5 or more, preferably 0.55 or more, and more preferably 0.6 or more. It is presumed that when the strength ratio is 0.5 or more, the resin component can be finely dispersed to the extent that the C phase is present, and the tear strength and wear resistance tend to be improved.
The maximum value of the intensity ratio is not particularly limited, but is preferably 3.0 or less, more preferably 2.5 or less, and further preferably 2.0 or less.
Examples of the method for increasing the strength ratio to 0.5 or more include a method using the above-mentioned modified block copolymer (a).

The distribution observation of each component in the cross section of the molded product of the resin composition of the present embodiment can be performed using a scanning transmission X-ray microscope (hereinafter referred to as STXM). As the STXM device, compact-STXM installed at the beamline 13A of Photon Factory, which is a synchrotron radiation facility of the High Energy Accelerator Research Organization, was used. For details of the compact-STXM device, refer to Non-Patent Document Rev. Sci. Instrument. It is shown in vol. 87, 13704 (2016).
STXM is a method of detecting a transmitted signal while scanning a focused X-ray beam on a sliced sample. By fixing the photon energy (hν) of X-rays and spatially scanning a certain range on the sample, an X-ray transmission image at that photon energy can be obtained. If the incident light intensity (I0) is monitored at the same time, it can be converted into a distribution image (mapping image) of the X-ray absorption coefficient. A set of X-ray absorption coefficient mapping images with a series of photon energies can be obtained by measuring the mapping image of this absorption coefficient within the range covering the absorption edge region of the element of interest while changing the photon energy little by little. Be done.
This set of mapping images is called an "image stack". By extracting the absorption spectrum of an arbitrary region from this image stack data, the absorption spectrum in a minute part can be obtained.
As the measurement sample, an ultrathin section having a cross section of a molded product having a thickness of about 100 nm can be used. An ultrathin section prepared by unstaining using a cryomicrotome and held on a copper grid for a transmission electron microscope can be used.
An appropriate location for the ultrathin section sample is selected and image stack measurements are performed at the carbon K-shell absorption edge. As the measurement range, a rectangle having a length and a width of 3 to 10 μm was set, and the number of pixels was set so that the size of one pixel was 30 to 60 nm square. At this time, in order to simultaneously monitor the incident light intensity (I0), it is necessary to include a portion where the sample does not exist in a part of the measurement range. The photon energy is varied in the range of 280 eV to 310 eV so as to cover the K-shell absorption edge of carbon. 280.0 to 283.5 eV are at 0.5 eV intervals, 283.5 to 291.0 eV are at 0.15 eV intervals, 291.0 to 295.0 eV are at 0.5 eV intervals, and 295.0 to 310.0 eV are at 0.5 eV intervals. Image stack data is obtained by changing the photon energy at 1.0 eV intervals and acquiring image data with each photon energy.

The obtained image stack data is analyzed by STXM data analysis software, aXis2000 (ver. 13-May-2016). The analysis is performed according to the following procedure.
First, drift correction is performed on a series of image data constituting the image stack.
Next, a region without a sample included in the measurement range is specified, and the transmitted light intensity is set to I0, and the region is converted into an image stack with an absorption coefficient.
Then, the spectrum is extracted from the characteristic region and the components are identified. To identify the components, the extracted spectral shape may be compared with existing literature and databases, or ultrathin sections of each individual polymer of the polymer constituting the molded product are prepared, and STXM measurement is performed to obtain the spectrum. May be compared with.
After extracting the spectra for each component, singular value decomposition is performed using them as reference spectra. The singular value decomposition is performed using "SVD", which is a function of aXis2000, under the conditions that the lower limit is 0 and the upper limit is a value sufficiently larger than the intensity of each component (for example, 1000).

<Manufacturing method of resin composition>
The method for producing the resin composition of the present embodiment is not particularly limited, and a known method can be used. For example, a method of melt-kneading each component using a general mixer such as a Banbury mixer, a single-screw screw extruder, a twin-screw screw extruder, a conider, or a multi-screw screw extruder, and dissolving or dispersing and mixing each component. After that, a method of heating and removing the solvent is used.
In the present embodiment, the melt-kneading method using an extruder is preferable from the viewpoint of productivity and good kneading.
The shape of the obtained composition is not particularly limited, and examples thereof include pellets, sheets, strands, and chips. Further, after melt-kneading, it can be directly molded.

The resin composition of the present embodiment is obtained by conventionally known methods such as extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotary molding, powder slush molding, foam molding, and lamination. It can be processed into a practically useful molded product by molding, calendar molding, blow molding, or the like. Further, if necessary, processing such as foaming, powdering, stretching, adhesion, printing, painting, and plating may be performed. Depending on such molding methods, a wide variety of sheets, films, injection molded products of various shapes, hollow molded products, pneumatic molded products, vacuum molded products, extrusion molded products, foam molded products, non-woven and fibrous molded products, synthetic leather, etc. It can be used as molded products, and these molded products can be used for automobile interior / exterior materials, building materials, toys, home appliance parts, medical instruments, industrial parts, and other miscellaneous goods.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to the Examples described below.
In the following Examples and Comparative Examples, the structure and physical properties of the polymer were measured as follows.

(1) Content of each polymer block in the modified block copolymer The polymer solution sampled for each step of the polymerization process of the modified block copolymer before hydrogenation was used as an internal standard with 0.50 mL of n-propylbenzene. Samples were prepared by injecting about 20 mL into a 100 mL bottle sealed with about 20 mL of toluene.
This sample was measured by gas chromatography (manufactured by Shimadzu Corporation: GC-14B) equipped with a backed column carrying apiison grease, and the polymer solution was obtained from the calibration curve of the butadiene monomer and the styrene monomer obtained in advance. The amount of residual monomer in the polymer was determined, it was confirmed that the polymerization rates of the butadiene monomer and the styrene monomer were 100%, and the content of each polymer block was calculated from the following formula.
The polymerization rate of butadiene was measured at a constant temperature of 90 ° C., and the polymerization rate of styrene was measured under the conditions of 90 ° C. (hold for 10 minutes) to 150 ° C. (10 ° C./min).
Content of each block (% by mass) = (total amount of monomers fed in each step) / (total amount of monomers) x 100

(2) Amount of vinyl bond before hydrogenation of the modified block copolymer The polymer sampled at each step of the polymerization process of the modified block copolymer before hydrogenation and during the polymerization of the polymer block (B) polymer is proton-nuclear magnetic. It was measured by the resonance ( ¹ H-NMR) method. The measuring instrument is ECS400 (manufactured by JEOL), deuterated chloroform is used as the solvent, the sample concentration is 50 mg / mL, the observation frequency is 400 MHz, tetramethylsilane is used as the chemical shift standard, the pulse delay is 2.904 seconds, and the number of scans is 64. The times were performed at a pulse width of 45 ° and a measurement temperature of 26 ° C. Vinyl bond amount, from the integral value of the signal attributable to 1,4-bonds and 1,2-bonds, after calculating the integral value per ¹ H each binding modes, 1,4-bonds and 1,2 -Calculated from the ratio with the bond.

(3) Hydrogenation rate of unsaturated bond based on conjugated diene compound unit of hydrogenated modified block copolymer The polymer after hydrogenation ^{was measured by proton nuclear magnetic resonance (1} H-NMR). The measurement conditions and the method for processing the measurement data were the same as in (2) above. For the hydrogenation rate, the integral value of the signal derived from the residual double bond of 4.5 to 5.5 ppm and the signal derived from the hydrogenated conjugated diene was calculated, and the ratio thereof was calculated.

(4) Ratio of butylene and / or propylene to a total of 100 mol% of conjugated diene compound units of hydrogenated block copolymers ^{Measured by proton nuclear magnetic resonance (1} H-NMR) using the polymer after hydrogenation. .. The measurement conditions and the method for processing the measurement data were the same as in (2) and (3) above. The signal derived from the total amount of conjugated diene compound units in the hydrogenated block copolymer, the amount of butylene and / or the integrated value derived from propylene were calculated, and the ratio was calculated. The integral value of the signal attributed to butylene (hydrogenated 1,2-bond) at 0-2.0 ppm of the spectrum was used to calculate the butylene ratio.

(5) Content of aromatic vinyl compound unit of modified block copolymer (hereinafter, also referred to as "styrene content")
It was measured by proton nuclear magnetic resonance ( ¹ H-NMR) method using a modified block polymer. The measuring instrument is ECS400 (manufactured by JEOL), deuterated chloroform is used as the solvent, the sample concentration is 50 mg / mL, the observation frequency is 400 MHz, tetramethylsilane is used as the chemical shift standard, the pulse delay is 2.904 seconds, and the number of scans is 64. The times were performed at a pulse width of 45 ° and a measurement temperature of 26 ° C. The styrene content was calculated using the integrated value of the total styrene aromatic signal at 6.2-7.5 ppm of the spectrum.
In addition, the content of the total aromatic vinyl compound and (A) can also be calculated by calculating the content of the aromatic vinyl compound unit for each sampled polymer for each step of the polymerization process of the block copolymer before hydrogenation. ) The styrene content of the block was confirmed.

(6) Weight average molecular weight and molecular weight distribution of the modified block copolymer Measured by GPC [device: LC-10 (manufactured by Shimadzu Corporation), column: TSKgelGMHXL (4.6 mm × 30 cm)]. Tetrahydrofuran was used as the solvent. The weight average molecular weight was determined from the peak molecular weight of the chromatogram using a calibration curve (prepared using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene. For the molecular weight when there are a plurality of peaks in the chromatogram, the weight average molecular weight was obtained from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram).
The molecular weight distribution was calculated from the ratio of the obtained weight average molecular weight (Mw) to the number average molecular weight (Mn).

(7) Ratio of modified copolymer in terminal-modified block copolymer By applying the property that modified components are adsorbed on a GPC column using silica gel as a filler, it contains modified block copolymer and low molecular weight internal standard polystyrene. Regarding the sample solution, the ratio of the modified block copolymer to the standard polystyrene in the chromatogram measured in (4) above, the silica-based column GPC [equipment: LC-10 (manufactured by Shimadzu Corporation), column: Zorbox (manufactured by DuPont). )], The ratio of the modified copolymer to the standard polystyrene in the chromatogram was compared, and the amount adsorbed on the silica column was measured from the difference between them, and this ratio was taken as the ratio of the modified copolymer.

(8) Addition of acid anhydride of acid anhydride-modified hydrogen block copolymer An acid anhydride-modified hydrogen block copolymer dissolved in toluene and a methanol solution of sodium methoxyde having a factor of 1 ± 0.05. The amount of acid anhydride was calculated by titrating with.

(9) Amount of reaction between a compound having NHx (x = 0 to 2) and an acid anhydride An infrared spectrophotometer (Nicollet iS10 FT-IR spectroscope manufactured by Thermo Fisher Scientific) was used to detect the peak of the acid anhydride. The reaction amount was calculated from the decrease amount. When the acid anhydride was maleic anhydride, the reaction amount was calculated from the amount of decrease in the peak derived from maleic anhydride near ^{1790 cm -1.}

(10) Specific Gravity of Modified Block Copolymer Resin Composition The specific gravity at 23 ° C. was measured according to the JIS K7112 A method. Lightness was evaluated according to the following evaluation criteria.
[Evaluation criteria]
◯: Specific gravity of the resin composition is less than 1.21 of the specific gravity of the TPU alone ×: Specific gravity of the resin composition is 1.21 or more of the specific gravity of the TPU alone

(11) Fracture elongation (Eb), tear strength (Tr)
According to JIS K6251, measurement was performed with a No. 3 dumbbell and a crosshead speed of 500 mm / min. Based on the mechanical properties of the modified block copolymer resin composition, the mechanical properties were evaluated according to the following evaluation criteria.
[Evaluation criteria]
〇: Eb of the modified block copolymer resin composition is 650% or more Δ: Eb of the modified block copolymer resin composition is 600% or more and less than 650% ×: Eb of the modified block copolymer resin composition Less than 600% Measured according to JIS K6252 with an angle type test piece and a crosshead speed of 500 mm / min. Based on the mechanical properties of the thermoplastic polyurethane resin composition, the mechanical properties were evaluated according to the following criteria.
[Evaluation criteria]
〇: Tr of the modified block copolymer resin composition is 85 kN / m or more Δ: Tr of the modified block copolymer resin composition is 75 kN / m or more and less than 85 kN / m ×: Modified block copolymer resin composition Tr is less than 75 kN / m

(12) Abrasion resistance (Taber wear test)
Using a Taber wear tester (manufactured by Tester Sangyo Co., Ltd., AB-101 type), a wear test of the resin composition was performed with a wear wheel H-22, a load of 1 kg, and 60 rpm to determine the resin reduction mass before and after 1000 rotations. It was measured. From the reduced mass of the resin composition, the wear resistance was evaluated according to the following criteria.
[Evaluation criteria]
〇: Reduced mass of modified hydrogenated block copolymer resin composition is less than 75 mg Δ: Reduced mass of modified hydrogenated block copolymer resin composition is 75 mg or more and less than 100 mg ×: Modified hydrogenated block copolymer The reduced mass of the resin composition is 100 mg or more.

(13) Observation of Morphology In the cross section of the molded product of the resin composition, the domain size of the modified block copolymer (a), the thermoplastic polyurethane (b), and the low-density polyethylene (c), which are the components of the composition, is 1 μm or more. It was a phase-separated structure in which the sea phase (A phase) of (b) and the island phase (B phase) of (a) and / or (c) were largely separated. Furthermore, the presence or absence of the island phase (b) having a major axis of 3 μm or less was observed in the B phase.
Whether or not the island phase (b) exists in the B phase was determined by the following method.
First, a spectrum was extracted from a characteristic region in the observation field of view, identified by comparison with the literature, etc., and the spectrum of (b) was obtained. The spectra of (a) and (c) were obtained in the same manner. Singular value decomposition was performed using the spectra of these three components as reference spectra.
In the intensity distribution of TPU obtained by singular value decomposition, the average intensity in phase A, which is a large phase-separated structure, was read. The average intensity was defined as the average value of a region of 0.5 μm square or more in the A phase (intensity L). Next, the average intensity of the small phase of TPU existing in the B phase was read. The average intensity of the small phase was defined as the average value of data for at least 4 pixels near the center of the small phase (referred to as intensity S).
When the ratio of the intensity S to the intensity L, that is, the value of the intensity S / intensity L is 0.5 or more, the smaller phase is determined to be the TPU phase.
The presence or absence of the island phase (b) in the resin composition was evaluated according to the following criteria.
○ (There is an island phase of (b)): The value of strength S / strength L is 0.5 or more and the major axis is 3 μm or less × (There is no island phase of (b)): The value of strength S / strength L is Less than 0.5 and / or major axis exceeds 3 μm

A modified hydrogenated block copolymer was produced using the following materials.
Maleic anhydride (manufactured by Fuso Chemical Industry Co., Ltd.)
Radical generator: Perhexa 25B (manufactured by NOF CORPORATION)
Compounds with secondary amines: N-benzylethylenediamine, 1,3-dimethyl-2-imidazolidinone (all manufactured by Tokyo Chemical Industry Co., Ltd.)

[Preparation of hydrogenated catalyst]
The hydrogenation catalyst used for the hydrogenation reaction of the hydrogenated block copolymer was prepared by the following method. 1 L of dried and purified cyclohexane is placed in a nitrogen-substituted reaction vessel, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride is added, and an n-hexane solution containing 200 mmol of trimethylaluminum is added with sufficient stirring. Then, it was reacted at room temperature for about 3 days.

[Production of unmodified block copolymer a-1]
[Step 1]
Batch polymerization was carried out using a stirrer having an internal volume of 10 L and a tank reactor with a jacket. 1 L of cyclohexane was added to the reactive group, n-butyllithium was added to 0.13 parts by mass with respect to 100 parts by mass of the total monoma, and N, N, N', N'-tetramethylethylenediamine (TMEDA) was added to n-. 0.3 mol was added to 1 mol of butyllithium. Next, a cyclohexane solution containing 9 parts by mass of butadiene (concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 20 minutes. Next, a cyclohexane solution (concentration: 20% by mass) containing 16 parts by mass of styrene was added, and polymerization was carried out at 70 ° C. for 45 minutes. Next, a cyclohexane solution containing 59 parts by mass of butadiene (concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 1 hour. Finally, a cyclohexane solution containing 16 parts by mass of styrene was added and polymerized at 70 ° C. for 45 minutes. The obtained polymer had a styrene content of 32% by mass, a vinyl bond content of the butadiene part of 36 mol%, a weight average molecular weight of 75,000, and a molecular weight distribution of 1.2.

[Step 2]
The hydrogenation catalyst is added to the obtained block copolymer so as to have a titanium equivalent concentration of 100 ppm per 100 parts by mass of the block copolymer, and a hydrogenation reaction is carried out at a hydrogen pressure of 0.7 MPa and a temperature of 70 ° C. It was. Methanol was then added, and then 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to the block copolymer. An unmodified hydrogenated block copolymer a-1 was produced.
The hydrogenation rate of the obtained a-1 was 99 mol%. The butylene content of the obtained polymer was 36 mol%.

[Production of modified block copolymer a-2]
[Step 3]
Next, 100 parts by mass of pelletized unmodified hydrogenated block copolymer, 0.5 parts by mass of maleic anhydride, and 0.1 parts by mass of perhexa 25B are dry-blended and biaxially extruded. Maleic anhydride-modified hydrogenated block copolymer a-2 was produced by melt-kneading with a machine TEX30 (manufactured by Japan Steel Works, Ltd.) at a cylinder set temperature of 210 ° C., a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour. .. The amount of maleic anhydride added was 0.4 parts by mass with respect to 100 parts by mass of the unmodified hydrogenated block copolymer.

[Production of modified block copolymer a-3]
[Step 4]
Next, pelletized a-2, maleic anhydride contained in a-2, and equimolar (B) N-benzylethylenediamine were dry-blended, and a twin-screw extruder TEX30 (Japan Steel Works, Ltd.) was manufactured. ), A-3 was manufactured by melt-kneading at a cylinder set temperature of 210 ° C., a screw rotation speed of 205 rpm, and a discharge rate of 3 kg / hour.

[Production of modified block copolymer a-4]
In [Step 3], maleic anhydride was 2.1 parts by mass, perhexa 25B was 0.12 parts by mass, and the cylinder set temperature was 180 ° C., but the conditions were the same as those for the production of a-3. Maleic anhydride-modified hydrogenated block copolymer a-4 was produced in which the amount of maleic anhydride added was 1.5 parts by mass with respect to 100 parts by mass of the unmodified hydrogenated block copolymer.

[Production of modified block copolymer a-5]
It was carried out under the same conditions as the production of a-3, except that a-4 pelleted in [Step 4] and N-benzylethylenediamine having an equimolar amount of maleic anhydride contained in a-4 were used. a-5 was manufactured.

[Production of modified block copolymer a-6]
To the polymer obtained in [Step 1], equimolar 1,3-dimethyl-2-imidazolidinone (hereinafter, also abbreviated as “DMI”) was added to 1 mol of n-butyllithium, and the temperature was 70 ° C. The reaction was carried out for 10 minutes. [Step 2] was carried out under the same conditions as the production of a-2 to produce a-6. The hydrogenation rate of a-6 was 72%, and the modification rate was 65%.

[Manufacturing of thermoplastic polyurethane resin composition]
Based on the compounding amounts (unit: "parts by mass") of Examples 1 to 12 and Comparative Examples 1 to 4 shown in Tables 1 and 2, a thermoplastic polyurethane resin composition was produced using the following materials. Further, the molded sheet was produced.
Hydrogenated block copolymers: a-1, a-3, a-5, a-6
TPU: Elastran ET-685 (manufactured by BASF Japan Ltd., specific gravity 1.21) (b)
Polyolefin: Low density polyethylene Suntech M2115 (manufactured by Asahi Kasei Corporation) (c)

(Examples 1, 4, 5, 6)
A-3, b, and c are dry-blended and melt-kneaded with a twin-screw extruder TEX30 (manufactured by Japan Steel Works, Ltd.) at a cylinder set temperature of 200 ° C., a screw rotation speed of 253 rpm, and a discharge rate of 5 kg / hour. The composition was produced. Then, it was rolled out with a 4-inch roll at 170 ° C., and then ^{press-molded at 200 ° C. and 100 kg / cm 2} with a hydraulic press to prepare a molded sheet having a thickness of 2 mm.

(Examples 2, 7, 8, 9)
It was carried out under the same conditions as in Example 1 except that a-5 was used to prepare a molded sheet having a thickness of 2 mm.

(Examples 3, 10, 11, 12)
It was carried out under the same conditions as in Example 1 except that a-6 was used to prepare a molded sheet having a thickness of 2 mm.

(Comparative Examples 1, 3, 4, 5)
It was carried out under the same conditions as in Example 1 except that a-1 was used to prepare a molded sheet having a thickness of 2 mm.

(Comparative Example 2)
It was carried out under the same conditions as in Example 1 except that only b and c were used, and a molded sheet having a thickness of 2 mm was prepared.

From Table 1, the resin compositions of Examples 1 to 3 had TPU islands having a major axis of 3 μm or less, and were excellent in tear strength and abrasion resistance.
On the other hand, Comparative Examples 1 and 2 did not have TPU islands with a major axis of 3 μm or less, resulting in inferior tear strength and wear resistance.

The resin composition of the present invention has an excellent balance between tear strength and abrasion resistance, which are the characteristics of thermoplastic polyurethane, and is lightweight. Since the composition containing the thermoplastic polyurethane of the present invention has the above-mentioned excellent properties, automobile parts, industrial parts, hoses, tubes, films, household appliances, electric wires and cables, medical / sanitary products, sports products, etc. It has industrial potential for use in industrial supplies and other miscellaneous goods.

Claims (3)

A resin composition comprising a modified block copolymer (a), a thermoplastic polyurethane (b), and a polyolefin (c).
The modified block copolymer (a) is a polymer block (A) mainly composed of a vinyl aromatic compound, a polymer block (B) mainly composed of a conjugated diene compound, and an atomic group (C) having a functional group. ) And, including
In the cross section of the molded product of the resin composition, the thermoplastic polyurethane (b) has a sea-island structure, and the modified block copolymer (a) and / or the polyolefin (c) forms an island phase.
Heat having a major axis of 3 μm or less in the island phase formed by the modified block copolymer (a) and / or the polyolefin (c) surrounded by the sea phase formed by the thermoplastic polyurethane (b). There is an island phase of thermoplastic polyurethane (b),
The ratio of the intensity obtained by singular value decomposition of the absorption spectrum obtained by scanning transmission electron X-ray microscope measurement between the island phase of (b) and the sea phase of (b) (intensity in the island phase of (b)). / (Strength in the sea phase of (b)) is 0.5 or more.
Resin composition. When the resin composition is 100% by mass, the modified block copolymer (a) is 1 to 98% by mass, the thermoplastic polyurethane (b) is 1 to 98% by mass, and the polyolefin (c) is 1. The resin composition according to claim 1, which comprises ~ 98% by mass. The resin composition according to claim 1 or 2, wherein the functional group is NHx (x = 0 to 2).