JP2022099692A - Hydrogenated copolymer and molded article - Google Patents

Abstract

To obtain a hydrogenated copolymer capable of improving wear resistance, low temperature mechanical characteristic and the balance of various characteristics in a resin composition mixed with a thermoplastic elastomer composition such as polypropylene.SOLUTION: There is provided a hydrogenated copolymer (X) comprising hydrogenated copolymers (a), (b1) and (b2) obtained by hydrogenating a polymer composed of a vinyl aromatic compound and a conjugated diene compound, wherein the mass ratio (a)/{(b1)+(b2)} of the content of the hydrogenated copolymer (a) to the content of the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2) is 45/55 to 95/5, the hydrogenated copolymer (X) has at least one peak where the tanδ peak temperature is 0°C or more and the tanδ peak height is 1.0 or more and has at least two peaks where the tanδ peak temperature is less than 0°C and the tanδ peak height is less than 0.2.SELECTED DRAWING: Figure 1

Description

The present invention relates to a hydrogenated copolymer and a molded product.

The hydrogenated block copolymer composed of a conjugated diene compound and a vinyl aromatic compound has elasticity similar to that of natural rubber or synthetic rubber at room temperature, and has molding processability similar to that of thermoplastic resin at high temperature. Furthermore, because of its excellent weather resistance and heat resistance, it has traditionally been used as a plastic modifier, automobile parts, medical molded products, asphalt modifiers, footwear, molded products such as food containers, and packaging materials. , Adhesive sheet, widely used in the fields of home appliances and industrial parts.

For example, Patent Document 1 describes a hydrogenated copolymer obtained by hydrogenating a non-hydrogenated copolymer containing a random copolymer of a conjugated diene monomer unit and a vinyl aromatic monomer unit. A resin composition of a hydrogenated copolymer and a thermoplastic resin or a rubber-like polymer is disclosed. It is described that this resin composition is excellent in mechanical properties, abrasion resistance, etc., and can be a substitute material for a soft vinyl chloride resin.

International Publication No. 2004/003027

However, the hydrogenated copolymer disclosed in Patent Document 1 has a problem that the compatibility with a thermoplastic resin such as polypropylene is poor, and further, the mechanical properties at low temperature are low. Therefore, it is difficult to apply it to applications that require compatibility with polypropylene, wear resistance, and low temperature characteristics, such as automobile members and medical members.

In the field of automobile parts such as automobile interior skin materials, medical parts such as infusion bags and infusion tubes, adhesive films based on polyolefin, foods, and packaging for clothing, thermoplastic resins such as polypropylene and rubber-like polymers are used. As the properties required for the resin composition of the above, it is required that the abrasion resistance, the low temperature mechanical property, and the balance of each property are good, but a resin composition satisfying these properties has not been obtained yet. do not have.

In view of the above-mentioned problems of the prior art, the present invention has a good balance between wear resistance, low temperature mechanical properties, and each property in a resin composition when mixed with a thermoplastic resin such as polypropylene or a rubbery polymer. It is an object of the present invention to provide a hydrogenated copolymer which can be obtained.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that a hydrogenated copolymer showing a specific loss tangent can solve the above-mentioned problems of the prior art, and have completed the present invention. ..

That is, the present invention is as follows.
[1]
A hydrogenated copolymer (X) containing a hydrogenated copolymer (a), (b1) and (b2) hydrogenated with a polymer composed of a vinyl aromatic compound and a conjugated diene compound.
The hydrogenated copolymer (a) has one or more tan δ peaks at 0 ° C. or higher in the viscoelasticity measurement (1 Hz).
The hydrogenated copolymer (b1) has one or more tanδ peaks at −25 ° C. or higher and lower than 0 ° C. in viscoelasticity measurement (1 Hz).
The hydrogenated copolymer (b2) has one or more tan δ peaks below −25 ° C. in viscoelasticity measurement (1 Hz).
Mass ratio (a) / {(b1) + ( b2)} is 45/55 to 95/5,
The hydrogenated copolymer (X) has at least one peak having a tanδ peak temperature of 0 ° C. or higher and a tanδ peak height of 1.0 or higher, and the tanδ peak temperature is less than 0 ° C. and the tanδ peak height. Hydroponic copolymer (X) having at least two peaks of less than 0.2.
[2]
The hydrogenated copolymer (a) has a block B1 composed of a vinyl aromatic compound and a conjugated diene compound and having a vinyl aromatic compound content of 20 to 90% by mass.
The hydrogenated copolymer (b1) has a block B2 composed of a vinyl aromatic compound and a conjugated diene compound and having a vinyl aromatic compound content of 5 to 40% by mass.
The hydrogenated copolymer (X) according to [1], wherein the hydrogenated copolymer (b2) has a block D containing a conjugated diene compound as a main component and having a vinyl bond amount of 40 mol% or more before hydrogenation.
[3]
The hydrogenated copolymer (X) according to [2], wherein the block D of the hydrogenated copolymer (b2) has a vinyl bond amount of 60 mol% or more before hydrogenation.
[4]
The hydrogenated copolymer (X) according to any one of [1] to [3] and a polypropylene resin (c).
A resin composition containing and.
[5]
A thermoplastic elastomer composition containing the hydrogenated copolymer (X) according to any one of [1] to [3] and a thermoplastic resin and / or a rubbery polymer.
[6]
A molded product of the resin composition according to [4] or the thermoplastic elastomer composition according to [5].

According to the present invention, in a resin composition when mixed with a thermoplastic resin such as polypropylene or a rubber-like polymer, the wear resistance, low-temperature mechanical properties and the balance of each property can be improved, and the water-added copolymer weight can be improved. Coalescence is obtained.

The temperature dependence of the loss tangent of Production Example 1 (A1) and Comparative Production Example 5 (A14) is shown. (A) An image of a molded body of the polypropylene resin composition of Example 1 observed by morphology with a transmission electron microscope (ruthenium staining) is shown. (B) An image observed by morphology with a transmission electron microscope (ruthenium staining) of the molded product of the polypropylene resin composition of Comparative Example 1 is shown (magnification 20,000 times in the upper part and 50,000 times magnification in the lower part). (A): The elastic modulus mapping diagram by AFM of the injection molded plate of Example 1 is shown. (B): The elastic modulus mapping diagram by AFM of the injection molded plate of the comparative example 2 is shown. (C): The elastic modulus mapping diagram by AFM of the injection molded plate of the comparative example 3 is shown.

Hereinafter, embodiments for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

[Hydrogenated copolymer (X)]
The hydrogenated copolymer (X) of the present embodiment contains hydrogenated copolymers (a), (b1) and (b2) obtained by hydrogenating a polymer composed of a vinyl aromatic compound and a conjugated diene compound. The hydrogenated copolymer (X) is a so-called polymer blend containing a plurality of hydrogenated copolymers. More specifically, the hydrogenated copolymer (X) is composed of a polymer block mainly composed of an aromatic vinyl compound, a polymer block mainly composed of a conjugated diene compound, and a conjugated diene compound and an aromatic vinyl compound. Hydrogenated product of one or more polymer blocks selected from the group consisting of polymer blocks (excluding polymer blocks mainly composed of aromatic vinyl compounds and polymer blocks mainly composed of conjugated diene compounds). It contains a hydrogenated copolymer (a), a hydrogenated copolymer (b1), and a hydrogenated copolymer (b2), which are composed of the same.

Mass ratio of the content of the hydrogenated copolymer (a) to the contents of the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2) (a) / {(b1) + (b2)} Is 45/55 to 95/5.

The hydrogenated copolymer (a) has one or more tanδ peaks at 0 ° C. or higher in the viscoelasticity measurement (1 Hz), and the hydrogenated copolymer (b1) has a tanδ peak in the viscoelasticity measurement (1 Hz). The hydrogenated copolymer (b2) has one or more tanδ peaks below -25 ° C in the viscoelasticity measurement (1 Hz). The hydrogenated copolymer (X) has at least one peak having a tan δ peak temperature of 0 ° C. or higher and a tan δ height of 1.0 or higher, a tan δ peak temperature of less than 0 ° C., and a tan δ peak height of 1.0 ° C. or higher. It has at least two peaks less than 0.2.

By providing the above-mentioned constitution, the hydrogenated copolymer of the present embodiment has abrasion resistance, low-temperature mechanical properties, and each of the resin compositions when mixed with a thermoplastic resin such as polypropylene or a rubber-like polymer. The balance of characteristics is good.

Hereinafter, each component will be described in detail.
In the present specification, "mainly" means that the target monomer unit is contained in the target polymer block in an amount of more than 70% by mass and 100% by mass or less, preferably 80% by mass. It means that it contains 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less.

(Aromatic vinyl compound)
The vinyl aromatic compound constituting the hydrogenated copolymer is not limited to the following, and for example, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, Examples thereof include N-dimethyl-p-aminoethylstyrene and N, N-diethyl-p-aminoethylstyrene.

Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferable from the viewpoint of availability and productivity. As the vinyl aromatic compound contained in the block containing the vinyl aromatic and the conjugated diene (so-called random block), styrene is preferable from the viewpoint of reactivity. Only one of these may be used, or two or more thereof may be used in combination. However, an unsaturated monomer other than the aromatic vinyl compound may be contained in a proportion of 10% by mass or less as long as it does not interfere with the object and effect of the present invention. Examples of the other unsaturated monomer include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and the like. At least one selected from 2-methyl-1,3-pentadiene, 1,3-hexadiene and the like can be mentioned, and the binding form is not particularly limited and may be random or tapered.

(Conjugated diene compound)
The conjugated diene compound constituting the hydrogenated copolymer is not particularly limited as long as it is a diolefin having a conjugated double bond, and is, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene). , 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene and the like.

Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of availability and productivity. These may be used alone or in combination of two or more.

The tan δ peak temperature (glass transition temperature) of polybutadiene is -90 ° C, the glass transition temperature of polyisoprene is -73 ° C, and the glass transition temperature of polystyrene is 100 ° C (Journal of the Japan Rubber Association, Vol. 41, No. 12, 1968, P1111 to P1117). ). The optimum content of the copolymerization ratio of the conjugated diene and the aromatic vinyl compound contained in the block (B1) differs depending on the type of the conjugated diene compound. In the block (B1), when the aromatic vinyl compound is styrene and isoprene is used as the conjugated diene compound, the glass transition temperature is higher than when butadiene is used as the conjugated diene compound, so that the fragrance in the block (B1) is high. Even if the content of the group vinyl compound is low, the tanδ peak temperature can be increased.

(Hydrogenation rate)
In the present embodiment, it is preferable that 80 mol% or more of the total conjugated diene compound of the hydrogenated copolymer (a), the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2) is hydrogenated. .. Since the hydrogenation rate also affects Tan δ of the copolymer, the preferable hydrogenation rate is set in consideration of the influence on Tan δ as well as the characteristics such as the compatibility between the copolymer and polypropylene. That is, the hydrogenation rate of all conjugated diene compound units of the hydrogenated copolymer (a), the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2) (carbon-carbon double derived from the conjugated diene unit). The hydrogenation rate of the bond) is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol%. The upper limit is not particularly limited, but is preferably 100 mol% or less.

When the hydrogenation rate is 80 mol% or more, the solubility parameter values of the hydrogenated block copolymer and polypropylene approach each other, and the dispersion becomes good. Therefore, the wear resistance and low temperature characteristics of the obtained resin composition, And scratch resistance is improved. This hydrogenation rate can be measured by the proton nuclear magnetic resonance (1H-NMR) method.

(Hydrogenated copolymer (a))
The hydrogenated copolymer (X) of the present embodiment contains the hydrogenated copolymer (a).

The hydrogenated copolymer (a) has a hydrogenated polymer block (hereinafter referred to as polymer block B1) composed of a vinyl aromatic compound and a conjugated diene compound.

Further, it is preferable that the hydrogenated copolymer (a) has at least one block mainly composed of a vinyl aromatic compound (hereinafter, may be referred to as polymer block A).

The hydrogenated copolymer (a) preferably has, for example, a structure represented by the following general formula. Further, the hydrogenated copolymer (a) may be a mixture containing a plurality of types of the following structures at an arbitrary ratio.
(AB1) n
A- (B1-A) n
B1- (AB1) n
[(B1-A) n] m-Z
[(AB1) n] m-Z
[(B1-A) n-B1] m-Z
[(AB1) n-A] m-Z
In each general formula representing the hydrogenated copolymer (a), A is a polymer block mainly composed of a vinyl aromatic compound, and B1 is a polymer block composed of a vinyl aromatic compound and a conjugated diene compound.

The tan δ peak that appears above 0 ° C. is mainly affected by the structure of the random block (B1) composed of the vinyl aromatic compound and the conjugated diene compound and the copolymerization ratio, rather than the block structure of the copolymer itself. From the viewpoint of controlling the temperature, it is preferable to pay attention to the B1 block in the design.

The polymer block A has a vinyl aromatic compound content of more than 90% by mass. The polymer block B1 is composed of a vinyl aromatic compound and a conjugated diene compound, and the content of the vinyl aromatic compound is 20 to 90% by mass. Thereby, the polymer block A and the polymer block (B1) are clearly distinguished.

The boundary line between the polymer block A and the polymer block (B1) does not necessarily have to be clearly distinguished.

Further, n is an integer of 1 or more, preferably an integer of 1 to 5.

m is an integer of 2 or more, preferably an integer of 2 to 11, and more preferably an integer of 2 to 8.

Z represents a coupling agent residue. Here, the coupling residue refers to the polymer block A and the polymer block (B1) as being between the polymer block A and the polymer block A, between the polymer block (B1) and the polymer block (B1), or. Polymer block means the post-binding residue of the coupling agent used to bind between the polymer block A and the polymer block (B1).

The coupling agent is not limited to the following, and examples thereof include polyhalogen compounds and acid esters described later.

When the polymer block A is a copolymer of a vinyl aromatic compound and another monomer unit, the vinyl aromatic compounds in the polymer block A are distributed in a tapered shape even if they are uniformly distributed. In addition, there may be a plurality of uniformly distributed portions and / or a plurality of tapered portions. Further, a plurality of portions having different contents of the vinyl aromatic compound may coexist in the polymer block A.

Further, the vinyl aromatic compound in the polymer block (B1) may be uniformly distributed or may be distributed in a tapered shape. Further, the vinyl aromatic compound may have a plurality of uniformly distributed portions and / or a plurality of tapered portions. Further, a plurality of portions having different contents of the vinyl aromatic compound may coexist in the polymer block (B1).

The content of the total vinyl aromatic compound in the hydrogenated copolymer (a) is preferably 30% by mass to 90% by mass, more preferably 35 to 80% by mass, and further preferably 40 to 70% by mass. %.

The content of the conjugated diene compound in the hydrogenated copolymer (a) is preferably 10% by mass to 70% by mass, more preferably 20 to 65% by mass, and further preferably 30 to 60% by mass. Is.

When the content of the total vinyl aromatic compound in the hydrogenated copolymer (a) is 30% by mass or more, the obtained resin composition has excellent wear resistance. When the content of the total vinyl aromatic compound is 90% by mass or less, the polypropylene resin composition using the hydrogenated copolymer of the present embodiment has excellent low-temperature mechanical properties.
The content of the total vinyl aromatic compound can be calculated from the absorption intensity at 262 nm using an ultraviolet spectrophotometer by the method described in Examples described later.

The content of the vinyl aromatic compound in the hydrogenated polymer block (B1) in the hydrogenated copolymer (a) is preferably 20 to 90% by mass. The upper limit of the content is more preferably 85% by mass, still more preferably 80% by mass. The lower limit of the content is preferably 30% by mass, more preferably 35% by mass, and further preferably 40% by mass.

When the content of the vinyl aromatic compound in the hydrogenated copolymer (B1) is 20% by mass or more, the resistance of the resin composition of the hydrogenated copolymer of the present embodiment to the polyprepylene resin or the rubbery polymer is achieved. The effect of excellent wear resistance can be obtained. When the content of the vinyl aromatic compound is 90% by mass or less, the effect that the low temperature mechanical properties of the resin composition are excellent can be obtained.
The content of the vinyl aromatic compound can be adjusted within the above numerical range by the feed amount of the vinyl aromatic compound at the time of polymerization, and can be measured by a nuclear magnetic resonance apparatus (NMR).

In the hydrogenated copolymer (a), the content of the polymer block A mainly composed of the vinyl aromatic compound is 1% by mass to 40% by mass with respect to the mass of the hydrogenated copolymer (a). It is preferably 5% by mass to 35% by mass, more preferably 10% by mass to 30% by mass.

When the content of the polymer block A in the hydrogenated copolymer (a) is 1% by mass or more, the obtained polypropylene resin composition tends to be excellent in CS (compressive permanent strain (C-set)) and low stickiness. It is in. When the content of the block polymer A is 40% by mass or less, the obtained polypropylene resin composition tends to be excellent in processability.
The content of the polymer block A can be adjusted by adjusting the amount of the monomer added.

The content of the polymer block A in the hydrogenated copolymer (a) is a method (I) in which the copolymer (a') before hydrogenation is oxidatively decomposed by t-butyl hydroperoxide using osmium tetroxide as a catalyst. M. KOLTHOFF, et al., Polym. Sci. 1,429 (1946)) (hereinafter referred to as osmium tetroxide decomposition method) of the polymer mainly composed of a vinyl aromatic compound. It can be calculated using the mass (however, vinyl aromatic compounds having an average degree of polymerization of about 30 or less are excluded).

Further, the content of the polymer block A in the hydrogenated copolymer (a) was determined by using the polymer after hydrogenation (hydrogenated copolymer (a)). Tanaka, et al. , RUBBER CHEMISTRY and TECHNOLOGY 54,685 (1981), which can be measured by a nuclear magnetic resonance apparatus (NMR).

The NMR method will be specifically described by taking as an example the case where the vinyl aromatic compound is styrene and the conjugated diene compound is 1,3-butadiene.

1H-NMR was measured using a sample in which 30 mg of the hydrogenated copolymer (a) was dissolved in 1 g of deuterated chloroform, and the content (Ns value) of the polymer block A (in this case, a polystyrene block) was determined. It was obtained from the ratio of the integrated values of the chemical shifts of 6.9 ppm to 6.3 ppm to the total integrated values.
Block styrene strength (b-St strength)
= (Integrated value from 6.9 ppm to 6.3 ppm) / 2
Random styrene strength (r-St strength)
= (Integrated value from 7.5 ppm to 6.9 ppm) -3 × (b-St)
Ethylene / butylene strength (EB strength)
= Total integrated value-3 x {(b-St strength) + (r-St strength)} / 8
Polystyrene block content (Ns value) obtained by NMR method
= 104 × (b-St strength)
/ [104 x {(b-St strength) + (r-St strength)} + 56 x (EB strength)]

Here, the content of the block polymer A (referred to as “Os value”) in the copolymer (a') before hydrogen addition measured by the angstrom tetroxide decomposition method and the water after hydrogenation measured by the NMR method. There is a correlation represented by the following formula between the content of the block polymer A (referred to as “Ns value”) in the subpolymer (a).
Os value = -0.012 (Ns value) 2 + 1.8 (Ns value) -13.0

The amount of vinyl bond in the conjugated diene compound in the hydrogenated copolymer (a) before hydrogenation is preferably 5 mol% to 95 mol%, more preferably 10 mol to 85 mol%, still more preferably 12 mol to 80 mol%. ..

When the vinyl bond amount of the hydrogenated copolymer (a) before hydrogenation is 5 mol% or more, in the polypropylene resin composition using the hydrogenated copolymer of the present embodiment, the hydrogenated copolymer and the polypropylene resin are used. It has excellent compatibility with.

The vinyl bond portion before hydrogenation becomes ethylene bonded to the main chain after hydrogenation, but since this structure is similar to polypropylene to which methyl is bonded to the main chain as a side chain, the amount of vinyl bond before hydrogenation is large. It is considered that the greater the amount, the greater the compatibility between the two, and the closer the SP value (solubility parameter) is.

When the vinyl bond amount before hydrogenation is 95 mol% or less, the polypropylene resin composition using the hydrogenated copolymer of the present embodiment tends to be excellent in low stickiness and processability.

In the present embodiment, the vinyl bond amount refers to the 1,2-vinyl bond amount (the conjugated diene incorporated in the polymer by the 1,2-bond) and the 3,4-vinyl bond amount with respect to the total conjugated diene. Total content of (conjugated diene incorporated into polymer by 3,4-bond) (where 1,3-vinyl bond content, conjugate when 1,3-butadiene is used as the conjugated diene) When isoprene is used as a diene, it means 3,4-vinyl bond content).

The vinyl bond content based on the conjugated diene prior to hydrogenation can be measured using a nuclear magnetic resonance apparatus (NMR). The microstructure (ratio of cis, trans, vinyl) derived from the conjugated diene compound monomer unit in the hydrogenated copolymer (a) can be arbitrarily changed by using a polar compound or the like described later.

(Hydrogenated copolymer (b1))
The hydrogenated copolymer (X) of the present embodiment contains the hydrogenated copolymer (b1).

The hydrogenated copolymer (b1) has a hydrogenated polymer block (hereinafter referred to as polymer block B2) composed of a vinyl aromatic compound and a conjugated diene compound.

Further, it is preferable that the hydrogenated copolymer (b1) has at least one block mainly composed of a vinyl aromatic compound (hereinafter, may be referred to as polymer block A').

The hydrogenated copolymer (b1) preferably has, for example, a structure represented by the following general formula. Further, the hydrogenated copolymer (b1) may be a mixture containing a plurality of types of the following structures at an arbitrary ratio.
(A'-B2) n
A'-(B2-A) n
B2- (A'-B2) n
[(B2-A') n] m-Z
[(A'-B2) n] m-Z
[(B2-A') n-B2] m-Z
[(A'-B2) n-A'] m-Z

In each general formula representing the hydrogenated copolymer (b1), A'is a polymer block mainly composed of a vinyl aromatic compound, and B2 is a polymer block composed of a vinyl aromatic compound and a conjugated diene compound. ..

The tanδ peak temperature that appears at -25 ° C or higher and lower than 0 ° C is mainly affected by the structure of the random block (B2) composed of the vinyl aromatic compound and the conjugated diene compound and the copolymerization ratio, rather than the block structure of the copolymer itself. Therefore, from the viewpoint of controlling the tan δ peak temperature, it is preferable to pay attention to the B2 block in the design.

The polymer block A'has a vinyl aromatic compound content of more than 90% by mass. The polymer block B2 is composed of a vinyl aromatic compound and a conjugated diene compound, and the content of the vinyl aromatic compound is 5 to 40% by mass. Thereby, the polymer block A'and the polymer block (B2) are clearly distinguished.

The boundary line between the polymer block A'and the polymer block (B2) does not necessarily have to be clearly distinguished.

Further, n is an integer of 1 or more, preferably an integer of 1 to 5.

m is an integer of 2 or more, preferably an integer of 2 to 11, and more preferably an integer of 2 to 8.

Z represents a coupling agent residue. Here, the coupling residue is a polymer block A'and a polymer block (B2), between the polymer block A'and the polymer block A', and the polymer block (B2) -polymer block (B2). It means the residue after binding of the coupling agent used for binding between, or between the polymer block A'-polymer block (B2).

The coupling agent is not limited to the following, and examples thereof include polyhalogen compounds and acid esters described later.

When the polymer block A'is a copolymer of a vinyl aromatic compound and another monomer unit, the vinyl aromatic compound in the polymer block A'is tapered even if it is uniformly distributed. There may be a plurality of uniformly distributed portions and / or a plurality of tapered portions. Further, a plurality of portions having different contents of the vinyl aromatic compound may coexist in the polymer block A'.

Further, the vinyl aromatic compound in the polymer block (B2) may be uniformly distributed or may be distributed in a tapered shape. Further, the vinyl aromatic compound may have a plurality of uniformly distributed portions and / or a plurality of tapered portions. Further, a plurality of portions having different contents of the vinyl aromatic compound may coexist in the polymer block (B2).

The content of the total vinyl aromatic compound in the hydrogenated copolymer (b1) is preferably 10% by mass to 50% by mass, more preferably 13 to 45% by mass, and further preferably 15 to 40% by mass. %.

The content of the conjugated diene compound in the hydrogenated copolymer (b1) is preferably 50% by mass to 90% by mass, more preferably 55 to 87% by mass, and further preferably 60 to 85% by mass. Is.

When the content of the total vinyl aromatic compound in the hydrogenated copolymer (b1) is 10% by mass or more, the obtained resin composition has excellent wear resistance. When the content of the total vinyl aromatic compound is 50% by mass or less, the polypropylene resin composition using the hydrogenated copolymer of the present embodiment has excellent low-temperature mechanical properties. The content of the total vinyl aromatic compound can be calculated from the absorption intensity at 262 nm using an ultraviolet spectrophotometer by the method described in Examples described later.

The content of the vinyl aromatic compound in the hydrogenated polymer block (B2) in the hydrogenated copolymer (b1) is 5 to 40% by mass. The upper limit of the content is more preferably 37% by mass, still more preferably 35% by mass. The lower limit of the content is preferably 7% by mass, more preferably 10% by mass, and even more preferably 12% by mass.

When the content of the vinyl aromatic compound in the hydrogenated copolymer (b1) is 5% by mass or more, the resistance of the resin composition of the hydrogenated copolymer of the present embodiment to the polyprepylene resin or the rubbery polymer is achieved. The effect of excellent wear resistance can be obtained. When the content of the vinyl aromatic compound is 40% by mass or less, the effect that the low temperature mechanical properties of the resin composition are excellent can be obtained. The content of the vinyl aromatic compound can be adjusted within the above numerical range by the feed amount of the vinyl aromatic compound at the time of polymerization, and can be measured by a nuclear magnetic resonance apparatus (NMR).

In the hydrogenated copolymer (b1), the content of the polymer block A'mainly composed of the vinyl aromatic compound is 3% by mass to 40% by mass with respect to the mass of the hydrogenated copolymer (b1). It is preferably 5% by mass to 35% by mass, more preferably 7% by mass to 30% by mass.

When the content of the polymer block A'in the hydrogenated copolymer (b1) is 3% by mass or more, the obtained polypropylene resin composition is excellent in CS (compressive permanent strain (C-set)) and low stickiness. There is a tendency. When the content of the block polymer A'is 40% by mass or less, the obtained polypropylene resin composition tends to be excellent in processability. The content of the polymer block A'can be adjusted by adjusting the amount of the monomer added.

The content of the polymer block A'in the hydrogenated copolymer (b1) is a method of oxidatively decomposing the unhydrated copolymer (b1') with osmium tetroxide as a catalyst by t-butyl hydroperoxide (. A polymer mainly composed of a vinyl aromatic compound obtained by IM KOLTHOFF, et al., Polym. Sci. 1,429 (1946)) (hereinafter referred to as an osmium tetroxide decomposition method). (However, vinyl aromatic compounds having an average degree of polymerization of about 30 or less are excluded) can be calculated.

Further, the content of the polymer block A'in the hydrogenated copolymer (b1) was determined by using the polymer after hydrogenation (hydrogenated copolymer (b1)). Tanaka, et al. , RUBBER CHEMISTRY and TECHNOLOGY 54,685 (1981), which can be measured by a nuclear magnetic resonance apparatus (NMR).

The NMR method will be specifically described by taking as an example the case where the vinyl aromatic compound is styrene and the conjugated diene compound is 1,3-butadiene.

1H-NMR was measured using a sample in which 30 mg of the hydrogenated copolymer (b1) was dissolved in 1 g of deuterated chloroform, and the content (Ns value) of the polymer block A'(in this case, a polystyrene block) was measured. Was obtained from the ratio of the integrated values of the chemical shifts of 6.9 ppm to 6.3 ppm to the total integrated values.
Block styrene strength (b-St strength)
= (Integrated value from 6.9 ppm to 6.3 ppm) / 2
Random styrene strength (r-St strength)
= (Integrated value from 7.5 ppm to 6.9 ppm) -3 × (b-St)
Ethylene / butylene strength (EB strength)
= Total integrated value-3 x {(b-St strength) + (r-St strength)} / 8
Polystyrene block content (Ns value) obtained by NMR method
= 104 × (b-St strength)
/ [104 x {(b-St strength) + (r-St strength)} + 56 x (EB strength)]

Here, the content of the block polymer A'in the copolymer (b1') before hydrogen addition measured by the osmium tetroxide decomposition method (referred to as "Os value") and the content after hydrogen addition measured by the NMR method. There is a correlation represented by the following formula between the content of the block polymer A'in the hydrogenated copolymer (b1) (referred to as "Ns value").
Os value = -0.012 (Ns value) 2 + 1.8 (Ns value) -13.0

The amount of vinyl bond in the conjugated diene compound in the hydrogenated copolymer (b1) before hydrogenation is preferably 50 mol% to 95 mol%, more preferably 55 mol to 90 mol%, still more preferably 60 mol to 85 mol%. ..

When the vinyl bond amount of the hydrogenated copolymer (b1) before hydrogenation is 50 mol% or more, in the polypropylene resin composition using the hydrogenated copolymer of the present embodiment, the hydrogenated copolymer and the polypropylene resin are used. It has excellent compatibility with.

The vinyl bond portion before hydrogenation becomes ethylene bonded to the main chain after hydrogenation, but since this structure is similar to polypropylene to which methyl is bonded to the main chain as a side chain, the amount of vinyl bond before hydrogenation is large. It is considered that the greater the amount, the greater the compatibility between the two, and the closer the SP value (solubility parameter) is.

When the vinyl bond amount before hydrogenation is 95 mol% or less, the polypropylene resin composition using the hydrogenated copolymer of the present embodiment tends to be excellent in low stickiness and processability.

In the present embodiment, the vinyl bond amount refers to the 1,2-vinyl bond amount (the conjugated diene incorporated in the polymer by the 1,2-bond) and the 3,4-vinyl bond amount with respect to the total conjugated diene. Total content of (conjugated diene incorporated into polymer by 3,4-bond) (where 1,3-vinyl bond content, conjugate when 1,3-butadiene is used as the conjugated diene) When isoprene is used as a diene, it means 3,4-vinyl bond content).

The vinyl bond content based on the conjugated diene prior to hydrogenation can be measured using a nuclear magnetic resonance apparatus (NMR). The microstructure (ratio of cis, trans, vinyl) derived from the conjugated diene compound monomer unit in the hydrogenated copolymer (b1) can be arbitrarily changed by using a polar compound or the like described later.

(Hydrogenated copolymer (b2))
The hydrogenated copolymer (X) of the present embodiment contains the hydrogenated copolymer (b2).

The hydrogenated copolymer (b2) has a polymer block mainly composed of at least one aromatic vinyl compound and a polymer block mainly composed of at least one conjugated diene compound.

In the present embodiment, the content of the total aromatic vinyl compound in the hydrogenated block copolymer (b2) is preferably 2 to 30% by mass. The content of the total aromatic vinyl compound in the hydrogenated block copolymer (b2) is preferably 2% by mass or more from the viewpoint of low stickiness of the obtained resin composition. On the other hand, from the viewpoint of low temperature mechanical properties and processability of the obtained resin composition, it is preferably 30% by mass or less. From the same viewpoint as described above, the content of the total aromatic vinyl compound unit in the hydrogenated block copolymer (b2) is more preferably 3 to 25% by mass, more preferably 4 to 22% by mass. Even more preferably, it is 5 to 20% by mass.

The content of the total aromatic vinyl compound unit in the hydrogenated block copolymer (b2) can be measured by the proton nuclear magnetic resonance (1H-NMR) method. Details will be described in Examples described later.

In the present embodiment, it is important that the amount of vinyl bond of the hydrogenated block copolymer (b2) before hydrogenation exceeds 40 mol%. The amount of vinyl bond in the total conjugated diene compound unit contained before hydrogenation of the hydrogenated block copolymer (b2) is from the viewpoint of improving the low temperature mechanical properties and processability of the obtained resin composition. It is preferably 45 mol% or more, more preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more. From the viewpoint of productivity, the upper limit is preferably 99 mol% or less, more preferably 95 mol% or less.

Here, the vinyl bond amount is defined as the 1,2-bond, 3,4-bond, and 1,4-bond of the conjugated diene before hydrogenation, among the 1,2-bond and 1,4-bond. It is the ratio of those incorporated by 3,4-bonding. The amount of vinyl bond in the total conjugated diene unit contained before hydrogenation can be measured by the proton nuclear magnetic resonance (1H-NMR) method.

The structure of the hydrogenated block copolymer (b2) may be in any form such as linear, branched, radial, comb-shaped, etc., but may be a suitable structure depending on desired physical properties and the like.

As long as the polymer block C made of an aromatic vinyl compound and the polymer block D made of a conjugated diene compound are bonded to the hydrogenated copolymer (b2), the bonding form thereof is not limited and is linear. , Branched, radial, comb-shaped or a combination of two or more of these. For example, diblock copolymers represented by CD, triblock copolymers represented by CDC, tetrablock copolymers represented by CDCD, CDC-. Examples thereof include a pentablock copolymer represented by DC, a (CD) nX-type copolymer (X represents a coupling agent residue, and n represents an integer of 3 or more). The vinyl bond amount before hydrogenation in the block D is preferably 40 mol% or more, more preferably 60 mol% or more. The upper limit of the vinyl bond amount before hydrogenation may be, for example, 95 mol%, 90 mol%, 85 mol% or the like.

Further, the hydrogenated block copolymer (b2) contains a polymer block made of other polymerizable monomers other than the polymer block C and the polymer block D, as long as the object of the present invention is not impaired. It may exist.

The hydrogenated copolymer (b2) used in the present embodiment has a total of 1,2-bonding amount and 3,4-bonding amount before hydrogenation of 5 to 30%, and is mainly composed of a conjugated diene compound. It may further have the polymer block E to be used. When the hydrogenated copolymer (b2) further contains the polymer block E, the low temperature mechanical properties and low stickiness of the resin composition tend to be further improved. The content of the polymer block E in the hydrogenated copolymer (b2) is preferably 2 to 30% by mass, more preferably 3 to 25% by mass, still more preferably 4 to 20% by mass. When the content of the polymer block E is within the above range, the low temperature mechanical properties of the obtained resin composition and the compatibility with polypropylene tend to be improved.

The hydrogenated copolymer (b2) used in the present embodiment may further have a polymer block F composed of a random conjugated diene compound and an aromatic vinyl compound. When the hydrogenated copolymer (b2) further contains the polymer block F, the scratch resistance, abrasion resistance, and low stickiness of the resin composition tend to be further improved. The content of the polymer block F in the hydrogenated copolymer (b2) is preferably 2 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass. When the content of the polymer block F is within the above range, the scratch resistance, abrasion resistance, and low stickiness of the obtained resin composition tend to be improved.

(Tanδ)
The hydrogenated copolymer (X) has a tan δ peak temperature of 0 ° C. or higher (preferably 0 ° C. or higher and 50 ° C. or lower) and a tan δ height of 1.0 or higher (preferably 1.0 or higher and 5.0 or lower). It has at least one peak (preferably 1 to 3), the tanδ peak temperature is less than 0 ° C (preferably -50 ° C or higher and less than 0 ° C), and the tanδ peak height is less than 0.2 (preferably 0). It has at least two (preferably 2-5) peaks of 0.01 or more and less than 0.2.

Although the tanδ peak height is also affected by the tanδ peak height originally possessed by each of the hydrogenated copolymer (a), the hydrogenated copolymer (b1), and the hydrogenated copolymer (b2). As the tan δ peak of the hydrogenated copolymer (X), the influence of the mixed mass ratio is dominant. Therefore, the tanδ peak height is the mass ratio (a) / {(b1) + of the contents of the hydrogenated copolymer (a), the hydrogenated copolymer (b1), and the hydrogenated copolymer (b2). It can be controlled by (b2)}. From the viewpoint of wear resistance, low temperature characteristics and various performance balances of the obtained resin composition, it is 45/55 to 95/5, preferably 50/50 to 93/7, and even more preferably 55/45 to 90/10. , 60/40 to 88/12 are even more preferable.

The hydrogenated copolymer (a), the hydrogenated copolymer (b1), and the hydrogenated copolymer (b2) have a predetermined mass ratio of the hydrogenated copolymer pellets obtained by different polymers. The blend may be blended in such a manner, or the blend of the polymerization solutions adjusted to have a predetermined mass ratio may be desolved and molded as a single pellet.

The tanδ peak temperature and the tanδ peak height can be controlled by the type of hydrogenated copolymer used.

The hydrogenated copolymer (a) has one or more tan δ peaks at 0 ° C. or higher (preferably 0 ° C. or higher and 50 ° C. or lower) and no peak below 0 ° C. in viscoelasticity measurement (1 Hz). Is preferable. The number of tan δ peaks at 0 ° C. or higher is preferably 1 to 3, and more preferably 1 to 2.

The hydrogenated copolymer (b1) may have one or more tanδ peaks at -25 ° C or higher and lower than 0 ° C in viscoelasticity measurement (1 Hz), and no peaks at 0 ° C or higher and lower than -25 ° C. preferable. The number of tan δ peaks of −25 ° C. or higher and lower than 0 ° C. is preferably 1 to 5, and more preferably 1 to 3.

The hydrogenated copolymer (b2) has one or more tanδ peaks at less than -25 ° C (preferably -50 ° C or higher and lower than -25 ° C) in viscoelasticity measurement (1 Hz), and peaks at -25 ° C or higher. It is preferable not to have it. The number of tan δ peaks below −25 ° C. is preferably 1 to 5, and more preferably 1 to 3.

It is easy to control the peak temperature to adjust the vinyl bond amount, hydrogenation rate, etc. after setting the block structure of each hydrogenated copolymer so that each polymer has a peak in a predetermined temperature range. This is a preferred embodiment from the viewpoint. Specifically, for the hydrogenated copolymer (a) and the hydrogenated copolymer (b1), the peak of the random block tends to exist in this temperature range, and for the hydrogenated copolymer (b2), the conjugated diene block. Since peaks are likely to exist in this temperature range, it is preferable to set the peak temperature by paying attention to each of these blocks.

Thereby, the hydrogenated copolymer (a), the hydrogenated copolymer (b1), and the hydrogenated copolymer (b2) can be clearly distinguished from each other. However, if the peak temperatures of (a) and (b1) and (b1) and (b2) are too close, the two peaks are combined and appear as one, so the peak tops of each are observed even after mixing. It is preferable to set the peak temperatures of the hydrogenated copolymer (a), the hydrogenated copolymer (b1), and the hydrogenated copolymer (b2) so as to show peaks at positions separated from each other.

The tan δ peak temperature and tan δ peak height of the hydrogenated copolymer are determined in the random copolymer block of the polymer block mainly composed of the conjugated diene compound and / or the polymer block composed of the conjugated diene compound and the aromatic vinyl compound. It can be controlled by adjusting the content of the aromatic vinyl compound, the amount of vinyl bond before hydrogenation, and the hydrogenation rate.

The content of the aromatic vinyl compound in the random copolymer block composed of the conjugated diene compound and the aromatic vinyl compound shall be controlled by adjusting the addition amount of each monomer in the production process of the hydrogenated copolymer. Can be done. The tanδ peak temperature tends to increase as the content of the aromatic vinyl compound in the random copolymer increases, and tends to decrease as the content of the aromatic vinyl compound decreases. The tanδ peak height tends to decrease as the content of the aromatic vinyl compound in the random copolymer increases, and tends to increase as the content of the aromatic vinyl compound decreases.

The vinyl bond amount of the copolymer before hydrogenation can be controlled by using a vinylizing agent such as a Lewis base, for example, ether or amine, or by adjusting the amount used and the polymerization temperature. When the vinyl bond amount before hydrogenation is 50% or more, the tan δ peak temperature tends to increase as the vinyl bond amount before hydrogenation increases, and tends to decrease as the vinyl bond amount decreases. The tanδ peak height tends to decrease due to the distribution of the vinyl bond amount. The distribution of the vinyl bond amount results from the instability of the polymerization temperature.

The hydrogenation rate can be controlled, for example, by adjusting the amount of catalyst and the amount of hydrogen feed during hydrogenation. The tan δ peak temperature tends to decrease as the hydrogenation rate increases, and tends to increase as the hydrogenation rate decreases. The tanδ peak height tends to decrease due to the distribution of hydrogenation rates. The distribution of hydrogenation rates arises from the instability of the hydrogenation reaction temperature.

(Method for producing hydrogenated copolymer (a), hydrogenated copolymer (b1) and hydrogenated copolymer (b2))
The method for producing the hydrogenated copolymer (a) and the hydrogenated copolymer (b) is not limited to the following, and for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, and Japanese Patent Publication No. 46. It is described in Japanese Patent Publication No. 32415, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 48-4106, Japanese Patent Publication No. 51-49567, Japanese Patent Application Laid-Open No. 59-166518, and the like. The method can be mentioned.

The copolymer before hydrogenation is not limited to the following, but for example, a method of performing living anionic polymerization using a predetermined monomer using a polymerization initiator such as an organic alkali metal compound in a hydrocarbon solvent and the like. Obtained by

The hydrocarbon solvent is not particularly limited, and for example, aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane, and n-octane, cyclohexane, cycloheptane, and methylcycloheptane. Examples thereof include alicyclic hydrocarbons such as benzene, toluene, xylene, and aromatic hydrocarbons such as ethylbenzene.

As the polymerization initiator, an organic alkali metal compound known to have anionic polymerization activity with respect to a conjugated diene compound and a vinyl aromatic compound can be generally used.

Examples thereof include an aliphatic hydrocarbon alkali metal compound having 1 to 20 carbon atoms, an aromatic hydrocarbon alkali metal compound having 1 to 20 carbon atoms, and an organic amino alkali metal compound having 1 to 20 carbon atoms.

Examples of the alkali metal contained in the polymerization initiator include, but are not limited to, lithium, sodium, potassium and the like.
The alkali metal may be contained alone or in combination of two or more in one molecule.

The polymerization initiator is not limited to the following, and is, for example, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, and the like. Examples thereof include a reaction product of trilylithium, diisopropenylbenzene and sec-butyllithium, and a reaction product of divinylbenzene, sec-butyllithium and a small amount of 1,3-butadiene.

Furthermore, a lithium compound in which 1 to several molecules of isoprene monomer are inserted to improve the solubility of 1- (t-butoxy) propyl lithium disclosed in US Pat. No. 5,708,092, UK patent. Syloxy group-containing alkyl lithium such as 1- (t-butyldimethylsiloxy) hexyl lithium disclosed in 2,241,239, amino group-containing disclosed in US Pat. No. 5,527,753. Aminolithiums such as alkyllithium, diisopropylamide lithium and hexamethyldisilazidolithium can also be used.

The amount of the lithium compound used as the polymerization initiator depends on the molecular weight of the target block copolymer, but generally 0.01 to 0.5 fm (part by mass with respect to 100 parts by mass of the monomer) should be used. Can be done. The amount of the lithium compound used as the polymerization initiator is preferably 0.03 to 0.3 fm, and more preferably 0.05 to 0.15 fm.

When a conjugated diene compound and a vinyl aromatic compound are copolymerized using an organic alkali metal compound as a polymerization initiator, a vinyl bond (1,2-bond or 3,4-bond) resulting from the conjugated diene compound incorporated into the copolymer is incorporated. A tertiary amine compound or an ether compound can be added as a vinyl bond amount adjusting agent in order to adjust the content of the bond) and the random copolymerization of the conjugated diene compound and the vinyl aromatic compound.

The tertiary amine compound is not particularly limited, and examples thereof include compounds represented by the following formulas.
R1R2R3N
(In the formula, R1, R2, and R3 are hydrocarbon groups having 1 to 20 carbon atoms or a tertiary amino group.)

Such compounds include, but are not limited to, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidin, N, N, N', N'-tetra. Methylethylenediamine, N, N, N', N'-tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N', N'', N''-pentamethylethylenetriamine , N, N'-dioctyl-p-phenylenediamine and the like. Of these, N, N, N', N'-tetramethylethylenediamine is preferable.

Further, as the ether compound, a linear ether compound, a cyclic ether compound or the like can be used.

Examples of the linear ether compound include 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, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. Examples thereof include dialkyl ether compounds of diethylene glycol.

Examples of the cyclic ether compound include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane, and furfuryl alcohol. Alkyl ether and the like can be mentioned.

The amount of the tertiary amine compound or ether compound used is preferably 0.1 to 4 (mol / 1 mol of alkali metal), more preferably 0.2 to 3 (mol) with respect to the polymerization initiator of the organic alkali metal compound. Mol / alkali metal 1 mol).

In the production process of the hydrogenated copolymers (a), (b1) and (b2), sodium alkoxide may coexist when the copolymerization is carried out.

The sodium alkoxide is, for example, a compound represented by the following formula, but is not limited to the following. In particular, sodium alkoxide having an alkyl group having 3 to 6 carbon atoms is preferable, and sodium t-butoxide and sodium t-pentoxide are more preferable.
NaOR
(In the formula, R is an alkyl group having 2 to 12 carbon atoms)

The amount of sodium alkoxide used in the polymerization steps of the hydrogenated copolymers (a), (b1) and (b2) is preferably 0.01 with respect to the vinyl bond amount adjusting agent (tertiary amine compound or ether compound). More than 0.1 (molar ratio), more preferably 0.01 or more and less than 0.08 (molar ratio), still more preferably 0.03 or more and less than 0.08 (molar ratio), still more preferably 0. It is 04 or more and less than 0.06 (molar ratio).

When the amount of sodium alkoxide is in this range, it has a copolymer block containing a conjugated diene compound having a high vinyl bond amount and a polymer block mainly containing a vinyl aromatic compound having a narrow molecular weight distribution, and the molecular weight distribution is large. There is a tendency that a polymer having a narrow width and high strength can be produced at a high production rate.

The method for copolymerizing the conjugated diene compound and the vinyl aromatic compound using the organic alkali metal compound as the polymerization initiator is not particularly limited, and may be batch polymerization, continuous polymerization, or a combination thereof. good.

The polymerization temperature is not particularly limited, but is usually 0 to 180 ° C, preferably 30 to 150 ° C.

The time required for polymerization varies depending on the conditions, but is usually within 48 hours, preferably 0.1 to 10 hours.

Further, it is preferable to polymerize in an atmosphere of an inert gas such as nitrogen gas.

The polymerization pressure may be set within a range of pressure sufficient to maintain the monomer and the solvent in the liquid phase in the above polymerization temperature range, and is not particularly limited.

Further, at the end of the polymerization, a required amount of a coupling agent having two or more functional groups may be added to carry out the coupling reaction.

The coupling agent having two or more functional groups is not particularly limited, and known ones can be used.

The bifunctional coupling agent is not limited to the following, but for example, dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenylbenzoate, and phthalates. And so on.

The polyfunctional coupling agent having a trifunctional or higher functional group is not limited to the following, but for example, polyalcohols having a trivalent or higher valence, epoxidized soybean oil, a polyvalent epoxy compound such as a diglycidyl bisphenol A, and a formula R1 (4-). n) Examples thereof include a silicon halide compound represented by SiXn (where R1 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n represents an integer of 3 or 4), and a tin halide compound. ..

Examples of the halogenated silicon compound include, but are not limited to, methylsilyl trichloride, t-butyl silyl trichloride, silicon tetrachloride, and bromines thereof.

Examples of the halogenated tin compound include, but are not limited to, polyvalent halogen compounds such as methyl tin trichloride, t-butyl tin trichloride, and tin tetrachloride. Further, dimethyl carbonate, diethyl carbonate and the like can also be used.

For the hydrogenated copolymers (a), (b1) and (b2), a modifying agent for forming a functional group-containing atomic group was added to the living end of the block copolymer obtained by the above method. It may be a thing.

The functional group-containing atomic group is not limited to the following, but for example, a hydroxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxyl group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, Carboxyl ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, Examples thereof include an atomic group containing at least one functional group selected from the group consisting of an isocyanate group, an isothiocyanate group, a silicon halide group, a silanol group, an alkoxysilicon group, a tin halide group, an alkoxytin group and a phenyltin group. ..

The modifying agent having a functional group-containing atomic group is not limited to the following, and for example, tetraglycidylmethoxylenidamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, δ-valerolactone, 4-methoxy. Benzophenone, γ-glycidoxyethyl trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, 1,3-dimethyl -2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N'-dimethylpropylene urea, N-methylpyrrolidone and the like can be mentioned.

The amount of the modifier added is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, still more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the hydrogenated copolymer before modification. It is a mass part.

The addition reaction temperature of the denaturant is preferably 0 to 150 ° C, more preferably 20 to 120 ° C.

The time required for the denaturation reaction varies depending on the denaturation reaction conditions, but is preferably within 24 hours, more preferably 0.1 to 10 hours.

The hydrogenated catalyst used for producing the hydrogenated copolymers (a), (b1) and (b2) is not particularly limited, and for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636. The hydrogenated catalyst described in Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-377970, Japanese Patent Publication No. 1-53851, Japanese Patent Publication No. 2-9041 and the like can be used.

Preferred hydrogenated catalysts include mixtures with titanocene compounds and / or reducing organometallic compounds.

The titanocene compound is not particularly limited, and examples thereof include the compounds described in JP-A-8-109219. Specific examples thereof include biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium. Examples thereof include compounds having at least one (substituted) cyclopentadienyl structure such as trichloride, an indenyl structure, and a ligand having a fluorenyl structure.

The reducing organic metal compound is not particularly limited, and examples thereof include organic alkali metal compounds such as organic lithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.

The reaction temperature of the hydrogenation reaction is usually 0 to 200 ° C, preferably 30 to 150 ° C.

The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to 15 MPa, more preferably 0.2 to 10 MPa, still more preferably 0.3 to 5 MPa.

The reaction time of the hydrogenation reaction is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours.

The hydrogenation reaction can be used in any of a batch process, a continuous process, or a combination thereof.

If necessary, the catalyst residue may be removed from the reaction solution after the hydrogenation reaction is completed.

The method for separating the hydrogenated copolymer and the solvent is not limited to the following, but for example, a polar solvent which is a poor solvent for the hydrogenated copolymer such as acetone or alcohol in the solution of the hydrogenated copolymer. , A method of precipitating and recovering the hydrogenated copolymer, or a method of pouring a solution of the hydrogenated copolymer into boiling water with stirring and removing the solvent by steam stripping to recover, water addition. Examples thereof include a method of distilling off the solvent by directly heating the solution of the copolymer.

The hydrogenation rate (also referred to as hydrogenation rate) of the aliphatic double bond derived from the conjugated diene compound in the hydrogenated copolymers (a), (b1) and (b2) is preferably 70% or more, more preferably. Is 80% or more, more preferably 90% or more.

When the hydrogenation rate is 70% or more, the thermal deterioration (oxidative deterioration) of the hydrogenated copolymer of the present embodiment can be suppressed, so that the thermoplastic elastomer containing the hydrogenated copolymer of the present embodiment can be suppressed. It is possible to suppress deterioration of performance such as mechanical strength due to thermal deterioration (oxidative deterioration) of the composition.

Further, when the hydrogenation rate is 80% or more, better weather resistance can be obtained. There is no particular upper limit to the hydrogenation rate, but it is preferably 100% or less, and preferably 99% or less.

The hydrogenation rate here refers to the ratio of hydrogenated aliphatic double bonds among the aliphatic double bonds based on the conjugated diene compound monomer unit before hydrogenation of the hydrogenated copolymer.

The hydrogen addition rate can be controlled by, for example, the amount of catalyst at the time of hydrogen addition, and the hydrogen addition rate can be controlled by, for example, the amount of catalyst at the time of hydrogen addition, the amount of hydrogen feed, pressure, temperature and the like.

The hydrogenation rate of the (aromatic) double bond based on the vinyl aromatic compound in the hydrogenated copolymer is not particularly limited, and is preferably 50% or less, more preferably 30% or less, still more preferably 20% or less. Is. Here, the hydrogenation rate of the aromatic double bond means the ratio of the hydrogenated double bond among the aromatic double bonds before hydrogenation.

The hydrogenation rate can be measured using a nuclear magnetic resonance apparatus (NMR).

The hydrogenated copolymer of the present embodiment may contain an antioxidant on the surface and / or inside thereof, for example, by adding an antioxidant during production.

The following antioxidant may be added to the resin composition of the present embodiment described later.

Examples of the antioxidant include, but are not limited to, phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like.

Specifically, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (4'-hydroxy-3', 5'-di-t-butyl-phenyl) propionate, tetrax- [Methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane], Tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-butylidene-bis- (3-methyl-6-t-butylphenol), 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy } -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxy) Phenol) propionate], 1,6-hexanediol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-Hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4) -Hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di- t-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) mixture of calcium and polyethylene wax (50%), octylated diphenylamine, 2,4- Bis [(octylthio) methyl] -o-cresol, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, butyric acid, 3,3-bis (3-t-butyl-4) -Hydroxyphenyl) ethylene ester, 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-tris (4-t-butyl-3-hydroxy) -2,6-dimethylbenzyl) isocyanurate, 2-t-butyl-6- (3'-t-butyl-5'-methyl -2'-Hydroxybenzyl) -4-methylphenyl-acrylate, and 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) -ethyl] -4,6-di-t-pentyl Examples include phenyl acrylate.

The hydrogenated copolymers (a), (b1) and (b2) may be pelletized.

As a method for pelletizing, for example, the hydrogenated copolymers (a), (b1) and (b2) are extruded in a strand shape from a single-screw or twin-screw extruder, and a rotary blade installed on the front surface of the die portion is used. Method of cutting in water; Method of extruding a hydrogenated copolymer in a strand shape from a uniaxial or biaxial extruder, water-cooled or air-cooled, and then cutting with a strand cutter; A method of forming the sheet into a sheet shape, cutting the sheet into a strip shape, and then cutting the sheet into cubic pellets with a pelletizer can be mentioned.

The size and shape of the pellets of the hydrogenated copolymers (a), (b1) and (b2) are not particularly limited.

As for the hydrogenated copolymers (a), (b1) and (b2), a pellet blocking inhibitor may be added to the pellets, if necessary, 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.

The preferable blending amount of the pellet blocking inhibitor is 500 to 6000 ppm with respect to the hydrogenated copolymers (a), (b1) and (b2), and the more preferable amount is 1000 to 5000 ppm. 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.

The weight average molecular weight of the hydrogenated copolymers (a), (b1) and (b2) is preferably 50,000 to 500,000, more preferably 80,000 to 450,000, still more preferably 100. It is 000-400,000.

When the weight average molecular weights of the hydrogenated copolymers (a), (b1) and (b2) are 50,000 or more, the handleability (blocking resistance) of the pellets tends to be good. When the weight average molecular weights of the hydrogenated copolymers (a), (b1) and (b2) are 500,000 or less, sufficient fluidity and moldability tend to be obtained.

The molecular weight distributions (Mw / Mn) of the hydrogenated copolymers (a), (b1) and (b2) are preferably 1.01 to 8.0, more preferably 1.01 to 6.0, and even more preferably 1.01 to 6.0. It is 1.01 to 5.0. If the molecular weight distribution is within the above range, better molding processability tends to be obtained.

The shape of the molecular weight distribution of the hydrogenated copolymers (a), (b1) and (b2) measured by GPC is not particularly limited, and may have a polymodal molecular weight distribution in which two or more peaks are present. However, it may have a monomodal molecular weight distribution having one peak.

The weight average molecular weight (Mw) and molecular weight distribution [Mw / Mn; ratio of weight average molecular weight (Mw) to number average molecular weight (Mn)] of the hydrogenated copolymers (a), (b1) and (b2) are The molecular weight of the peak of the chromatogram measured by gel permeation chromatography (GPC) by the method described in Examples described later is measured by a calibration line obtained from the measurement of a commercially available standard polystyrene (using the peak molecular weight of the standard polystyrene). Can be found using Create).

The melt flow rate (MFR; ISO 1133 compliant) of the hydrogenated copolymer (a), the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2) is 0.01 to less than 100 g / 10 minutes. It is preferably in the range, more preferably 0.1 to 80 g / 10 minutes or less, and even more preferably 1.0 to 50 g / 10 minutes or less. When it is 0.01 g / 10 minutes or more, the fluidity of the obtained resin composition tends to be sufficiently secured, and when it is 100 g / 10 minutes or less, the low stickiness of the obtained resin composition and the sheet-shaped molded product is obtained. It tends to be sufficiently secured.

[Resin composition]
The resin composition of the present embodiment contains the hydrogenated copolymer (X) of the present embodiment containing the hydrogenated copolymers (a), (b1) and (b2) described above, and the polypropylene resin (c). contains.

(Polypropylene resin (c))
As the polypropylene resin (c), in addition to homopolypropylene, random polypropylene and block polypropylene can also be used.

Here, "random" in random polypropylene means that propylene and a monomer other than propylene are copolymerized, and the monomer other than propylene is randomly incorporated into the propylene chain, and the monomer other than propylene is not substantially chained. To say.

The random polypropylene is not particularly limited as long as the content of the propylene unit is less than 99% by mass.

Examples of the random polypropylene include a random copolymer of propylene and ethylene or a random copolymer of propylene and an α-olefin having 4 to 20 carbon atoms.

The α-olefin is not limited to the following, and is, for example, ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-. Examples thereof include pentene, 1-hexene, 1-octene, 1-nonen, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene. Preferred are α-olefins having 2 to 8 carbon atoms, and examples thereof include ethylene, 1-butene, 3-methyl-1-butene, 1-hexene and 4-methyl-1-pentene.

These α-olefins can be used alone or in combination of two or more. Further, homopolypropylene and random polypropylene can also be used alone or in combination of two or more.

In the resin composition of the present embodiment, the mass ratio (a) / {of the content of the hydrogenated copolymer (a) to the contents of the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2). (B1) + (b2)} is preferably 45/55 to 95/5, and from the viewpoint of wear resistance, low-temperature mechanical properties, and characteristic balance of the resin composition containing the polypropylene resin (c). It is more preferable that {(a) + (b1) + (b2)} / (c) = 5/95 to 95/5, and 10/90 to 90 from the viewpoint of low stickiness and processability of the resin composition. It is even more preferably / 10, and even more preferably 15/85 to 85/15. From the viewpoint of low stickiness of the obtained resin composition, the hydrogenated copolymer (a) is preferably 95% by mass or less, and from the viewpoint of processability, the hydrogenated copolymer (b1) + (b2) is 95% by mass. % Or less is preferable.

The resin composition of the present embodiment may be used in combination with other additives depending on the required performance. The additive is not particularly limited, and is, for example, a lubricant, a flame retardant, a stabilizer, a colorant, a pigment, an antioxidant, an antioxidant, a dispersant, a flow enhancer, a mold release agent such as a metal stearate salt, and silicone. Examples thereof include oils, mineral oil-based softeners, synthetic resin-based softeners, copper damage inhibitors, cross-linking agents, and nucleating agents.

(Manufacturing method of resin composition)
Examples of the method for producing the resin composition of the present embodiment include a hydrogenated copolymer (a), a hydrogenated copolymer (b1), a hydrogenated copolymer (b2) and a polypropylene resin, and if necessary, other materials. Examples thereof include a method of dry blending the components in an amount according to the characteristics of each component, and a method of preparing the components by an apparatus subjected to mixing of ordinary polymer materials.

Examples of the mixing device include, but are not limited to, a kneading device such as a Banbury mixer, a lab plast mill, a single-screw extruder, and a twin-screw extruder. It is preferable from the viewpoint of kneadability. The melting temperature at the time of kneading can be appropriately set, but is usually in the range of 130 to 300 ° C, preferably in the range of 150 to 250 ° C.

[Molded product of resin composition]
The molded product of the present embodiment is the molded product of the resin composition of the present embodiment described above.

The molded body includes an injection molded plate, an extruded sheet-shaped molded body (sheet, film), a tube, a bag, a medical molded body, for example, a medical tube, a medical film, an automobile member, for example, an automobile interior skin material, a medical infusion solution. Examples thereof include a bag and a packaging material such as a food packaging material and a clothing packaging material, but the molded product of the present embodiment is not limited to the above.

The molded product of this embodiment can be molded by the method described below. The resin composition of the present embodiment can be molded by softening or melting with heat. For example, molding can be performed using conventional molding methods such as compression molding, injection molding, gas assisted injection molding, hollow molding, sheet molding, rotary molding, laminating molding, calendar molding, vacuum molding, heat molding, and extrusion molding. can.

These molding techniques may be used alone or in combination of two or more. Among these, injection molding is preferable from the viewpoint of productivity.

On the other hand, for example, the method for forming the tube is not particularly limited, but for example, the resin composition of the present embodiment is put into an extruder to be melted, passed through a die to form a tubular shape, and water-cooled or air-cooled to form a tube. There is a way to do it.

As the extruder, a single-screw or multi-screw extruder can be used, and a plurality of extruders can be used to form a multi-layer extruded multi-layer tube. Further, it can also be molded as a tube directly from the extruder used in producing the resin composition using the polypropylene resin (c).

The tube, which is a molded body, may be made into a multilayer tube by laminating other polymers as long as the object of the present embodiment is not impaired. The above-mentioned other polymers may be used alone or in combination of two or more, and may be used by laminating in a single layer or a multilayer in which the types may be different for each layer.

The layer made of the other polymer of the tube having the multi-layer structure may be any of the innermost layer, the intermediate layer, and the outermost layer depending on the desired performance to be imparted.

In the present embodiment, in order to further suppress an increase in wall thickness, maintain flexibility, and improve pressure resistance and the like, a braided reinforcing thread or a spiral reinforcing body can be wound to form a pressure resistant tube (hose). ..

The braided reinforcing thread is provided inside or between layers in the thickness direction, and vinylon, polyamide, polyester, aramid fiber, carbon fiber, metal wire, etc. can be used, and the spiral reinforcing body is provided on the outer periphery, and metal, plastic, etc. Can be used.

The method for producing the sheet-shaped molded product is not particularly limited, and examples of the molding method in which the resin composition is put into an extruder and extruded include a T-die method and an inflation method.

As the inflation molding, normal air-cooled inflation molding, air-cooled two-stage inflation molding, high-speed inflation molding, water-cooled inflation molding and the like can be adopted.

Further, a blow molding method such as direct blow or injection blow, or a press molding method can also be adopted. As the extruder to be used, a single-screw or multi-screw extruder can be used, and a multi-layer extrusion sheet can be formed by using a plurality of extruders.

It can also be molded as a sheet directly from the extruder used to manufacture the resin composition.

The sheet-shaped molded product may be a single-layer sheet, but may be a multilayer sheet by laminating other polymers as long as the gist of the present embodiment is not impaired. Such other polymers include, but are not limited to, olefin polymers such as polypropylene, polyethylene, ethylene-propylene copolymer rubber (EPM) and ethylene-propylene-non-conjugated diene copolymer rubber (EPDM); polyester. Polyester-based polymers such as elastomers, polyethylene terephthalates and polybutylene terephthalates; polyamide-based resins such as polyamide 6, polyamides 6, 6, polyamides 6, 10, polyamide 11, polyamide 12, and polyamides 6, 12; methyl polyacrylate and Acrylic resins such as polymethylmethacrylate; polyoxymethylene resins such as polyoxymethylene homopolymers and polyoxymethylene copolymers; styrene resins such as styrene homopolymers, acrylonitrile-styrene resins, and acrylonitrile-butadiene-styrene resins. Polycarbonate resin; styrene-based elastomers such as styrene-butadiene copolymer rubber and styrene-isoprene copolymer rubber and hydrogenated products thereof or modified products thereof; natural rubber; synthetic isoprene rubber and liquid polyisoprene rubber and hydrogenated products thereof. Substance or modified product; chloroprene rubber; acrylic rubber; butyl rubber; acrylonitrile-butadiene rubber; epichlorohydrin rubber; silicone rubber; fluororubber; chlorosulfonated polyethylene; urethane rubber; polyurethane-based elastomer; polyamide-based elastomer; polyester-based elastomer; soft Examples include vinyl chloride resin. One or more blends of these other polymers may be laminated in a single layer or in multiple layers of different types for each layer.

For lamination with other polymers, co-extrusion molding methods such as multi-layer T-die method, multi-layer inflation method and extrusion lamination method, general multilayer sheet or film molding methods such as wet lamination, dry lamination and press molding. , A multi-layer injection blow such as a coin injection blow and a blow molding method such as a multi-layer direct blow can be adopted.

Further, the molded multilayer laminate may remain unstretched, or may be uniaxially or biaxially stretched.

The bag refers to a bag-shaped molded product that can be molded from the sheet-shaped molded product. Examples of the bag include a food packaging bag, a clothing packaging bag, a medical bag, for example, a medical infusion bag, a drug packaging bag, and the like.

As shown in Examples described later, the resin composition of the present embodiment is excellent in wear resistance, low temperature mechanical properties, and a balance of each property, and can be used without particular limitation. Taking advantage of this characteristic, packaging of various clothing, packaging of various foods, packaging of daily miscellaneous goods, packaging of industrial materials, laminating of various rubber products, resin products, leather products, elastic tapes used for paper diapers, dicing films, etc. Industrial supplies, adhesive protective films used to protect building materials and steel plates, adhesive film base materials, meat trays for fresh fish, fruit and vegetable packs, sheet supplies such as frozen food containers, household appliances such as TVs, stereos, and vacuum cleaners. Bumper parts, body panels, side seals, interiors (instrument panels, door trims, airbag covers, etc.) Automotive interior / exterior parts such as skin materials, road paving materials, waterproof materials, impermeable sheets, civil engineering packing, daily necessities, leisure goods, etc. It can be suitably used for a wide range of applications such as toys, industrial supplies, furniture supplies, writing tools, transparent pockets, holders, stationery such as file spines, and medical tools such as infusion bags.

[Thermoplastic Elastomer Composition]
The hydrogenated copolymer (X) of the present embodiment including the above-mentioned hydrogenated copolymer (a), hydrogenated copolymer (b1), and (b2) is wear-resistant by combining with a rubber-like polymer. A thermoplastic elastomer composition having an excellent balance between properties, low-temperature mechanical properties, and various performances can be obtained. The thermoplastic elastomer composition typically contains a high molecular weight SEBS / PP / oil as a basic composition and a hydrogenated copolymer of the present embodiment as a medium molecular weight component.

The rubber-like polymer contains a vinyl aromatic compound, preferably contains at least one polymer block mainly composed of the vinyl aromatic compound, and also contains the vinyl aromatic compound and is a vinyl aromatic compound. A rubber or elastomer having a content of 60% by mass or less is also preferable. Specifically, styrene-butadiene rubber and its hydrogenated material (however, the hydrogenated copolymer (a), the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2) of the present embodiment are excluded). Examples thereof include a styrene-butadiene block copolymer and a hydrogenated product thereof, a styrene-butadiene / isoprene block copolymer and a hydrogenated product thereof, and the like. The weight average molecular weight of the rubber-like polymer is preferably 10,000 to 1,500,000, more preferably 20,000 to 1,000,000, and even more preferably 30,000 to 800,000. When the weight average molecular weight of the rubber-like polymer is 10,000 or more, sufficient mechanical strength tends to be obtained, and when the weight average molecular weight is 1.5 million or less, the molding processability tends to be good.

By mixing the above-mentioned hydrogenated copolymer (a), hydrogenated copolymer (b1) and hydrogenated copolymer (b2), thermoplastic resin and / or rubber-like polymer, wear resistance and low temperature can be obtained. A thermoplastic elastomer composition having an excellent balance of mechanical properties and various performances can be obtained. The thermoplastic resin and the rubbery polymer may contain both, or may contain only one of them.

The sum of the masses of the hydrogenated copolymer (a), the hydrogenated copolymer (b1), and the hydrogenated copolymer (b) contained in the thermoplastic elastomer composition, and the total mass of the thermoplastic resin and the rubber-like polymer. The ratio to (when only one of the thermoplastic resin and the rubbery polymer is contained, the mass of the contained one) is [(a) + (b1) + (b2)] / (heat). The total of the thermoplastic resin composition and the rubbery polymer) = 20/80 to 100/0, more preferably 25/75 to 95/5, and even more preferably 30/70 to 90/10.

When the content of the sum of masses of the hydrogenated copolymer (a), the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2) is in the above range, the thermoplastic elastomer composition has abrasion resistance. Excellent low-temperature mechanical properties and various performance balance.

When the thermoplastic elastomer composition contains both the thermoplastic resin and the rubber-like polymer, the mass ratio of the thermoplastic resin / rubber-like polymer is preferably 95/5 to 5/95, more preferably. , 80/20 to 20/80, more preferably 70/30 to 30/70.

The thermoplastic elastomer composition may contain a softening agent.

Examples of the softening agent include paraffin-based oils, naphthen-based oils, aromatic oils, paraffin waxes, liquid paraffins, white mineral oils, plant-based softeners and the like. Among these, paraffin oil, liquid paraffin, and white mineral oil are more preferable from the viewpoint of low temperature characteristics, bleed resistance, and the like of the thermoplastic elastomer composition and the molded product. The kinematic viscosity of the softener at 40 ° C. is preferably 500 mm ² / sec or less. The lower limit of the kinematic viscosity of the softener at 40 ° C. is not particularly limited, but is preferably 10 mm ² / sec. When the kinematic viscosity of the softener at 40 ° C. is 500 mm ² / sec or less, the fluidity of the thermoplastic elastomer composition tends to be further improved, and the formability tends to be further improved. The kinematic viscosity of the softener can be measured by a method of testing using a glass capillary viscometer or the like. In the thermoplastic elastomer composition, the blending amount of the softening agent may be 5 to 100 parts by mass with respect to 100 parts by mass of the total amount of the hydrogenated copolymer, the thermoplastic resin and the rubber-like polymer of the present embodiment. It is preferably more preferably 10 to 80 parts by mass, still more preferably 15 to 60 parts by mass.

The thermoplastic elastomer composition may further contain an olefin-based elastomer. Examples of the olefin resin and the olefin elastomer include α-olefin polymers or copolymers having 2 to 20 carbon atoms, and copolymers of ethylene and unsaturated carboxylic acids or unsaturated carboxylic acid esters. The olefin-based elastomer is not limited to the following, and is, for example, an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-4-methylpentene copolymer, or an ethylene-. 1-octene copolymer, propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene- Co., Ltd., propylene copolymer, 4-methylpentene homopolymer, 4-methylpentene-1-propylene copolymer, 4-methylpentene-1-butene copolymer, 4-methylpentene-1-propylene-1-butene Examples thereof include polymers, propylene-1-butene copolymers, ethylene-vinyl acetate copolymers, ethylene-methacrylic acid copolymers, and ethylene-methyl methacrylate copolymers.

The thermoplastic elastomer composition may contain a tackifier. The tackifier is not limited to the following, but is not limited to, for example, kumaron-inden resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, terpene resin, hydrocarbon terpene resin, and the like. Terpen-phenolic resin, hydrogenated terpene phenolic resin, aromatic-modified terpene resin, aromatic-modified hydrogenated phenolic resin, styrene resin, alphamethylstyrene resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin, aliphatic Cyclic hydrocarbon resin, aliphatic / alicyclic petroleum resin, aliphatic / aromatic hydrocarbon resin, hydrogenated modified alicyclic hydrocarbon resin, hydrogenated alicyclic hydrocarbon resin, hydrocarbon adhesive Examples thereof include chemical resin, polybutene, liquid polybutadiene, cis-1,4-polyisoprene rubber, hydrocarbon polyisoprene rubber, liquid polyisoprene rubber, rosin-based resin and the like.

The thermoplastic elastomer composition containing the hydrogenated copolymer of the present invention may further contain other additives in addition to the above-mentioned components as long as the object of the present invention is not impaired. Such additives include heat stabilizers, antioxidants, UV absorbers, antioxidants, plasticizers, light stabilizers, crystal nucleating agents, impact improvers, pigments, lubricants, antistatic agents, flame retardants, and flame retardants. Auxiliary agents, compatibilizers, tackifiers and the like can be mentioned. Only one of these additives may be used, or two or more of these additives may be used in combination.

(Manufacturing method of thermoplastic elastomer composition)
The method for producing the thermoplastic elastomer composition is not particularly limited, and the thermoplastic elastomer composition can be produced by a conventionally known method. For example, melting using a general mixer such as a pressurized kneader, a van barry mixer, an internal mixer, a lab plast mill, a mix lab, a single-screw extruder, a twin-screw extruder, a conider, and a multi-screw screw extruder. A kneading method, a method of dissolving or dispersing and mixing each component, and then heating and removing the solvent is used. The shape of the thermoplastic elastomer is not particularly limited, and examples thereof include a pellet shape, a sheet shape, a strand shape, and a chip shape. Further, after melt-kneading, a directly molded product can be obtained.

(Molded product of thermoplastic elastomer composition)
The thermoplastic elastomer composition is excellent in abrasion resistance, low temperature mechanical properties and various performance balances, and by taking advantage of these properties, extrusion molded products, injection molded products, hollow molded products, pneumatic molded products, vacuum molded products, high frequency. It is suitably used for fused molded products, overmolded products, slush molded products and the like.

In particular, it is suitable for molded products that require wear resistance, low stickiness, and various performance balances. For example, packaging materials for food, beverages, pharmaceuticals, precision equipment, tubes (including catheters), bags, containers, trays, other parts, automobile parts and automobile interior skin materials (door trims, instrument panels, airbag covers, etc.), Examples include home appliances / OA equipment-related parts, industrial parts, household goods, toys, and the like. The above-mentioned extrusion-molded product or injection-molded product may be a multi-layer extrusion-molded product or a multi-layer injection-molded product. At this time, the hydrogenated copolymer of the present embodiment or the above-mentioned thermoplastic elastomer composition may be used for all layers, or may be used for only one layer or for two or more layers.

Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

First, the evaluation method and the method for measuring the physical properties applied to Examples and Comparative Examples are shown below.

[Method for specifying the structure of hydrogenated copolymer (a), hydrogenated copolymer (b1) and hydrogenated copolymer (b2), method for measuring physical properties]
(Contents of total vinyl aromatic compounds (total styrene content))
The content (% by mass) of the total vinyl aromatic compound of each copolymer from the absorption intensity of 262 nm using an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation) using the copolymer before hydrogenation. Was calculated.
Since the content of the total vinyl aromatic compound monomer unit does not change significantly before and after hydrogenation, the total vinyl aromatic compound monomer unit (styrene monomer) obtained for the copolymer before hydrogenation is obtained. The content of the unit) was defined as the content of the total vinyl aromatic compound monomer unit of the hydrogenated copolymer (total styrene content).

(Amount of vinyl bond of polymer blocks B1, B2 or D)
The polymer sampled for each step of the polymerization process of the copolymer before hydrogenation is vinyl-bonded by the proton nuclear magnetic resonance (1H-NMR) method using a nuclear magnetic resonance apparatus (DPX-400, manufactured by BRUKER). 1,2-Binding amount) was measured. Deuterated chloroform was used as the solvent, the sample concentration was 50 mg / mL, the observation frequency was 400 MHz, tetramethylsilane was used as the chemical shift standard, the pulse delay was 2.904 seconds, the number of scans was 64, the pulse width was 45 °, and the measurement was performed. The temperature was 26 ° C. The vinyl bond amount is determined by calculating the integral value per 1H of each bond mode from the integral value of the signals attributable to 1,4-bond and 1,2-bond, and then 1,4-bond and 1,2-bond. It was calculated from the ratio of 1,2-bonds to the total of.

(Polystyrene block content (Os value) of hydrogenated copolymer (a), hydrogenated copolymer (b1) and hydrogenated copolymer (b2))
Using the copolymer before hydrogenation, I. M. KOLTHOFF, et al. , J. Polym. Soi. It was measured by the osmium tetroxide decomposition method described in 1,429 (1946).
A 0.1 g / 125 mL tertiary butanol solution of osmic acid was used for the decomposition of the copolymer before hydrogenation. The content of the polystyrene block obtained here is referred to as "Os value".

(Amount of vinyl aromatic compound in polymer block B1 or B2)
Using a hydrogenated block copolymer as a measurement sample, it is composed of a polymer block mainly composed of a vinyl aromatic compound, a vinyl aromatic compound and a conjugated diene by a proton nuclear magnetic resonance method (1H-NMR, ECS400 manufactured by JOEL RESONABCE). A distinction was made between polymer blocks or polymer blocks consisting of vinyl aromatic compounds and conjugated diene compounds.
Deuterated chloroform was used as the solvent, the sample concentration was 50 mg / mL, the observation frequency was 400 MHz, tetramethylsilane was used as the chemical shift standard, the pulse delay was 2.904 seconds, the number of scans was 256, and the measurement temperature was 23 ° C. .. After calculating the random and blocking aromatics from the integrated value per 1H of each binding mode from the integrated intensity of the signal attributed to the aromatic, the total styrene content is calculated by the method (1) above and contained. The ratio was calculated.

(Weight average molecular weight of hydrogenated copolymer)
Measurement was performed using GPC [device: Tosoh HLC8220, column TSKgel SuperH-RC x 2]. Tetrahydrofuran was used as the solvent. The measurement conditions were a temperature of 35 ° C. Using a calibration curve prepared using commercially available standard polystyrene having a known weight average molecular weight, the polystyrene-equivalent weight average molecular weight was determined.

(Hydrogenation rate of hydrogenated copolymer (hydrogenation rate))
The hydrogenation rate of the hydrogenated copolymer was measured by a nuclear magnetic resonance apparatus (DPX-400, manufactured by BRUKER). It was measured by proton nuclear magnetic resonance (1H-NMR) using a hydrogenated copolymer which is a copolymer after hydrogenation. Specifically, 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 was calculated.

(Measurement of viscoelasticity of hydrogenated copolymer (tanδ peak))
The dynamic viscoelasticity spectrum was measured by the following method to obtain a peak temperature (tanδ peak temperature) having a loss coefficient of tanδ. First, the hydrogenated copolymer was formed into a sheet having a thickness of 2 mm and then cut into a size having a width of 10 mm and a length of 35 mm to prepare a sample for measurement. A measurement sample is set in the twist type geometry of the device ARES-G2 (manufactured by TA Instruments Co., Ltd., trade name), and the effective measurement length is 25 mm, strain 0.5%, frequency 1 Hz, measurement range- The measurement was carried out from 100 ° C. to 100 ° C. under the condition of a heating rate of 3 ° C./min.

[Manufacturing of polypropylene resin composition]
Based on the blending ratio (parts by mass) shown in Table 3, melt-knead the polypropylene resin composition pellets at a set temperature of 220 ° C. using a twin-screw extruder (Japan Steel Works "TEX-30αII", cylinder diameter 30 mm). Obtained. Molding was performed at an injection molding temperature of 220 ° C. and a mold temperature of 40 ° C. to obtain a molded product (thickness 2.0 mm, mirror finish, no grain) of a polypropylene resin composition.
As the polypropylene resin (component (c)), PM801A (PP / manufactured by SunAllomer; MFR = 15, described as "h-pp" in Table 3) was used. A1 to A15 were used as the hydrogenated copolymer (X).

(Evaluation of physical properties of polypropylene resin composition molded product)
(Scratch resistance)
Using an injection molded product (without skin grain) (5 cm x 15 cm) as a test piece, using a scratch tester KK-01 (manufactured by Kato Tech Co., Ltd.), scratch load: 1 N, scratch distance: 100 mm, scratch speed: according to ISO19252. The test was performed at 100 mm / sec, chip: stainless steel φ = 1.0 mm, and the measured portion was visually observed.
4: No scars are observed even if light is reflected 3: Scars are slightly observed when light is reflected 2: Scars are clearly observed when light is reflected Level 1: Light is observed A level at which scars are clearly observed without reflection

(Low temperature mechanical properties (tensile elongation (-30 ° C)))
In accordance with JIS K6251, a tensile test with a constant temperature bath (Minebea, Tg-5kN) was used to perform the following tensile test at -30 ° C, No. 3 dumbbell, and crosshead speed of 500 mm / min to determine the elongation at break. evaluated.
5: Fracture elongation is 500% or more and 4: Fracture elongation is 400% or more and less than 500% 3: Fracture elongation is 300% or more and less than 400% 2: Fracture elongation is 200% or more and less than 300% 1: Tension elastic modulus is less than 200%

(Morphology observation (TEM observation))
After the cross section of the injection molded product of the polypropylene resin composition was stained with ruthenium tetroxide, the ultrathin sections obtained by the microtome were observed using a transmission electron microscope (TEM) at a magnification of 5000 to 100,000 times.

(Morphology observation (AFM observation))
A smooth surface of a molded product (press molding or injection molding) of a polypropylene resin composition was prepared by a microtome to obtain a sample piece. The smooth surface of the sample piece was observed with an AFM (Bruker Dimension Icon, Peak Force QNM mode / OLTESPA type Si single crystal probe) under the above-mentioned measurement conditions, and an elastic modulus mapping diagram was obtained.

[Manufacturing of Thermoplastic Elastomer Composition]
Based on the blending ratio (parts by mass) shown in Table 4, the pellets of the thermoplastic elastomer composition are melt-kneaded at a set temperature of 220 ° C. by a twin-screw extruder (“TEX-30αII” manufactured by Japan Steel Works, cylinder diameter 30 mm). Got
It was molded at an injection molding temperature of 220 ° C. and a mold temperature of 40 ° C. to obtain a molded body (thickness 2.0 mm, no skin grain, with skin grain) of a thermoplastic elastomer composition. As the hydrogenated copolymer (X), A1 to A15 were used.
PM801A (PP / SunAllomer; MFR = 15) was used as the polypropylene resin. A styrene-based thermoplastic elastomer, Tuftec N504 (styrene content 32% by mass, manufactured by Asahi Kasei) was used as the rubber-like polymer. Paraffin oil, PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) was used as a softener. In Table 4, it is described as "oil".

(Evaluation of physical properties of thermoplastic elastomer composition molded product)
(Abrasion resistance)
Using a Gakushin type friction tester (manufactured by Tester Sangyo Co., Ltd., AB-301 type), the surface of the molded body (skin textured surface) is rubbed with friction cloth Kanakin No. 3 cotton and a load of 500 g, and then the texture depth is measured. Then, it was judged according to the following criteria based on the residual rate of grain depth (calculated by the following (Equation 1)). The grain depth was measured with a surface roughness meter E-35A manufactured by Tokyo Seimitsu Co., Ltd.
Remaining grain depth (%) = (texture depth after friction) / (texture depth before friction) x 100 (Equation 1)
5: After 10000 frictions, the residual grain depth is 80% or more 4: After 10000 frictions, the residual grain depth is less than 80% 65% or more 3: After 10000 frictions, the residual grain depth is Is less than 65% 50% or more 2: After 10,000 times of friction, the residual rate of grain depth is less than 50% 25% or more 1: After 10,000 times of friction, the residual rate of grain depth is less than 25%

(Low temperature breaking elongation)
In accordance with JIS K6251, a tensile test with a constant temperature bath (Minebea, Tg-5kN) was used to perform the following tensile test at -30 ° C, No. 3 dumbbell, and crosshead speed of 500 mm / min to determine the elongation at break. evaluated.
4: Break elongation is 200% or more 3: Break elongation is 100% or more and less than 200% 2: Break elongation is 50% or more and less than 100% 1: Tension elastic modulus is less than 50%

(Oil resistance)
According to JIS K6258, the test piece was immersed in IRM902 oil manufactured by Nippon Sun Oil Co., Ltd., and the mass before and after the immersion was measured. The mass fraction (%) increased by the immersion was calculated as the swelling ratio, with the mass of the test piece before immersion as 100%.
4; Swelling rate is 30% or less 3; Swelling rate is 30% or more and less than 50% 2; Swelling rate is 50% or more and less than 70% 1; Swelling rate is 70% or more

(Tactile)
Using an injection-molded sheet, evaluation was performed according to the following criteria from the viewpoint of moistness, smoothness, and softness. The evaluation was based on the average of 10 evaluators.
A: It has a good balance of moistness, smoothness and softness, and is an extremely comfortable sensation.
B: The balance of moistness, smoothness, and softness is a little out of order, but there is no discomfort.
C: The balance between moistness, smoothness, and softness is poor, and it is an unpleasant sensation.

[Manufacturing of hydrogenated copolymer] (Preparation of hydrogenated catalyst)
The hydrogenation catalyst used for the hydrogenation reaction of the copolymer was prepared by the following method.
1 liter of dried and purified cyclohexane was charged in a nitrogen-substituted reaction vessel, 100 mmol of biscyclopentadienyltitanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added with sufficient stirring to add room temperature. The reaction was carried out for about 3 days to obtain a hydrogenated catalyst.

(Hydrogenated copolymer)
Hydrogenated copolymers (a-1) to (a-4), hydrogenated copolymers (b1-1), and hydrogenated copolymers (b2-1) to (b2-5) are as follows. I made it.

<Hydrogenated copolymer (a-1)>
Batch polymerization was performed using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 20 parts by mass of styrene was added.
Next, 0.084 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and 0.35 mol of N, N, N', N'-tetramethylethylenediamine with respect to 1 mol of n-butyllithium. It was added and polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution containing 47 parts by mass of styrene and a cyclohexane solution containing 33 parts by mass of butadiene (concentration 20% by mass) were added and polymerized at 70 ° C. for 1 hour.
Next, 0.25 mol of ethyl benzoate was added to 1 mol of n-butyllithium, and the mixture was reacted at 70 ° C. for 10 minutes.
Then, methanol was added to terminate the polymerization reaction.
The copolymer obtained as described above has a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a vinyl bond amount of the polymer block (B1) before addition of 25%, and a weight average molecular weight of 19. It was 30,000.
The coupling rate obtained from the peak area ratio of the GPC curve was 50%.
Further, to the obtained copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the copolymer based on Ti, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out.
The hydrogenation ratio of the obtained hydrogenated copolymer was 99%, and the tanδ peak temperature was 18 ° C.
Next, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the hydrogenated copolymer, and water was added. A hydrogenated copolymer (a-1) was obtained.

<Hydrogenated copolymer (a-2)>
Batch polymerization was performed using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added.
Next, 0.067 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and 0.35 mol of N, N, N', N'-tetramethylethylenediamine with respect to 1 mol of n-butyllithium. It was added and polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution containing 47 parts by mass of styrene and a cyclohexane solution containing 33 parts by mass of butadiene (concentration 20% by mass) were added and polymerized at 70 ° C. for 1 hour.
Next, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of styrene was added, and the mixture was polymerized at 70 ° C. for 20 minutes.
Then, methanol was added to terminate the polymerization reaction.
The copolymer obtained as described above has a styrene content of 67% by mass, a polystyrene block content of 20% by mass, a polymer block (B1) having a vinyl bond content of 21% before water addition, and a weight average molecular weight of 15. It was 40,000.
Further, to the obtained copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the copolymer based on Ti, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out.
The hydrogenation ratio of the obtained hydrogenated copolymer was 99%, and the tanδ peak temperature was 9 ° C.
Next, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the hydrogenated copolymer, and water was added. A hydrogenated copolymer (a-2) was obtained.

<Hydrogenated copolymer (a-3)>
Batch polymerization was carried out using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 15 parts by mass of styrene was added.
Next, 0.085 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and 0.8 mol of N, N, N', N'-tetramethylethylenediamine with respect to 1 mol of n-butyllithium. It was added and polymerized at 70 ° C. for 5 minutes.
Next, a cyclohexane solution containing 3 parts by mass of butadiene (concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 5 minutes.
Next, a cyclohexane solution containing 29 parts by mass of butadiene and 50 parts by mass of styrene (concentration 20% by mass) was supplied so that the reaction temperature became constant, and polymerized at 70 ° C. for 45 minutes.
Next, a cyclohexane solution containing 3 parts by mass of butadiene was added, and the mixture was polymerized at 70 ° C. for 5 minutes.
Finally, 0.2 mol of tetraethoxysilane was added to 1 mol of n-butyllithium, and the reaction was carried out at 70 ° C. for 30 minutes.
Then, methanol was added to terminate the polymerization reaction.
The copolymer obtained as described above has a styrene content of 65% by mass, a polystyrene block content of 15% by mass, a block copolymer (B1) having a vinyl bond content of 25% before hydrogenation, and a weight average molecular weight. It was 301,000.
The coupling rate obtained from the peak area ratio of the GPC curve was 70%.
Further, to the obtained copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the copolymer based on Ti, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out.
The hydrogenation ratio of the obtained hydrogenated copolymer was 98%, and the tanδ peak temperature was 25 ° C.
Next, as a stabilizer, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added in an amount of 0.3 parts by mass based on 100 parts by mass of the hydrogenated copolymer, and water was added. A hydrogenated copolymer (a-3) was obtained.

<Hydrogenated copolymer (a-4)>
Batch polymerization was carried out using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 7.5 parts by mass of styrene was added.
Next, 0.080 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and 0.35 mol of N, N, N', N'-tetramethylethylenediamine with respect to 1 mol of n-butyllithium. It was added and polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution containing 36 parts by mass of styrene and a cyclohexane solution containing 49 parts by mass of butadiene (concentration 20% by mass) were added and polymerized at 70 ° C. for 1 hour.
Next, a cyclohexane solution containing 7.5 parts by mass of styrene was added, and the mixture was polymerized at 60 ° C. for 20 minutes.
Then, methanol was added to terminate the polymerization reaction.
The copolymer obtained as described above has a styrene content of 51% by mass, a polystyrene block content of 51% by mass, a vinyl bond amount of the polymer block (B1) before addition of 22%, and a weight average molecular weight of 15. It was 10,000.
Further, to the obtained copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the copolymer based on Ti, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out.
The hydrogenation ratio of the obtained hydrogenated copolymer was 99%, and the tanδ peak temperature was −14 ° C.
Next, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the hydrogenated copolymer, and water was added. A hydrogenated copolymer (a-4) was obtained.

<Hydrogenated copolymer (b1-1)>
Batch polymerization was performed using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 7.5 parts by mass of styrene was added.
Next, 0.066 parts by mass of n-butyllithium with respect to 100 parts by mass of all monomers and 1.8 mol of N, N, N', N'-tetramethylethylenediamine with respect to 1 mol of n-butyllithium. Further, 0.05 mol of sodium-t-pentoxide was added to 1 mol of n-butyllithium, and the mixture was polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution containing 22 parts by mass of styrene and a cyclohexane solution containing 63 parts by mass of butadiene (concentration 20% by mass) were added and polymerized at 70 ° C. for 1 hour.
Next, a cyclohexane solution containing 7.5 parts by mass of styrene was added, and the mixture was polymerized at 60 ° C. for 20 minutes.
Then, methanol was added to terminate the polymerization reaction.
The copolymer obtained as described above has a styrene content of 37% by mass, a polystyrene block content of 15% by mass, a polymer block (B2) having a vinyl bond content of 70% before water addition, and a weight average molecular weight of 15. It was .60,000.
Further, to the obtained copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the copolymer based on Ti, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out.
The hydrogenation ratio of the obtained hydrogenated copolymer was 99%, and the tanδ peak temperature was −25 ° C.
Next, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the hydrogenated copolymer, and water was added. A hydrogenated copolymer (b1-1) was obtained.

<Hydrogenated copolymer (b2-1)>
Batch polymerization was performed using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 10 parts by mass of butadiene was added.
Next, n-butyllithium was added to 0.05 parts by mass with respect to 100 parts by mass of all the monomers, and N, N, N', N'-tetramethylethylenediamine (TMEDA) was added to 0 with respect to 1 mol of n-butyllithium. 0.05 mol was added and polymerized at 70 ° C. for 10 minutes.
Next, a cyclohexane solution containing 85 parts by mass of butadiene was added, and TMEDA was added to 1.5 mol per mol of n-butyllithium and sodium-t-pentoxide was 0.05 to 1 mol of n-butyllithium. Mole was added and the mixture was polymerized at 60 ° C. for 1 hour.
Next, a cyclohexane solution containing 5 parts by mass of styrene was added and polymerized at 60 ° C. for 20 minutes.
Then, methanol was added to terminate the polymerization reaction.
The copolymer obtained as described above has a styrene content of 5% by mass, a polystyrene block content of 5% by mass, a polymer block block E content of 10% by mass, and a polymer block D of vinyl before hydrogenation. The binding amount was 74% and the weight average molecular weight was 254,000.
Further, to the obtained copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the copolymer based on Ti, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out.
The hydrogenation ratio of the obtained hydrogenated copolymer was 98%, and the tanδ peak temperature was −31 ° C.
Next, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the hydrogenated copolymer, and water was added. A hydrogenated copolymer (b2-1) was obtained.

<Hydrogenated copolymer (b2-2)>
Batch polymerization was performed using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 6.5 parts by mass of styrene was added.
Next, n-butyllithium was added to 0.065 parts by mass with respect to 100 parts by mass of all the monomers, and N, N, N', N'-tetramethylethylenediamine (TMEDA) was added to 1 mol with respect to 1 mol of n-butyllithium. .8 mol Further, 0.045 mol of sodium-t-pentoxide was added to 1 mol of TMEDA, and the mixture was polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution containing 82 parts by mass of butadiene was added, and the mixture was polymerized at 60 ° C. for 1 hour.
Next, a cyclohexane solution containing 6.5 parts by mass of styrene was added, and the mixture was polymerized at 60 ° C. for 20 minutes.
Next, a cyclohexane solution containing 5 parts by mass of butadiene was added, and the mixture was polymerized at 60 ° C. for 10 minutes.
Then, methanol was added to terminate the polymerization reaction.
The copolymer obtained as described above has a styrene content of 13% by mass, a polystyrene block content of 13% by mass, a vinyl bond amount of the polymer block D before addition of 80%, and a weight average molecular weight of 208,000. Met.
Further, to the obtained copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the copolymer based on Ti, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out.
The hydrogenation ratio of the obtained hydrogenated copolymer was 99%, and the tanδ peak temperature was −28 ° C.
Next, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the hydrogenated copolymer, and water was added. A hydrogenated copolymer (b2-2) was obtained.

<Hydrogenated copolymer (b2-3)>
Batch polymerization was performed using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 12 parts by mass of styrene was added.
Next, n-butyllithium was added to 0.158 parts by mass with respect to 100 parts by mass of all the monomers, and N, N, N', N'-tetramethylethylenediamine was added to 1.8 mol with respect to 1 mol of n-butyllithium. It was added and polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution containing 88 parts by mass of butadiene (concentration: 20% by mass) was added, and the mixture was polymerized at 70 ° C. for 1 hour.
Next, 0.24 mol of tetraethoxysilane was added to 1 mol of n-butyllithium, and the mixture was reacted at 70 ° C. for 10 minutes.
Then, methanol was added to terminate the polymerization reaction.
The copolymer obtained as described above has a styrene content of 12% by mass, a polystyrene block content of 12% by mass, a vinyl bond amount of the polymer block D before addition of 81%, and a weight average molecular weight of 25.3. It was 10,000.
The coupling rate obtained from the peak area ratio of the GPC curve was 92%.
Further, to the obtained copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the copolymer based on Ti, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out.
The hydrogenation ratio of the obtained hydrogenated copolymer was 98%, and the tanδ peak temperature was −30 ° C.
Next, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the hydrogenated copolymer, and water was added. A hydrogenated copolymer (b2-3) was obtained.

<Hydrogenated copolymer (b2-4)>
Batch polymerization was performed using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 9 parts by mass of styrene was added.
Next, 0.084 parts by mass of n-butyllithium with respect to 100 parts by mass of all the monomers and 1.8 mol of N, N, N', N'-tetramethylethylenediamine with respect to 1 mol of n-butyllithium. Further, 0.05 mol of sodium-t-pentoxide was added to 1 mol of n-butyllithium, and the mixture was polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution containing 25 parts by mass of styrene and a cyclohexane solution containing 21 parts by mass of butadiene (concentration 20% by mass) were added and polymerized at 70 ° C. for 45 minutes.
Next, a cyclohexane solution containing 45 parts by mass of butadiene was added and polymerized at 60 ° C. for 1 hour.
Then, methanol was added to terminate the polymerization reaction.
The polymer obtained as described above has a styrene content of 34% by mass, a polystyrene block content of 9% by mass, a polymer block block F content of 46% by mass, and a vinyl bond content of the polymer block D of 77 mol%. The weight average molecular weight was 148,000.
Further, to the obtained copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the copolymer based on Ti, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out.
The hydrogenation ratio of the obtained hydrogenated copolymer was 98%, and the tanδ peak temperatures were 25 ° C and -30 ° C.
Next, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the hydrogenated copolymer, and water was added. A hydrogenated copolymer (b2-4) was obtained.

<Hydrogenated copolymer (b2-5)>
Batch polymerization was performed using a tank reactor (internal volume 10 L) equipped with a stirrer and a jacket.
First, a cyclohexane solution (concentration: 20% by mass) containing 9 parts by mass of styrene was added.
Next, n-butyllithium is 0.11 part by mass with respect to 100 parts by mass of all the monomers, and N, N, N', N'-tetramethylethylenediamine (TMEDA) is 0 with respect to 1 mol of n-butyllithium. .45 mol was added and polymerized at 70 ° C. for 20 minutes.
Next, a cyclohexane solution containing 82 parts by mass of butadiene was added, and the mixture was polymerized at 60 ° C. for 1 hour.
Next, a cyclohexane solution containing 9 parts by mass of styrene was added and polymerized at 60 ° C. for 20 minutes.
Then, methanol was added to terminate the polymerization reaction.
The copolymer obtained as described above has a styrene content of 18% by mass, a polystyrene block content of 18% by mass, a vinyl bond amount of the polymer block D before addition of 50%, and a weight average molecular weight of 10.2. It was 10,000.
Further, to the obtained copolymer, 100 ppm of the hydrogenated catalyst prepared as described above was added per 100 parts by mass of the copolymer based on Ti, and hydrogenated at a hydrogen pressure of 0.7 MPa and a temperature of 80 ° C. The reaction was carried out.
The hydrogenation ratio of the obtained hydrogenated copolymer was 99%, and the tanδ peak temperature was −50 ° C.
Next, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added as a stabilizer to 100 parts by mass of the hydrogenated copolymer, and water was added. A hydrogenated copolymer (b2-5) was obtained.

The physical properties of each hydrogenated copolymer and the composition and physical properties of the hydrogenated copolymer (X) are shown in Tables 1 and 2 below.

[Polypropylene resin composition]
From Table 3 below, in Examples 1 to 9, the polypropylene resin composition containing the hydrogenated copolymer (a), the hydrogenated copolymer (b1), and the hydrogenated copolymer (b2) having a specific constitution. It was found that the product was excellent in terms of scratch resistance, low-temperature mechanical properties, and the balance of each property, with no score of "1".

From Table 3, it was found that in Comparative Examples 1 to 6, a score of "1" was present and inferior in the scratch resistance, the low temperature mechanical property, and the balance of each property of the polypropylene resin composition.

FIG. 1 shows the temperature dependence of the loss tangent of Production Example 1 (A1) and Comparative Production Example 5 (A14), which are hydrogenated copolymers. According to FIG. 1, Production Example 1 (A1), which is a hydrogenated copolymer, has one peak having a tan δ peak temperature of 0 ° C. or higher and a tan δ height of 1.0 or higher in viscoelasticity measurement (1 Hz). In addition, Comparative Production Example 5 (A14), which is a hydrogenated copolymer having two peaks having a tan δ peak temperature of less than 0 ° C. and a tan δ peak height of less than 0.2, is a viscoelastic measurement (1 Hz). ), There is one peak having a tan δ peak temperature of 0 ° C. or higher and a tan δ height of less than 1.0, and two peaks having a tan δ peak temperature of less than 0 ° C. and a tan δ peak height of 0.2 or more. I have one.

Images of the molded product of the resin composition of the hydrogenated copolymer and the polypropylene resin of Example 1 and Comparative Example 1 morphologically observed with a transmission electron microscope (ruthenium staining) are shown in FIGS. 2 (A) and 2 (B). ) (The upper part has a magnification of 20000 times, and the lower part has a magnification of 50,000 times). (A) An image of a molded body of the polypropylene resin composition of Example 1 observed by morphology with a transmission electron microscope (ruthenium staining) is shown. (B) An image of a molded body of the polypropylene resin composition of Comparative Example 1 observed by morphology with a transmission electron microscope (ruthenium staining) is shown. In FIG. 2, the black portion indicates a hydrogenated copolymer, and the white portion indicates a polypropylene resin.

From FIG. 2, in the resin composition of Example 1, the hydrogenated copolymer A1 forms a co-continuous structure in the polypropylene resin, and in the resin composition of Comparative Example 1, the hydrogenated copolymer A10 is It forms a sea-island structure with polypropylene resin. According to this, in the polypropylene resin composition, the polypropylene resin composition is obtained by using the hydrogenated copolymer (a), the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2) in combination at a specific ratio. It was found that the morphology of the resin changed from a sea-island structure to a copolymer structure.

The "sea-island structure" indicates a state in which a polypropylene resin and a hydrogenated copolymer are present independently, and the "co-continuous structure" is a state in which a hydrogenated block copolymer as a matrix component is present and is a polypropylene resin. However, it indicates a state in which it has a continuously connected shape in a state of covering a part or the whole thereof. Since the polypropylene resin composition forms a co-continuous structure without forming such a simple sea-island structure, it is possible to highly satisfy the wear resistance, the low temperature mechanical properties, and the balance of each property. Whether or not the polypropylene resin composition forms a co-continuous structure can be confirmed by using a transmission electron microscope.

Elastic modulus mapping diagram by AFM (atomic force microscope) of the injection molded plate of the polypropylene resin composition of Example 1, Comparative Example 2 and Comparative Example 3 (the elastic modulus is displayed by a color gradation, and the elastic modulus in the resin composition is displayed. The rate distribution) is shown in FIGS. 3 (A) to 3 (C).

FIG. 3A shows an elastic modulus mapping diagram of the molded plate of Example 1 by AFM.
FIG. 3B shows an elastic modulus mapping diagram of the molded plate of Comparative Example 2 by AFM.
FIG. 3C shows an elastic modulus mapping diagram of the molded plate of Comparative Example 3 by AFM.

According to this, by using the hydrogenated copolymer (a), the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2) in combination at a specific ratio, the injection molded plate (A) of the polypropylene resin composition is used. Then, the hydrogenated copolymer (b1) and the hydrogenated copolymer (b2) surround the interface between the hydrogenated copolymer (a) (a-1: black) and the polypropylene resin (white) as a compatibilizer. It can be seen that they are unevenly distributed. On the other hand, the presence of an interface was not suggested in the injection molded plates (B) and (C) of the polypropylene resin composition.

The polypropylene resin composition of the present embodiment, which contains a hydrogenated copolymer having a characteristic structure in a specific ratio, has enhanced interfacial strength between polypropylene and the hydrogenated copolymer, and has wear resistance, low-temperature mechanical properties, and each. The balance of characteristics can be highly satisfied.

[Thermoplastic Elastomer Composition]
From Table 4 below, in Examples 10 to 18, the hydrogenated copolymer (a), the hydrogenated copolymer (b1), and the hydrogenated copolymer (b2) in a specific range satisfying the constituent requirements of the present invention. ) Was found to be excellent in terms of abrasion resistance, low temperature mechanical properties, and various performance balances without scores "1" and "C".

In Comparative Examples 7 to 12, since the constituent requirements of the present invention are not satisfied, the thermoplastic elastomer composition has points "1" and "C" in terms of wear resistance, low temperature mechanical properties, and various performance balances. Turned out to be inferior.

The polypropylene resin composition, thermoplastic elastomer composition and adhesive film using the hydrogenated copolymer (X) of the present invention can be used for various clothing packaging, various food packaging, daily miscellaneous goods packaging, industrial material packaging, and various types. Laminating rubber products, resin products, leather products, etc., elastic tapes used for paper diapers, industrial products such as dicing films, adhesive protective films used to protect building materials and steel plates, adhesive film base materials, trays for fresh meat, Sheet supplies such as fruit and vegetable packs, frozen food containers, home appliances such as TVs, stereos, vacuum cleaners, bumper parts, body panels, side seals, interiors (instrument panels, door trims, airbag covers, etc.) Parts Applications Materials, road paving materials, waterproof materials, impermeable sheets, civil engineering packing, daily necessities, leisure goods, toys, industrial goods, furniture goods, writing tools, transparent pockets, holders, stationery such as file spine, infusion bag, etc. It has industrial applicability in a wide range of fields such as medical devices.

Claims (6)

A hydrogenated copolymer (X) containing a hydrogenated copolymer (a), (b1) and (b2) hydrogenated with a polymer composed of a vinyl aromatic compound and a conjugated diene compound.
The hydrogenated copolymer (a) has one or more tan δ peaks at 0 ° C. or higher in the viscoelasticity measurement (1 Hz).
The hydrogenated copolymer (b1) has one or more tanδ peaks at −25 ° C. or higher and lower than 0 ° C. in viscoelasticity measurement (1 Hz).
The hydrogenated copolymer (b2) has one or more tan δ peaks below −25 ° C. in viscoelasticity measurement (1 Hz).
Mass ratio (a) / {(b1) + ( b2)} is 45/55 to 95/5,
The hydrogenated copolymer (X) has at least one peak having a tanδ peak temperature of 0 ° C. or higher and a tanδ peak height of 1.0 or higher, and the tanδ peak temperature is less than 0 ° C. and the tanδ peak height. Hydroponic copolymer (X) having at least two peaks of less than 0.2. The hydrogenated copolymer (a) has a block B1 composed of a vinyl aromatic compound and a conjugated diene compound and having a vinyl aromatic compound content of 20 to 90% by mass.
The hydrogenated copolymer (b1) has a block B2 composed of a vinyl aromatic compound and a conjugated diene compound and having a vinyl aromatic compound content of 5 to 40% by mass.
The hydrogenated copolymer (X) according to claim 1, wherein the hydrogenated copolymer (b2) has a block D containing a conjugated diene compound as a main component and having a vinyl bond amount of 40 mol% or more before hydrogenation. The hydrogenated copolymer (X) according to claim 2, wherein the block D of the hydrogenated copolymer (b2) has a vinyl bond amount of 60 mol% or more before hydrogenation. A resin composition containing the hydrogenated copolymer (X) according to any one of claims 1 to 3 and a polypropylene resin (c). A thermoplastic elastomer composition containing the hydrogenated copolymer (X) according to any one of claims 1 to 3 and a thermoplastic resin and / or a rubbery polymer. A molded product of the resin composition according to claim 4 or the thermoplastic elastomer composition according to claim 5.

Images