JP7064909B2 - Thermoplastic resin compositions and molded products - Google Patents

Description

The present invention relates to thermoplastic resin compositions and molded articles.

The packaging container is required to have impact resistance and molding processability that can withstand transportation and use. In addition to this, in recent years, in food applications, heat resistance and gas barrier properties are required for food preservation due to the spread of microwave ovens and the like.
Conventionally, composite materials made of different thermoplastic resins have been used in order to impart the respective performances to such required performances.
For example, a container made of a double-structured resin material in which the outer layer is either a polystyrene-based resin, a polypropylene-based resin, or a polyester-based resin and the inner layer is either a polypropylene-based resin or a polyester-based resin has been proposed ( For example, see Patent Document 1).
Further, from the inner layer side, it is made of a resin material having a multi-layer structure, which is a resin layer selected from polypropylene, polystyrene, polyethylene terephthalate and the like / a polyester resin, a resin layer selected from a polyamide resin, a polyolefin resin and the like / other layers. Molded containers have been proposed (see, for example, Patent Document 2).

Japanese Unexamined Patent Publication No. 2001-72037 Japanese Unexamined Patent Publication No. 2001-55216

On the other hand, in order to control global warming and save resources, recycling of containers and packaging is required, and as mentioned above, the development of materials to meet the performance required for the containers themselves is progressing. , The idea of selecting the material of the container on the premise of recycling the container and packaging is not well known, and the conditions on the material suitable for recycling have not been sufficiently examined.
Therefore, the above-mentioned conventionally proposed container is also not a suitable material for recycling.
Specifically, the thermoplastic resins constituting each layer of the double container described in Patent Document 1 are incompatible materials having different polarities and the like, and a step of separating each layer is required when recycling. There is a problem that the process is complicated.
Further, regarding the multi-layer molded container described in Patent Document 2, when mixed for recycling, the recycled product has problems such as a decrease in strength, cracking when cutting a burr portion, and generation of chips. From a practical point of view, it has a problem that it is difficult to recycle.

Therefore, in the present invention, the thermoplastic resin composition and the molded product containing a plurality of types of resins constituting the container and the packaging material may be incompatible even if the respective resins are incompatible when melt-mixed. It is an object of the present invention to provide a thermoplastic resin composition and a molded product having excellent impact resistance, rigidity, and moldability without cracking or generation of chips during cutting.

Therefore, as a result of diligent research on the above problems, the present inventors have obtained a predetermined structure for an incompatible resin composition containing a polyester resin, a polystyrene resin, and a polyolefin resin. It has been found that the thermoplastic resin composition containing the block copolymer having the above-mentioned can solve the above-mentioned problems of the prior art, and has completed the present invention.
That is, the present invention is as follows.

[1]
70 to 99 parts by mass of a resin composition (A) containing a polyester-based resin (A-1), a polystyrene-based resin (A-2), and a polyolefin-based resin (A-3).
Hydrogenated block copolymer (B) 1 to 30 parts by mass and
Is a thermoplastic resin composition containing
The resin composition (A) contains 5 to 50% by mass of the polyester resin (A-1), 40 to 85% by mass of the polystyrene resin (A-2), and the polyolefin resin (A-3). Is contained in an amount of 10 to 50% by mass, respectively.
The polyester resin (A-1) is polyethylene terephthalate and / or polybutylene terephthalate.
The hydrogenated block copolymer (B) comprises a polymer block (a) mainly composed of at least one vinyl aromatic hydrocarbon compound monomer unit and at least one conjugated diene compound monomer unit. Containing a polymer block (b) as a main component,
The hydrogenated block copolymer (B) has a weight average molecular weight of 30,000 to 500,000.
The content of the total vinyl aromatic hydrocarbon compound monomer unit of the hydrogenated block copolymer (B) is 10% by mass to 80% by mass.
Thermoplastic resin composition.
[2]
The hydrogenated block copolymer (B) has a weight average molecular weight of 30,000 to 300,000.
The thermoplastic resin composition according to the above [1], wherein the content of the total vinyl aromatic hydrocarbon compound monomer unit of the hydrogenated block copolymer (B) is 20% by mass to 80% by mass.
[3]
The thermoplastic resin composition according to the above [1] or [2] , wherein the polyester resin (A-1) is an aromatic polyester containing an aromatic hydrocarbon compound monomer unit.
[4]
The hydrogenated block copolymer (B) contains one or more modified block copolymers (B-1) having one or more functional groups.
The modified block copolymer (B-1) is a modified block copolymer to which an atomic group having an amino group and / or an imino group is bonded.
The thermoplastic resin composition according to any one of the above [1] to [3] .
[5]
The hydrogenated block copolymer (B) contains 30 to one or more modified block copolymers (B-1) having one or more functional groups in the hydrogenated block copolymer (B). It contains 100% by mass and 0 to 70% by mass of the non-modified block copolymer (B-2).
The thermoplastic resin composition according to any one of the above [1] to [3] .
[6]
The modified block copolymer (B-1)
Modification to which an atomic group having at least one functional group selected from the group consisting of an amino group, an imino group, a hydroxyl group, an epoxy group, a carboxyl group, an acid anhydride group, an isocyanate group, a silyl group and an alkoxysilane group is bonded. It is a block copolymer,
The thermoplastic resin composition according to the above [5] .
[7]
The modified block copolymer (B-1)
The thermoplastic resin composition according to the above [5] or [6] , which is a modified block copolymer to which an atomic group having an amino group and / or an imino group is bonded.
[8]
A molded product comprising the thermoplastic resin composition according to any one of the above [1] to [7] .
[9]
The molded product according to the above [8] , which is a sheet-shaped molded product.
[10]
The molded product according to the above [8] , which is a container.

According to the present invention, even if different types of resins, which are incompatible with each other, are melt-mixed, the obtained molded product has less cracks and chips during cutting, and is excellent in impact resistance, rigidity, and moldability. A plastic resin composition is obtained.

Hereinafter, embodiments for carrying out the present invention (hereinafter, 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.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present embodiment is
70 to 99 parts by mass of a resin composition (A) containing a polyester-based resin (A-1), a polystyrene-based resin (A-2), and a polyolefin-based resin (A-3).
Block copolymer (B) 1 to 30 parts by mass and
Is a thermoplastic resin composition containing
The block copolymer (B) is mainly composed of a polymer block (a) containing at least one vinyl aromatic hydrocarbon compound monomer unit and at least one conjugated diene compound monomer unit. Containing the polymer block (b) to be
The block copolymer (B) has a weight average molecular weight of 30,000 to 500,000.
The content of the total vinyl aromatic hydrocarbon compound monomer unit of the block copolymer (B) is 10% by mass to 80% by mass.

By having the above-mentioned structure, the thermoplastic resin composition of the present embodiment has no cracks or chips at the time of cutting, and is excellent in impact resistance, rigidity, and moldability.
Hereinafter, the components of the thermoplastic resin composition of the present embodiment will be described in detail.

(Composition of thermoplastic resin composition)
The thermoplastic resin composition of the present embodiment includes a resin composition (A) containing a polyester resin (A-1), a polystyrene resin (A-2), and a polyolefin resin (A-3). , And the block copolymer (B).
The content of the resin composition (A) is 70 to 99% by mass, and the content of the block copolymer (B) is 1 to 30 parts by mass.
The content of the resin composition (A) / block copolymer (B) is preferably 75 to 98% by mass / 2 to 25% by mass, and more preferably 80 to 97% by mass from the viewpoint of hardness and elastic modulus. % / 3 to 20% by mass, more preferably 85 to 96% by mass / 4 to 15% by mass.

<Resin composition (A)>
The resin composition (A) contains a polyester resin (A-1), a polystyrene resin (A-2), and a polyolefin resin (A-3).

[Polyester resin (A-1)]
The polyester resin (A-1) may be any resin having an ester group in the molecule and is not particularly limited.
Since polyester has a chain hydrocarbon and / or an aromatic ring in the molecule, it exhibits affinity with St, ethylene and butylene contained in the block copolymer (B) described later. In particular, when the block copolymer (B) has a polar group, it tends to be more compatible with the polar group portion due to the ester bond.
The polyester resin (A-1) is not limited to the following, but is, for example, an aliphatic glycol such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, hexamethylene glycol; cyclohexanedimethanol. Alicyclic glycols such as; aromatic dihydroxy compounds such as bisphenol or dihydroxy compounds (diol compounds) selected from two or more of these, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalindicarboxylic acid. Acids; aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, and undecadicarboxylic acid; alicyclic dicarboxylic acids such as hexahydrodicarboxylic acid or dicarboxylic acids selected from two or more of these. Examples thereof include those formed by a condensation reaction.
Further, examples of the polyester resin (A-1) include those formed by ring-opening polymerization of lactides which are cyclic diesters and lactones which are cyclic esters.
These polyester-based resins (A-1) may be modified with other components such as epoxy resins.

The polyester-based resin (A-1) is not limited to the following, but is, for example, polyethylene terephthalate (hereinafter, also referred to as “PET”), polybutylene succinate (hereinafter, also referred to as “PBS”), and poly. Butylene succinate adipate (hereinafter also referred to as "PBSA"), polybutylene adipate terephthalate (hereinafter also referred to as "PBAT"), polybutylene terephthalate (hereinafter also referred to as "PBT"), polyethylene naphthalate, polyallylate, ethylene terephthalate. -One or more selected from polyhydroxyalkanoic acids (hereinafter, also referred to as "PHA") such as isophthalate copolymers, polylactic acid (hereinafter, also referred to as "PLA"), and polybutene succinic acid are preferable.
Among these, from the viewpoints of industrial productivity, mechanical strength, and processability, aromatic polyesters containing an aromatic hydrocarbon compound monomer unit in the molecule are more preferable, and polyethylene terephthalate, polybutylene terephthalate, and the like are more preferable. One or more selected from polybutylene succinate and polyhydroxyalkanoic acid, and even more preferably polyethylene terephthalate and polybutylene terephthalate.
The polyester resin may be used alone or in combination of two or more.

The resin composition (A) preferably contains a polyester resin (A-1) in an amount of 5 to 50% by mass from the viewpoint of heat resistance deformability.
It is more preferably 5 to 40% by mass, further preferably 5 to 30% by mass, and even more preferably 5 to 20% by mass.

[Polystyrene resin (A-2)]
The polystyrene-based resin (A-2) is not limited to the following, but for example, general-purpose polystyrene (GPPS), impact-resistant polystyrene reinforced with a rubber component (HIPS), a styrene-butadiene copolymer, and the like. Polystyrene-butadiene copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-methacrylic acid other than the block copolymer (a) used in this embodiment. Examples include methyl copolymers.
These copolymers may be random copolymers or block copolymers.
Since the polystyrene-based resin (A-2) has a chain hydrocarbon or an aromatic ring in the molecule, it exhibits affinity with styrene (St), ethylene, and butylene contained in the block copolymer (B) described later. ..
Among these, polystyrene is preferable from the viewpoint of industrial productivity, rigidity and moldability.
As the polystyrene-based resin, only one type may be used alone, or two or more types may be used in combination.

The polystyrene-based resin (A-2) preferably has a melt flow rate value (MFR) of 0.1 to 30 g / 10 minutes, more preferably 0.5 to 10 minutes, as determined under the conditions of a temperature of 200 ° C. and a load of 5 kg. 25 g / 10 minutes, more preferably 1.0 to 20 g / 10 minutes.
When the MFR of the polystyrene-based resin (A-2) is within the above range, a thermoplastic resin composition having better molding processability tends to be obtained.

The resin composition (A) preferably contains 40 to 85% by mass of the polystyrene-based resin (A-2) from the viewpoint of hardness, elastic modulus, and dimensional stability.
It is more preferably 40 to 80% by mass, further preferably 50 to 75% by mass, and even more preferably 50 to 70% by mass.

[Polyolefin-based resin (A-3)]
Since the polyolefin-based resin has a chain hydrocarbon in the molecule, it exhibits affinity with St, ethylene, and butylene contained in the block copolymer (B) described later.
The polyolefin-based resin (A-3) is not limited to the following, but is, for example, a block common weight of propylene homopolymer or propylene and an olefin other than propylene, preferably an α-olefin having 2 to 20 carbon atoms. Examples thereof include coalescing or random copolymers, or blends thereof.
The number of carbon atoms and the distinction between the block copolymer and the random copolymer do not significantly affect the compatibility with the block copolymer (B) described later.
Examples of the α-olefin having 2 to 20 carbon atoms include, but are not limited to, ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like. It is preferably an α-olefin having 2 to 8 carbon atoms, and more preferably ethylene, 1-butene, 1-hexene, or 4-methyl-1-pentene.
The olefin resin (A-3) may be used alone or in combination of two or more.

The polyolefin resin (A-3) preferably has a melt flow rate value (MFR) of 0.1 to 50 g / 10 minutes obtained under the conditions of a temperature of 230 ° C. and a load of 2.16 kg, and more preferably 0. It is 5 to 45 g / 10 minutes, more preferably 1.0 to 40 g / 10 minutes. If the MFR is within the above range, the heat resistance tends to be further improved.

The method for producing the polyolefin resin (A-3) is not limited to the following, but for example, the above-mentioned monomer is used using a Ziegler-Natta type catalyst in which a titanium-containing solid transition metal component and an organometallic component are combined. Examples thereof include a production method for polymerizing.
The transition metal component used in the Ziegler-Natta type catalyst is not limited to the following, and examples thereof include a solid component containing titanium, magnesium and halogen as essential components and an electron donating compound as an optional component, or titanium trichloride. The organometallic component is not limited to the following, and examples thereof include aluminum compounds.
The polymerization method for producing the polyolefin resin (A-3) is not limited to the following, but is, for example, a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, or a combination thereof. Examples include a multi-stage polymerization method. In these polymerization methods, when a propylene homopolymer is obtained, only propylene is polymerized, and when a copolymer is obtained, propylene and a monomer other than propylene are polymerized.

The resin composition (A) preferably contains 10 to 50% by mass of the polyolefin resin (A-3) from the viewpoint of oil resistance, toughness, and fluidity. It is more preferably 10 to 45% by mass, further preferably 10 to 40% by mass, and even more preferably 10 to 35% by mass.

<Block Copolymer (B)>
The thermoplastic resin composition of the present embodiment contains the block copolymer (B).
The block copolymer (B) is mainly composed of a polymer block (a) containing at least one vinyl aromatic hydrocarbon compound monomer unit and at least one conjugated diene compound monomer unit. Includes the polymer block (b).
From the viewpoint of compatibility with the resin composition (A), it is not essential that the block copolymer (B) is hydrogenated (hydrogenated), but the thermoplastic resin composition of the present embodiment is a container or the like. In order to improve the heat resistance of the thermoplastic resin composition, especially when it is recycled afterwards, especially when it is recycled over and over again, or when the content ratio of the recycled material in the container etc. is high. , The block copolymer (B) is preferably a hydrogenated block copolymer.

The polymer block (a) mainly composed of the vinyl aromatic hydrocarbon compound monomer unit has a content of 50% by mass of the vinyl aromatic hydrocarbon compound monomer unit in the polymer block (a). It means that it exceeds, and from the viewpoint of mechanical strength and heat-resistant deformability, it is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass. That is all.

The polymer block (b) mainly composed of the conjugated diene compound monomer unit means that the content of the conjugated diene compound monomer unit in the polymer block (b) exceeds 50% by mass. From the viewpoint of impact resistance, it is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more.

In this embodiment, the naming of each monomer unit constituting the block copolymer follows the naming of the monomer from which the monomer unit is derived. For example, the "vinyl aromatic hydrocarbon compound monomer unit" means a structural unit of a polymer produced as a result of polymerizing a vinyl aromatic hydrocarbon compound which is a monomer, and its structure is a substituted vinyl group. It is a molecular structure in which the two carbons of the substituted ethylene group derived from the above are the bonding sites. Further, the "conjugated diene compound monomer unit" means a constituent unit of a polymer produced as a result of polymerizing a conjugated diene compound which is a monomer, and its structure is derived from the conjugated diene compound monomer. It is a molecular structure in which two carbons of an olefin are bonded sites.

In the present embodiment, the monomer that can be used as the vinyl aromatic hydrocarbon compound monomer unit in the polymer block (a) means a compound having a vinyl group and an aromatic ring.
The vinyl aromatic hydrocarbon compound monomer is not limited to the following, and is, for example, styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-. Examples thereof include aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like. Among these, styrene, α-methylstyrene and divinylbenzene are preferably used from the viewpoint of polymerizability. As these vinyl aromatic hydrocarbon compound monomers, only one kind may be used alone, or two or more kinds may be used.

The monomer that can be used as the conjugated diene compound monomer unit in the polymer block (b) is a diolefin having a pair of conjugated double bonds (two double bonds bonded so as to be conjugated). Is. The conjugated diene compound monomer is not limited to the following, and is, for example, 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, 1, Examples thereof include 3-pentadiene, 2-methyl-1,3-pentadiene and 1,3-hexadiene. Among these, 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene) are preferably used from the viewpoint of polymerizable property. As these conjugated diene compound monomers, only one kind may be used alone, or two or more kinds may be used.

The block copolymer (B) has a weight average molecular weight of 30,000 to 500,000 from the viewpoint of compatibility with the resin composition (A), and has a weight average molecular weight of 30,000 to 300,000 (SEBS particle size and SEBS particle size). Contributes to homogenization of dispersibility) is preferable. Further, the content of the total vinyl aromatic hydrocarbon compound monomer unit is 10% by mass to 80% by mass or less, preferably 20% by mass to 80% by mass or less.
Examples of the block copolymer (B) include those having a structure represented by the following general formulas (1) to (7). Further, the block copolymer (B) may be a mixture containing a plurality of types and arbitrary ratios of copolymers having a structure represented by the following general formulas (1) to (7).
(Ab) _n (1)
a- (ba) _n (2)
b- (ab) _n (3)
[(B-a) _n ] _m -Z (4)
[(A-b) _n ] _m -Z (5)
[(B-a) _n -b] _m -Z (6)
[(A-b) _n -a] _m -Z (7)

In the general formulas (1) to (7), (a) is a polymer block mainly composed of a vinyl aromatic hydrocarbon compound monomer unit, and (b) is mainly composed of a conjugated diene compound monomer unit. It is a polymer block. The boundary line between the polymer block (a) and the polymer block (b) 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 plurality of copolymers of a conjugated diene compound monomer unit and a vinyl aromatic hydrocarbon compound monomer unit, which are polymer block (a) -polymer block (a). Means the residue after binding of the coupling agent used for binding between the polymer block (b) and the polymer block (b), or between the polymer block (a) and the polymer block (b). do.
The coupling agent is not limited to the following, and examples thereof include polyhalogen compounds and acid esters described later.

In the general formulas (1) to (7), the vinyl aromatic hydrocarbon compound monomer units in the polymer block (a) and the polymer block (b) are distributed in a tapered shape even if they are uniformly distributed. You may be doing it.
When the polymer block (a) and the polymer block (b) are copolymer blocks of a vinyl aromatic hydrocarbon compound monomer unit and a conjugated diene compound monomer unit, the copolymer block is concerned. The vinyl aromatic hydrocarbon compound monomer unit in the polymer may have a plurality of uniformly distributed portions and / or a plurality of tapered portions. Further, a plurality of portions having different contents of vinyl aromatic hydrocarbon compound monomer units may coexist in the copolymer block portion.

The weight average molecular weight of the block copolymer (B) is 30,000 to 500,000 as described above. It is preferably 35,000 or more, more preferably 40,000 or more.
Further, 300,000 or less is preferable, 200,000 or less is more preferable, and 100,000 or less is further preferable.
When the weight average molecular weight of the block copolymer (B) is 30,000 or more, the impact resistance of the thermoplastic resin composition of the present embodiment tends to be good. When the weight average molecular weight of the block copolymer (B) is 500,000 or less, preferably 300,000 or less, good fluidity can be obtained in the thermoplastic resin composition of the present embodiment, and excellent molding processing can be obtained. Sex is obtained.

The molecular weight distribution (Mw / Mn) of the block copolymer (B) is preferably 1.01 to 8.0, more preferably 1.01 to 6.0, and even more preferably 1.01 to 5.0. ..
If the molecular weight distribution of the block copolymer (B) is within the above range, better mechanical strength tends to be obtained.
The shape of the molecular weight distribution of the block copolymer (B) measured by GPC is not particularly limited, and it may have a polymodal molecular weight distribution having two or more peaks, or it may have one peak. It may have a modal molecular weight distribution.
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 block copolymer (B) are described in Examples described later. The molecular weight of the peak of the chromatogram measured by gel permeation chromatography (GPC) can be determined using a calibration line (prepared using the peak molecular weight of standard polystyrene) obtained from the measurement of commercially available standard polystyrene. can.

The content of the total vinyl aromatic hydrocarbon compound monomer unit in the block copolymer (B) is 10% by mass to 80% by mass.
From the viewpoint of recoverability related to mechanical properties and resealability, the content is 10% by mass or more, preferably 20% by mass or more, more preferably 22% by mass or more, still more preferably 24% by mass or more, and further. It is more preferably 26% by mass or more, and even more preferably 28% by mass or more. Further, it is 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, still more preferably 40% by mass or less.

When the content of the total vinyl aromatic hydrocarbon compound monomer unit in the block copolymer (B) is 10% by mass or more, the elastic ratio of the thermoplastic resin composition of the present embodiment tends to be improved. When the content of the total vinyl aromatic hydrocarbon compound is 80% by mass or less, the impact resistance of the thermoplastic resin composition of the present embodiment tends to be improved.
The content of the total vinyl aromatic hydrocarbon compound monomer unit can be controlled within the above numerical range by adjusting the addition amount of the monomer in the polymerization step of the block copolymer (B). It can be calculated from the absorption intensity at a wavelength of 262 nm using an ultraviolet spectrophotometer by the method described in Examples described later.

The microstructure (ratio of cis, trans, vinyl) of the polymer block (b) in the block copolymer (B) can be arbitrarily controlled by using a polar compound or the like described later.

The amount of vinyl bonds in the conjugated diene compound monomer unit in the block copolymer (B) before hydrogenation is preferably 30 mol% to 60 mol%, more preferably 31 to 57 mol%. It is even more preferably 31 to 54 mol%, even more preferably 32 to 51 mol%, and even more preferably 32 to 45 mol% or less.
When the vinyl bond amount before hydrogenation in the conjugated diene compound monomer unit is 30 mol% or more, the compatibility between the block copolymer (B) and the above-mentioned polyolefin resin (A-3) is further improved. There is a tendency, and when the vinyl bond amount before hydrogenation in the conjugated diene compound monomer unit is 60 mol% or less, the elasticity tends to be further improved.

As described above, in the present embodiment, the content of the total vinyl aromatic hydrocarbon compound monomer unit in the block copolymer (B) is 10% by mass to 80% by mass, and further, a single amount of the conjugated diene compound. The amount of vinyl bond in the body unit before hydrogenation is preferably 30 mol% to 60 mol%.

In the present embodiment, the vinyl bond amount is, for example, a single amount of conjugated diene incorporated in the bonding mode of 1,2-bond, 3,4-bond and 1,4-bond in butadiene before hydrogenation. The ratio of the total molar amount of the conjugated diene monomer unit incorporated by 1,2-bond and 3,4-bond to the total molar amount of the body unit.
After hydrogenation, 1,2-bond without hydrogenation, 1,2-bond after hydrogenation, 3,4-bond without hydrogenation, 3,4-bond after hydrogenation, no hydrogenation 1,4-bonds without hydrogenation and 1,2-bonds after hydrogenation with respect to the total molar amount of conjugated diene monomer units incorporated in the 1,4-bond and 1,4-bond bond modes after hydrogenation. The percentage of the total molar amount of conjugated diene monomer units incorporated in 1,2-bonds, non-hydrogenated 3,4-bonds and post-hydrogenated 3,4-bonds is the conjugated diene before hydrogenation. Equal to the amount of vinyl bond in the monomer unit. Therefore, the vinyl bond amount of the conjugated diene monomer unit before hydrogenation can be measured by nuclear magnetic resonance spectrum analysis (NMR) using the block copolymer after hydrogenation, and more specifically, in the examples described later. It can be measured by the method described.

The hydrogenation rate of the aliphatic double bond derived from the conjugated diene compound in the block copolymer (B) is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more. be. When the hydrogenation rate is 50% or more, there is a tendency that the deterioration of mechanical properties due to thermal deterioration (oxidative deterioration) of the block copolymer (B) can be more effectively suppressed. Further, when the hydrogenation rate is 70% or more, better weather resistance tends to be obtained. The upper limit of the hydrogenation rate is not particularly limited, but is preferably 100% or less, and more preferably 99% or less.

The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon compound monomer unit in the block copolymer (B) is not particularly limited, but is preferably 50% or less, more preferably 30%. It is less than or equal to, more preferably 20% or less.

The method for producing the block copolymer (B) is not limited to the following, and for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957 Examples thereof include the methods described in 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 copolymer of the block copolymer (B) containing the conjugated diene compound monomer unit before hydrogenation and the vinyl aromatic hydrocarbon compound monomer unit is not limited to the following, but is not limited to, for example, a hydrocarbon solvent. It can be obtained by a method of performing anionic living polymerization using an initiator such as an organic alkali metal compound.
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.

The polymerization initiator is not particularly limited, but is generally an organic alkali metal compound known to have anionic polymerization activity with respect to the conjugated diene compound monomer and the vinyl aromatic hydrocarbon compound monomer. The above is not particularly limited, and for example, an aliphatic hydrocarbon alkali metal compound having 1 to 20 carbon atoms, an aromatic hydrocarbon alkali metal compound having 1 to 20 carbon atoms, an organic amino alkali metal compound having 1 to 20 carbon atoms, and the like. Can be mentioned.
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 reaction products of trilllithium, diisopropenylbenzene and sec-butyllithium, and reaction products 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.

A vinyl bond resulting from the conjugated diene compound monomer incorporated into the copolymer when the conjugated diene compound monomer and the vinyl aromatic hydrocarbon compound monomer are copolymerized using the organic alkali metal compound as a polymerization initiator. As an adjusting agent for adjusting the content of (1,2-bond or 3,4-bond) and adjusting the random copolymerizability of the conjugated diene compound monomer and the vinyl aromatic hydrocarbon compound monomer. For example, a tertiary amine compound, an ether compound, and a metal alcoholate compound can be added.
As the adjusting agent, only one kind may be used alone, or two or more kinds may be used in combination.

As the tertiary amine compound of the adjusting agent, the general formula R ₁ R ₂ R ₃ N (where R ₁ , R ₂ and R ₃ are hydrocarbon groups having 1 to 20 carbon atoms or tertiary amino groups are used. The compound represented by) (indicating the hydrocarbon group having) can be applied.
The tertiary amine compound is not limited to the following, but is not limited to, for example, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N'. , N'-Tetramethylethylenediamine, N, N, N', N'-Tetraethylethylenediamine, 1,2-dipiperidinoetan, Trimethylaminoethylpiperazine, N, N, N', N ", N" -penta Examples thereof include methylethylenetriamine, N, N'-dioctyl-p-phenylenediamine and the like.

As the ether compound of the adjusting agent, a linear ether compound, a cyclic ether compound and the like can be applied.
The linear ether compound is not limited to the following, but for example, ethylene glycol dialkyl ether compounds such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and ethylene glycol dibutyl ether. Examples thereof include diethylene glycol dialkyl ether compounds such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.
The cyclic ether compound is not limited to the following, but is not limited to, for example, tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2). -Oxolanyl) Propane, alkyl ethers of furfuryl alcohol and the like can be mentioned.

Examples of the metal alcoholate compound of the adjusting agent include, but are not limited to, sodium-t-pentoxide, sodium-t-butoxide, potassium-t-pentoxide, potassium-t-butoxide and the like.

The method for copolymerizing the conjugated diene compound monomer and the vinyl aromatic hydrocarbon compound monomer using an organic alkali metal compound as a polymerization initiator is not particularly limited, and may be batch polymerization or continuous polymerization. Alternatively, it may be a combination thereof. The batch polymerization method is preferable from the viewpoint of adjusting the molecular weight distribution to a preferable appropriate range.
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. Examples of the bifunctional coupling agent include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenylbenzoate, and phthalates.

The polyfunctional coupling agent having a trifunctional or higher functional group is not limited to the following, and is, for example, a polyhydric compound having a trivalent or higher valence, an 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. Be done.

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.

The hydrogenated catalyst used for producing a hydrogenated block copolymer is not particularly limited, and for example, Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, and Japanese Patent Publication No. 63-4841. Hydrogenated catalysts described in JP-A-3-77970, JP-B-1-53871, JP-B-2-9041 and the like can be used.
Preferred hydrogenated catalysts include 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 organometallic compound is not particularly limited, and examples thereof include organoalkali metal compounds such as organolithium, 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 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 block copolymer and the solvent is not limited to the following, but for example, the solution of the hydrogenated block copolymer is mixed with a poor solvent for the hydrogenated block copolymer such as acetone or alcohol. A method of precipitating and recovering the hydrogenated block copolymer by adding a polar solvent, or a solution of the hydrogenated block copolymer is poured into boiling water with stirring, and the solvent is removed and recovered by steam stripping. A method of distilling off the solvent by directly heating the solution of the hydrogenated block copolymer and the like.

An antioxidant may be added to the reaction solution for producing the block copolymer (B).
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, tetrakis- [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) Phenyl) 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, butyl 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.

[Modified block copolymer (B-1)]
In the thermoplastic resin composition of the present embodiment, the block copolymer (B) is one or more modified block copolymers having one or more functional groups in the block copolymer (B). It is preferable to include B-1). The content of the modified block copolymer (B-1) is preferably 30 to 100% by mass in the block copolymer (B).
From the viewpoint of compatibility with the resin composition (A), it is not essential that the modified block copolymer (B-1) is hydrogenated (hydrogenated), but the thermoplastic resin composition of the present embodiment is not essential. Improves the heat resistance of the thermoplastic resin composition when it is used for a container, etc. and then recycled, especially when it is recycled over and over again, or when the content ratio of the recycled material in the container, etc. is high. Therefore, the modified block copolymer (B-1) is preferably a hydrogenated modified block copolymer.
When the modified block copolymer (B-1) is a hydrogenated modified block copolymer, the hydrogenation rate of the aliphatic double bond derived from the conjugated diene compound in the hydrogenated modified block copolymer is determined. It is preferably 50% or more, more preferably 60% or more, and further preferably 70% or more. When the hydrogenation rate is 50% or more, there is a tendency that the deterioration of mechanical properties due to thermal deterioration (oxidative deterioration) of the hydrogenated block copolymer (B-1) can be more effectively suppressed. Further, when the hydrogenation rate is 70% or more, better weather resistance tends to be obtained. The upper limit of the hydrogenation rate is not particularly limited, but is preferably 100% or less, and more preferably 99% or less.
As the hydrogenation method, the same method as the hydrogenation method of the block copolymer (B) described above can be used.

The fact that the modified block copolymer (B-1) is a polymer having one or more functional groups, that is, a polymer in which atomic groups containing functional groups are bonded, is a polyester resin (A-). It is preferable from the viewpoint of further improving the affinity with 1).

The functional group is not particularly limited as long as it imparts polarity to the block copolymer by binding to the unmodified block copolymer. Functional groups to which atoms with high electronegativity such as F, O, Cl, N, S, and P are bonded have polarity, and by having such polar functional groups, modified block copolymers (B-1) has a particularly good affinity with polyester having a polar structure due to an ester bond in the molecule.
Examples of the atomic group containing a functional group include 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 and a carboxylic acid ester group. , Amid group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, cyano group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, iso At least one functional group selected from a thiocyanate group, a silicon halide group, a silyl group, a silanol group, an alkoxysilane group, a tin halide group, an alkoxytin group, a phenyltin group, a boronic acid group, a boronic acid base, a boron-containing group and the like. Examples include seed-containing atomic groups.
Among these functional groups, a hydroxyl group, a carbonyl group, an acid anhydride group, a carboxyl group, an epoxy group, an amino group, an imino group, and an isocyanate group from the viewpoint of affinity and compatibility with the polyester resin (A-1). , Cyril group, alkoxysilane group is preferable, amino group and / or imino group is more preferable.
The modified block copolymer to which an atomic group having an amino group and / or an imino group is bonded as a modifying group has higher compatibility with the polyester resin (A-1), and is the thermoplastic resin of the present embodiment. The impact resistance of the composition tends to be high.
In the present embodiment, the amino group means a functional group having a structure of a primary to tertiary amine. Further, the imino group means a group in which a nitrogen atom is bonded to the same carbon atom by a double bond, that is, = NH. By using the modified block copolymer (B-1) to which an atomic group having such a functional group is bonded, the mechanical strength and elastic modulus of the thermoplastic resin composition of the present embodiment are improved.

As a method for obtaining a hydrogenated modified block copolymer (B-1) by hydrogenating the modified block copolymer, for example, a polymerization initiator having a functional group or an unsaturated monomer having a functional group is used. A method of hydrogenating a non-hydrogenated block copolymer obtained by polymerization, a method of forming a functional group in a non-hydrogenated block copolymer having a living end obtained by anion polymerization, or a modification having a functional group. Examples thereof include a method in which an agent is subjected to an addition reaction and then hydrogenated.
Further, as another method for obtaining the hydrogenated block copolymer (B-1), an organic alkali metal compound such as an organic lithium compound is reacted with the non-hydrogenated block copolymer, that is, a metallation reaction is carried out to make it organic. Examples thereof include a method in which a modifier having a functional group is added to a non-hydrogenated block copolymer to which an alkali metal is added, and then a hydrogenated reaction is carried out.
In the other method, a hydrogenated block copolymer (B-1) is obtained by subjecting it to a metallation reaction after obtaining a hydrogenated block copolymer and then reacting it with a modifier having a functional group. You can also.
In any of the above-mentioned modification methods, the reaction temperature is preferably 0 to 150 ° C, more preferably 20 to 120 ° C.
The time required for the denaturation reaction varies depending on other conditions, but is preferably within 24 hours, more preferably 0.1 to 10 hours. Depending on the type of modifier, the hydroxyl group or amino group may generally be an organic metal salt at the stage of reaction of the modifier, but in that case, it should be treated with a compound having active hydrogen such as water or alcohol. Therefore, it can be a hydroxyl group, an amino group, or the like.
In the modified block copolymer (B-1), a partially unmodified block copolymer may be mixed.

The modified block copolymer (B-1) preferably contains 20 mol% or more of functional groups on average, and more preferably 30 mol% or more on average, in the copolymer. It is preferable that the content is 40 mol% or more on average.
When the content of the functional group is in the above range, the affinity and compatibility with the polyester resin (A-1) tend to be good.

The modifying agent having a functional group is not limited to the following, and is, for example, tetraglycidylmethoxylenidamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, ε-caprolactone, 4-methoxybenzophenone, tetraglycidyl. -P-Phenylenediamine, Tetraglycidyldiaminodiphenylmethane, Diglycidylaniline, Diglycidyl orthotoluidine, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, Examples thereof include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, and γ-glycidoxypropyltributoxysilane.
In addition, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyl Diethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-gly Examples thereof include sidoxylpropyldiethylethoxysilane and γ-glycidoxypropyldimethylethoxysilane.

Furthermore, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropeneoxysilane, bis (γ-glycidoxypropyl) dimethoxysilane, bis (γ) -Glysidoxypropyl) diethoxysilane, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis Examples thereof include (γ-glycidoxypropyl) methylmesisilane and bis (γ-glycidoxypropyl) methylethoxysilane.
Furthermore, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, bis (γ-glycidoxypropyl) methylphenoxysilane, tris (γ-glycidoxypropyl) ) Methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis (γ-methacryloxypropyl) dimethoxysilane , Tris (γ-methacryloxypropyl) methoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

In addition, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, β-( 3,4-Epoxycyclohexyl) propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethylethyldimethoxysilane, β- (3,4-epoxy) Cyclohexyl) Ethylethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldipropoxysilane, β- (3,4-epoxycyclohexyl) Ethylmethyldibutoxysilane can be mentioned.

Furthermore, β- (3,4-epoxycyclohexyl) ethylmethyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyldiethylethoxysilane, β- (3,4-Epoxycyclohexyl) Ethyldimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyldimethylbutoxysilane, β- (3,4-) Epoxycyclohexyl) ethyldimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyldiethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiisopropenoxysilane, 1,3-dimethyl-2-imidazole Lydinone, 1,3-diethyl-2-imidazolidinone, N, N'-dimethylpropylene urea, N-methylpyrrolidone, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1 -Propaneamine and the like can be mentioned.
Among these, denaturants having an imidazolidinone skeleton, such as 1,3-dimethyl-2-imidazolidinone and 1,3-diethyl-2-imidazolidinone, are particularly preferable.

Further, the modified block copolymer (B-1) may be obtained by further reacting the modified block copolymer with a secondary modifier having reactivity with a functional group.
The secondary modifier is a modifier having a functional group reactive with the functional group of the modified block copolymer, preferably a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, or an alkoxysilane group. It is a secondary modifier having a functional group selected from.
The secondary denaturing agent is preferably a secondary denaturing agent having at least two functional groups selected from these functional groups. When the functional group is an acid anhydride group, the acid anhydride group may be one secondary modifier.
When the secondary modifier is reacted with the modified block copolymer, the secondary modifier is preferably 0.3 to 10 mol per 1 equivalent of the functional group bonded to the modified block copolymer. It is preferably 0.4 to 5 mol, more preferably 0.5 to 4 mol. When the content of the functional group is within the above range, the balance of compatibility with the polystyrene-based resin (A-2), the polyolefin-based resin (A-3) and the polyester-based resin (A-1) tends to be good. be. The method for obtaining the secondary-modified modified block copolymer (B-1) by reacting the modified block copolymer with the secondary modifier is not particularly limited, and a known method can be used. For example, a method of melt-kneading described later, a method of dissolving or dispersing and mixing each component in a solvent or the like, and the like can be mentioned.

Particularly preferable secondary modifiers are not limited to the following, but are carboxylic acids having two or more carboxyl groups or acid anhydrides thereof, or acid anhydride groups, isocyanate groups, epoxy groups, silanol groups, and alkoxys. Examples thereof include secondary modifiers having at least two or more selected from the group consisting of silane groups, and specific examples thereof include maleic anhydride, pyromellitic anhydride, and 1,2,4,5-benzenetetracarboxylic acid. Bianhydride, toluylene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane, bis- (3-triethoxysilylpropyl) -tetrasulfan and the like can be preferably used.

The modified block copolymer (B-1) is a modified block copolymer graft-modified with an α, β-unsaturated carboxylic acid or a derivative thereof, for example, an anhydride thereof, an esterified product, an amidated product, or an imidized product. There may be.
The α, β-unsaturated carboxylic acid or a derivative thereof is not limited to the following, and for example, maleic anhydride, maleic anhydride imide, acrylic acid or an ester thereof, methacrylic acid or an ester thereof, endo-. Examples thereof include cis-bicyclo [2,2,1] -5-heptene-2,3-dicarboxylic acid or an anhydride thereof, and among these, maleic anhydride is preferable.
The amount of α, β-unsaturated carboxylic acid or its derivative added is usually 0.01 to 20% by mass, preferably 0.1 to 17% by mass, and more preferably 1 to 15% by mass in the fully modified block copolymer. Is. When the addition amount is within the above range, the balance of compatibility with the polystyrene-based resin (A-2), the polyolefin-based resin (A-3), and the polyester-based resin (A-1) tends to be good.
The reaction temperature for graft modification is preferably 100 to 300 ° C, more preferably 120 to 280 ° C. For details of the method of graft denaturation, for example, Japanese Patent Application Laid-Open No. 62-79211 can be referred to.

The block copolymer (B) is a modified block copolymer (B-1) having a mass of 30 to 100 from the viewpoint of preventing cracks and chips during cutting and improving impact resistance, rigidity, and elongation. % Is preferably contained. It is more preferably 35 to 100% by mass, still more preferably 40 to 100% by mass, still more preferably 50 to 100% by mass, still more preferably 50 to 90% by mass, and particularly preferably 50 to 80% by mass.
Further, from the viewpoint of improving the molding appearance by improving the fluidity during molding and preventing cracks and chips during cutting, the block copolymer (B) is a non-modified block copolymer (B-2) of 0. It is preferably contained in an amount of about 70% by mass. It is more preferably 0 to 65% by mass, still more preferably 0 to 60% by mass, still more preferably 0 to 50% by mass, still more preferably 10 to 50% by mass, and particularly preferably 20 to 50% by mass. By using the modified block copolymer (B-1) and the non-modified block copolymer (B-2) in combination, the fluidity of the thermoplastic resin composition of the present embodiment can be easily improved, and molding strain can be prevented. It tends to decrease. Therefore, when the thermoplastic resin composition of the present embodiment is molded into a larger shape and / or a complicated shape, the modified block copolymer (B-1) is particularly effective in preventing cracking and improving impact resistance. It is effective to use the non-modified block copolymer (B-2) in combination.

<Additives>
In the thermoplastic resin composition of the present embodiment, in addition to the above-mentioned resin composition (A) and block copolymer (B), any additive can be added, if necessary.

The type of the additive may be any one generally used for blending a thermoplastic resin or a rubber-like polymer, and is not limited to the following, for example, silica, talc, mica, calcium silicate, and the like. Examples thereof include inorganic fillers such as hadrotal site, kaolin, diatomaceous soil, graphite, calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, calcium sulfate and barium sulfate, and organic fillers such as carbon black.

Also, lubricants such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bisstearoamide; plasticizers such as mold release agents, organic polysiloxanes, and mineral oils; hindered phenolic antioxidants. Antioxidants such as phosphorus-based, sulfur-based and amine-based heat stabilizers; hindered amine-based light stabilizers, benzotriazole-based ultraviolet absorbers, flame retardants, antistatic agents, organic fibers, glass fibers (GF), carbon fibers, Reinforcing agents such as metal whisker; Colorants such as titanium oxide, iron oxide, carbon black, etc .; Others described in "Rubber / Plastic Blended Chemicals" (edited by Rubber Digest) and the like can be mentioned.

(Manufacturing method of thermoplastic resin composition)
The method for producing the thermoplastic resin composition of the present embodiment is not particularly limited, and known methods can be used.
For example, a method of melting and kneading each component using a general miscible machine such as a Banbury mixer, a single-screw screw extruder, a twin-screw screw extruder, a conider, or a multi-screw screw extruder, and dissolving or dispersing and mixing each component. After that, a method of heating and removing the solvent can be mentioned.
In the present embodiment, the melt kneading method using an extruder is preferable from the viewpoint of productivity and good kneading property.
The shape of the thermoplastic resin composition 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.

〔Molding〕
The thermoplastic resin composition of the present embodiment is obtained by conventionally known methods, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotation molding, powder slush molding, foam molding. , Laminate molding, calendar molding, blow molding, etc., can be processed into practically useful molded products. Further, if necessary, processing such as foaming, powdering, stretching, adhesion, printing, painting, and plating may be performed. By such a molding method, it can be utilized as a wide variety of molded products such as sheets, films, injection molded products of various shapes, hollow molded products, pneumatic molded products, vacuum molded products, extrusion molded products, foam molded products, etc., and these molded products can be used. It can be used for various packaging materials such as industrial, food, home appliances, automobiles, building materials, sports, leisure, etc., and various containers.

PET films and the like may be mixed when recycling containers and packaging made of polystyrene / polypropylene resin compositions, and after recycling, the containers may become polystyrene / polypropylene resin compositions containing a small amount of PET.
When the thermoplastic resin composition of the present embodiment is adopted as the material for the container and packaging, the polyester resin is contained from the time of the virgin material, so that the performance as a container and packaging is high, and when some PET film or the like is mixed by recycling. However, recycled products can fully exert their intended functions.
In addition, even if polyester-based resin, polystyrene-based resin, or polypropylene-based resin is used for containers and packaging and is recovered for recycling, it cannot be recycled into containers and packaging with the same composition due to deterioration of the resin or the like. However, by blending the recovered product so as to include a part and / or all of it and using it as the thermoplastic resin composition of the present embodiment, it is possible to obtain a container and packaging that functions sufficiently while effectively utilizing resources. This is a preferred embodiment from the viewpoint of utilization.

Hereinafter, the present embodiment will be described in detail with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples.
The evaluation method and the method for measuring the physical properties applied to the examples and comparative examples are shown below.

[Evaluation method for block copolymer (B)]
((1) Content of total vinyl aromatic hydrocarbon compound monomer unit (total styrene content))
A certain amount of block copolymer was dissolved in chloroform, measured with an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation), and the peak intensity of the absorption wavelength (262 nm) due to the vinyl aromatic compound component (styrene). The content of the vinyl aromatic hydrocarbon compound monomer unit (styrene) was calculated from the calibration curve.

((2) Vinyl bond amount)
The vinyl bond amount (vinyl bond amount in the polybutadiene block) of the conjugated diene monomer unit in the block copolymer was measured under the following conditions using a nuclear magnetic resonance apparatus (NMR).
By adding a large amount of methanol to the reaction solution after completion of all the reactions, the block copolymer was precipitated and recovered. Next, the block copolymer is extracted with acetone, the extract is vacuum dried, and the conditions for 1H-NMR measurement used as a sample for 1H-NMR measurement are described below.
(Measurement condition)
Measuring equipment: JNM-LA400 (manufactured by JEOL)
Solvent: Deuterated chloroform Sample concentration: 50MG / ML
Observation frequency: 400MHZ
Chemical shift criteria: TMS (tetramethylsilane)
Pulse delay: 2.904 seconds Number of scans: 64 times Pulse width: 45 °
Measurement temperature: 26 ° C
The amount of vinyl bond is the 1,2-bond and 1,2-bond to the total area of all peaks (1,2-bond, 3,4-bond, 1,4-bond) related to the conjugated diene monomer unit in the obtained peak. It was determined by the ratio of the peak total area of 3,4-bonds.

((3) Weight average molecular weight, number average molecular weight, molecular weight distribution)
The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the block copolymer (hydrogenated block copolymer) (B) are calibration lines obtained from the measurement of commercially available standard polystyrene. (Made using the peak molecular weight of standard polystyrene) was used to determine based on the peak molecular weight of the chromatogram.
HLC-8320ECOSEC collection was used as the measurement software, and HLC-8320ECOSEC analysis was used as the analysis software.
(Measurement condition)
GPC; HLC-8320GPC (manufactured by Tosoh Corporation)
Detector; RI
Detection sensitivity; 3MV / min Sampling pitch; 600MSEC
Column; TSKGEL SUPERHZM-N (6MMID × 15CM) 4 pieces (manufactured by Tosoh Corporation)
Solvent; THF
Flow rate; 0.6ML / min Concentration; 0.5MG / ML
Column temperature; 40 ° C
Injection volume; 20ML

((4) Amino group modification rate)
The amino group modification rate of the block copolymer (B-1) was defined as the ratio (mol%) of the modified block copolymer in the total block copolymer.
As a measurement method, the property that the modified component is adsorbed on the GPC column using silica gel as a filler is applied, and the chromatograph measured in (3) above is applied to the sample solution containing the modified block copolymer and the low molecular weight internal standard polystyrene. Ratio of hydrogenated block copolymer to standard polystyrene in gram and standard in chromatogram measured by silica gel column GPC [equipment: LC-10 (manufactured by Shimadzu Corporation), column: Zorbax (manufactured by DuPont)]. The ratio of the modified block copolymer to the polystyrene was compared, and the amount adsorbed on the silica column was measured from the difference between them.
The proportion of the non-modified block copolymer that was not adsorbed on the silica column was defined as the proportion of the non-modified block copolymer, and the proportion of the other was defined as the proportion of the modified block copolymer.

((5) Addition of acid anhydride group)
The addition amount of the acid anhydride group-modified product of the block copolymer (B-1) was the addition amount (mass%) of the acid anhydride groups undergoing an addition reaction in the total hydrogenated block copolymer.
As a measuring method, first, the modified block copolymer (B-1) was boiled in acetone for 60 minutes, then vacuum-dried, and then dissolved in toluene. Next, a phenolphthalein indicator was added, titration was performed with a methanol solution of sodium methylate (CH ₃ ONa), and the amount of acid anhydride group added was calculated from the amount of sodium methylate added to the acid anhydride group.

((6) Hydrogenation rate (hydrogenation rate))
The hydrogenation rate of the double bond of the conjugated diene monomer unit in the block copolymer (B) is the same as that of the above ((4) vinyl bond amount) using a nuclear magnetic resonance apparatus (NMR). It was measured.
The hydrogenation rate is water with respect to the total area of all peaks (1,2-bond, 3,4-bond, 1,4-bond) involved in the double bond in the conjugated diene monomer unit in the obtained peak. It was determined by the ratio of the peak total areas of hydrogenated 1,2-bonds, hydrogenated 3,4-bonds and hydrogenated 1,4-bonds.

[Manufacturing of thermoplastic resin composition]
(Examples 1 to 3, Reference Example 4, Examples 5 to 14), (Comparative Examples 1 to 3)
Cylinder set maximum temperature 260 by the same direction double-screw extruder ("TEX-30αII" manufactured by Japan Steel Works, cylinder diameter 30 mm) based on the compounding ratio (parts by mass) shown in Table 2 below using the materials described later. Pellets of the thermoplastic resin composition were obtained by melt-kneading at ° C.

[Evaluation method of thermoplastic resin composition]
((7) Melt flow rate (MFR))
The melt flow rate (MFR) of the pellets of the thermoplastic resin composition obtained as described above was measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kg in accordance with JIS K7210 (ISO1133 compliant).
If the MFR is 5 (g / 10 minutes) or more, it is judged that the MFR has sufficient molding processability.

[Manufacturing of injection molded products]
Using the pellets of the thermoplastic resin composition obtained as described above, the injection molding machine (“FE-120S18A” manufactured by Nissei Plastic Industry Co., Ltd.) is used for multiple purposes at a cylinder setting maximum temperature of 220 ° C. and a mold temperature of 40 ° C. Test piece A type (dumbbell shape, total length 170 mm, width of parallel part / length 10 mm / 80 mm, thickness 4 mm), strip-shaped test piece (length 110 mm, width 10 mm, thickness 4 mm), small plate test piece (length 90 mm, width) 50 mm, thickness 2 mm) were produced respectively.
Using the obtained test piece, the physical properties were measured according to the following measuring method.

[Evaluation method for injection molded products]
((8) Rockwell hardness)
Using a small flat plate test piece, the measurement was performed on an R hardness scale using a Rockwell hardness tester in accordance with JIS K7202-2 (ISO2039-2 compliant).
If the Rockwell hardness was 70 (−) or more, it was judged to have sufficient rigidity.

((9) Tensile breaking strength, tensile elastic modulus, tensile breaking elongation)
Using a multipurpose test piece A type (dumbbell shape), conforming to JIS K7161 (ISO527-1 compliant), using a tensile tester (Minebea's "Technograph TG-5kN"), crosshead speed 500 mm / min The tensile test was carried out as follows.
Tensile breaking strength: The stress at the time of breaking was measured.
Tensile elastic modulus: The elastic modulus at the time of tension was measured.
Tension fracture elongation: The elongation at break was measured.
If the tensile breaking strength was 30 (MPa) or more, it was judged to have sufficient strength.
When the tensile elastic modulus was 1300 (MPa) or more, it was judged to have sufficient rigidity.
If the tensile elongation at break was 4 (%) or more, it was judged to have sufficient rigidity.

((10) Maximum bending strength)
Using a strip-shaped test piece, conforming to JIS K7171 (ISO178 compliant), using a tensile tester (Minebea's "Technograph TG-5kN"), crosshead speed 2 mm / min, distance between fulcrums 64 mm, indenter R5 mm The bending test was carried out as follows.
Maximum bending strength: Maximum stress was measured.
Bending elastic modulus: The elastic modulus at the time of bending was measured.
Presence or absence of breakage: The presence or absence of breakage before the maximum stress was reached was visually confirmed.
If the maximum bending strength is 50 (MPa) or more, it is judged that the maximum bending strength is sufficient.
If the flexural modulus was 1400 (MPa) or more, it was judged to have sufficient rigidity.
If there is no breakage, it is judged that the product has sufficient strength, and is indicated by "○" in Table 2 below.

((11) Charpy impact strength)
Using a strip-shaped test piece, JIS K7110-1 (ISO179-1 compliant), Charpy impact tester, hitting direction edgewise, no notch, swing angle 150 °, distance between support bases 62 mm, hammer capacity The test was carried out at 15J.
If the Charpy impact strength was 30 (kJ / m ² ) or more, it was judged to have sufficient impact resistance.

((12) Vicat softening point)
Using a strip-shaped test piece, in accordance with JIS K7206 (ISO306 compliant), using a softening point measuring machine ("HDT tester 6M-2" manufactured by Toyo Seiki), needle insertion amount 1 mm, load 10 N, temperature rise rate 120 ° C. The test was carried out at / h.
If the Vicat softening point was 100 (° C.) or higher, it was judged to have sufficient heat-resistant deformability.

[Preparation of press sheet]
Using the pellets of the thermoplastic resin composition obtained as described above, a 50t electric heating press (manufactured by Toho Press Mfg. Co., Ltd.) was used at a set temperature of 200 ° C., 100 kgf / cm ² , width 110 mm, length 220 mm, and thickness 0. A 5.5 mm press sheet was prepared. Using the obtained press sheet, the physical properties were measured according to the following measuring method.

((13) Cracks and chips during cutting)
For cracks during cutting, use a 0.5 mm thick press sheet and a punching device (Dumbbell's "SDL-200") to punch a razor blade type with a width of 10 mm and a length of 60 mm (Dumbbell's "SSK"). When punching out 10 places in "-1000"), it was visually confirmed whether there were any cracks in the punched inner and outer sheets.
Regarding the chips at the time of cutting, it was visually confirmed whether or not the chips adhered to the razor blade after punching out the above 10 places.
If there are no cracks or chips, it is judged that the product has sufficient cutability, and is indicated by "○" in Table 2 below.

Next, the resin composition (A) and the hydrogenated block copolymer (B) contained in the thermoplastic resin composition will be described.

(Constituents of Resin Composition (A))
<Polyester resin (A-1)>
The following commercially available products were used as the polyester resin (A-1).
Polyester resin (A-1-1): Teijin Limited TR-BB, polyethylene terephthalate, melting point 245 ° C.
Polyester resin (A-1-2): Unitika Ltd. TE-2000, polylactic acid, melting point 170 ° C.
<Polystyrene resin (A-2)>
The following commercially available products were used as the polystyrene resin (A-2).
Polystyrene resin (A-2): PS Japan Corporation 685, polystyrene, MFR (200 ° C, 5 kg) 2 g / 10 minutes <polyolefin resin (A-3)>
The following commercially available products were used as the polyolefin resin (A-3).
Polypropylene resin (A-3): SunAllomer Ltd. PC630A, propylene random polymer, MFR (230 ° C, 2.16 kg) 7.5 g / 10 minutes

(Manufacturing of block copolymer (hydrogenated block copolymer) (B))
<Preparation of hydrogenated catalyst>
In Examples and Comparative Examples described later, hydrogenated catalysts used for producing hydrogenated block copolymers were prepared by the following methods.
A reaction vessel equipped with a stirrer was replaced with nitrogen, and 1 L of dried and purified cyclohexane was charged therein.
Next, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added. While sufficiently stirring this, an n-hexane solution containing 200 mmol of trimethylaluminum was added and reacted at room temperature for about 3 days to obtain a hydrogenated catalyst.

<Hydrogenated block copolymer (1)>
A stirrer having an internal volume of 10 L and a tank reactor with a jacket were washed, dried, and replaced with nitrogen to perform batch polymerization.
First, after adding a cyclohexane solution containing 5 parts by mass of 1,3-butadiene monomer, 0.155 parts by mass of n-butyllithium and n-butyl of tetramethylethylenediamine (hereinafter, TMEDA) with respect to 100 parts by mass of all the monomers. 0.28 mol was added to 1 mol of lithium, and the mixture was polymerized at 70 ° C. for 15 minutes.
Then, a cyclohexane solution containing 17 parts by mass of a styrene monomer was added and polymerized at 70 ° C. for 25 minutes, and a cyclohexane solution containing 63 parts by mass of a 1,3-butadiene monomer was added and polymerized at 70 ° C. for 40 minutes.
Finally, a cyclohexane solution containing 15 parts by mass of styrene monomer was added and polymerized at 70 ° C. for 25 minutes.
After completion of the polymerization reaction, 0.95 mol of methanol was added to 1 mol of n-butyllithium to inactivate the reaction catalyst to obtain a polymer.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C.
After completion of the hydrogenation reaction, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the polymer as a stabilizer, and the hydrogenation block was added. The block polymer (1) was obtained.
The obtained hydrogenated block copolymer (1) has a total styrene content of 32.3% by mass, a vinyl bond amount of 35.5 mol% before hydrogenation in the polybutadiene block, and a weight average molecular weight of 7.9 of the entire polymer. The molecular weight distribution was 1.33. The hydrogenation rate of the aliphatic double bond derived from 1,3-butadiene was 99.5%.

<Hydrogenated block copolymer (2)>
The hydrogenated block copolymer (1) is desolvated, dried, pelletized with a single-screw extruder, and then 2.1 parts by mass of maleic anhydride is added to 100 parts by mass of the hydrogenated block copolymer (1). Addition of 0.12 parts by mass of 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and performing an addition reaction at a set temperature of 200 ° C. with a twin-screw extruder, together with the hydrogenated block. The polymer (2) was obtained.
In the obtained hydrogenated block copolymer (2), the amount of the acid anhydride group added by maleic anhydride was 1.8% by mass.

<Hydrogenated block copolymer (3)>
A stirrer having an internal volume of 10 L and a tank reactor with a jacket were washed, dried, and replaced with nitrogen to perform batch polymerization.
First, after adding a cyclohexane solution containing 16 parts by mass of a styrene monomer, 0.180 parts by mass of n-butyllithium and 1 mol of n-butyllithium (hereinafter, TMEDA) are added to 100 parts by mass of all the monomers. 0.23 mol was added thereto, and the mixture was polymerized at 70 ° C. for 25 minutes, and then a cyclohexane solution containing 69 parts by mass of 1,3-butadiene monomer was added and polymerized at 70 ° C. for 40 minutes.
Finally, a cyclohexane solution containing 15 parts by mass of styrene monomer was added and polymerized at 70 ° C. for 25 minutes.
After completion of the polymerization reaction, 0.8 mol of 1,3-dimethyl-2-imidazolidinone was added to 1 mol of n-butyllithium, and the reaction was carried out at 70 ° C. for 15 minutes.
After completion of the reaction, 0.15 mol of methanol was added to 1 mol of n-butyllithium to inactivate the reaction catalyst to obtain a polymer.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C.
After completion of the hydrogenation reaction, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the polymer as a stabilizer, and the hydrogenation block was added. The block polymer (3) was obtained.
The obtained hydrogenated block copolymer (3) has a total styrene content of 31.2% by mass, a vinyl bond amount of 35.8 mol% before hydrogenation in the polybutadiene block, and a weight average molecular weight of 6.4 of the entire polymer. The molecular weight distribution was 1.26. The hydrogenation rate of the aliphatic double bond derived from 1,3-butadiene was 82.3%, and the amino group modification rate was 75.3 mol%.

<Hydrogenated block copolymer (4)>
A stirrer having an internal volume of 10 L and a tank reactor with a jacket were washed, dried, and replaced with nitrogen to perform batch polymerization.
First, after adding a cyclohexane solution containing 16 parts by mass of a styrene monomer, 0.095 parts by mass of n-butyllithium and 1 mol of n-butyllithium (hereinafter, TMEDA) are added to 100 parts by mass of all the monomers. 0.26 mol was added thereto, and the mixture was polymerized at 70 ° C. for 25 minutes, and then a cyclohexane solution containing 69 parts by mass of 1,3-butadiene monomer was added and polymerized at 70 ° C. for 40 minutes.
Finally, a cyclohexane solution containing 15 parts by mass of styrene monomer was added and polymerized at 70 ° C. for 25 minutes.
After completion of the polymerization reaction, 0.8 mol of 1,3-dimethyl-2-imidazolidinone was added to 1 mol of n-butyllithium, and the reaction was carried out at 70 ° C. for 15 minutes.
After completion of the reaction, 0.15 mol of methanol was added to 1 mol of n-butyllithium to inactivate the reaction catalyst to obtain a polymer.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C.
After completion of the hydrogenation reaction, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the polymer as a stabilizer, and the hydrogenation block was added. The block polymer (4) was obtained.
The obtained hydrogenated block copolymer (4) has a total styrene content of 30.8% by mass, a vinyl bond amount of 36.9 mol% before hydrogenation in the polybutadiene block, and a weight average molecular weight of 15.3 of the entire polymer. The molecular weight distribution was 1.28. The hydrogenation rate of the aliphatic double bond derived from 1,3-butadiene was 84.7%, and the amino group modification rate was 72.8 mol%.

<Hydrogenated block copolymer (5)>
A stirrer having an internal volume of 10 L and a tank reactor with a jacket were washed, dried, and replaced with nitrogen to perform batch polymerization.
First, after adding a cyclohexane solution containing 11 parts by mass of a styrene monomer, 0.180 parts by mass of n-butyllithium and 1 mol of n-butyllithium (hereinafter, TMEDA) are added to 100 parts by mass of all the monomers. 0.23 mol was added thereto, and the mixture was polymerized at 70 ° C. for 25 minutes, and then a cyclohexane solution containing 79 parts by mass of 1,3-butadiene monomer was added and polymerized at 70 ° C. for 40 minutes.
Finally, a cyclohexane solution containing 10 parts by mass of styrene monomer was added and polymerized at 70 ° C. for 25 minutes.
After completion of the polymerization reaction, 0.8 mol of 1,3-dimethyl-2-imidazolidinone was added to 1 mol of n-butyllithium, and the reaction was carried out at 70 ° C. for 15 minutes.
After completion of the reaction, 0.15 mol of methanol was added to 1 mol of n-butyllithium to inactivate the reaction catalyst to obtain a polymer.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C.
After completion of the hydrogenation reaction, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the polymer as a stabilizer, and the hydrogenation block was added. The block polymer (5) was obtained.
The obtained hydrogenated block copolymer (5) has a total styrene content of 20.6% by mass, a vinyl bond amount of 35.7 mol% before hydrogenation in the polybutadiene block, and a weight average molecular weight of 6.6 of the entire polymer. The molecular weight distribution was 1.24. The hydrogenation rate of the aliphatic double bond derived from 1,3-butadiene was 86.1%, and the amino group modification rate was 77.6 mol%.

<Hydrogenated block copolymer (6)>
A stirrer having an internal volume of 10 L and a tank reactor with a jacket were washed, dried, and replaced with nitrogen to perform batch polymerization.
First, after adding a cyclohexane solution containing 16 parts by mass of a styrene monomer, 0.055 parts by mass of n-butyllithium and 1 mol of n-butyllithium (hereinafter, TMEDA) are added to 100 parts by mass of all the monomers. 0.28 mol was added thereto, and the mixture was polymerized at 70 ° C. for 25 minutes, and then a cyclohexane solution containing 69 parts by mass of 1,3-butadiene monomer was added and polymerized at 70 ° C. for 40 minutes.
Finally, a cyclohexane solution containing 15 parts by mass of styrene monomer was added and polymerized at 70 ° C. for 25 minutes.
After completion of the polymerization reaction, 0.8 mol of 1,3-dimethyl-2-imidazolidinone was added to 1 mol of n-butyllithium, and the reaction was carried out at 70 ° C. for 15 minutes.
After completion of the reaction, 0.15 mol of methanol was added to 1 mol of n-butyllithium to inactivate the reaction catalyst to obtain a polymer.
Next, 100 ppm of the hydrogenation catalyst was added to the obtained polymer as titanium per 100 parts by mass of the polymer, and a hydrogenation reaction was carried out at a hydrogen pressure of 0.8 MPa and a temperature of 85 ° C.
After completion of the hydrogenation reaction, 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the polymer as a stabilizer, and the hydrogenation block was added. The block polymer (6) was obtained.
The obtained hydrogenated block copolymer (6) has a total styrene content of 31.3% by mass, a vinyl bond amount of 35.2 mol% before hydrogenation in the polybutadiene block, and a weight average molecular weight of 35.4 of the entire polymer. The molecular weight distribution was 1.26. The hydrogenation rate of the aliphatic double bond derived from 1,3-butadiene was 85.3%, and the amino group modification rate was 73.2 mol%.

The thermoplastic resin composition of the present invention and a molded product using the same can be used industrially as various packaging material containers for industrial use, food use, home appliances, automobiles, building materials, sports, leisure, etc. Has the potential.

Claims (10)

70 to 99 parts by mass of a resin composition (A) containing a polyester-based resin (A-1), a polystyrene-based resin (A-2), and a polyolefin-based resin (A-3).
Hydrogenated block copolymer (B) 1 to 30 parts by mass and
Is a thermoplastic resin composition containing
The resin composition (A) contains 5 to 50% by mass of the polyester resin (A-1), 40 to 85% by mass of the polystyrene resin (A-2), and the polyolefin resin (A-3). Is contained in an amount of 10 to 50% by mass, respectively.
The polyester resin (A-1) is polyethylene terephthalate and / or polybutylene terephthalate.
The hydrogenated block copolymer (B) comprises a polymer block (a) mainly composed of at least one vinyl aromatic hydrocarbon compound monomer unit and at least one conjugated diene compound monomer unit. Containing a polymer block (b) as a main component,
The hydrogenated block copolymer (B) has a weight average molecular weight of 30,000 to 500,000.
The content of the total vinyl aromatic hydrocarbon compound monomer unit of the hydrogenated block copolymer (B) is 10% by mass to 80% by mass.
Thermoplastic resin composition. The hydrogenated block copolymer (B) has a weight average molecular weight of 30,000 to 300,000.
The content of the total vinyl aromatic hydrocarbon compound monomer unit of the hydrogenated block copolymer (B) is 20% by mass to 80% by mass.
The thermoplastic resin composition according to claim 1. The polyester resin (A-1) is an aromatic polyester containing an aromatic hydrocarbon compound monomer unit.
The thermoplastic resin composition according to claim 1 or 2 . The hydrogenated block copolymer (B) contains one or more modified block copolymers (B-1) having one or more functional groups.
The modified block copolymer (B-1) is a modified block copolymer to which an atomic group having an amino group and / or an imino group is bonded.
The thermoplastic resin composition according to any one of claims 1 to 3 . The hydrogenated block copolymer (B) contains 30 to one or more modified block copolymers (B-1) having one or more functional groups in the hydrogenated block copolymer (B). It contains 100% by mass and 0 to 70% by mass of the non-modified block copolymer (B-2).
The thermoplastic resin composition according to any one of claims 1 to 3 . The modified block copolymer (B-1)
Modification to which an atomic group having at least one functional group selected from the group consisting of an amino group, an imino group, a hydroxyl group, an epoxy group, a carboxyl group, an acid anhydride group, an isocyanate group, a silyl group and an alkoxysilane group is bonded. It is a block copolymer,
The thermoplastic resin composition according to claim 5 . The modified block copolymer (B-1)
The thermoplastic resin composition according to claim 5 or 6 , which is a modified block copolymer to which an atomic group having an amino group and / or an imino group is bonded. A molded product comprising the thermoplastic resin composition according to any one of claims 1 to 7 . The molded product according to claim 8 , which is a sheet-shaped molded product. The molded product according to claim 8 , which is a container.