JPH11130932A - Thermoplastic resin composition containing block copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin compsn. excellent in the balance among physical properties such as impact resistance, clarity, flexibility, resistance to impact whitening, resistance to bending whitening, etc. SOLUTION: This compsn. comprises 99-1 wt.% thermoplastic resin and 1-99 wt.% block copolymer which has a mol.wt. of 20,000-1,000,000 and a mol.wt. distribution Mw/Mn of 1-5 and comprises at least two polystyrene blocks (S) contg. 90 mol.% or higher styrene monomer units, at least one ethylene-1-butene random copolymer block (B1) contg. 20-45 mol.% 1-butene units (a) and 80-55 mol.% ethylene units (b) provided (a)+(b)>=90 mol.%, and at least one ethylene-1- butene random copolymer block (B2) contg. 45-100 mol.% units (a) and 55-0 mol.% units (b) provided (a)+(b)>=90 mol.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides not only excellent weatherability and excellent processability that can be pelletized alone, but also by compatibilizing when blended with a thermoplastic resin, Thermoplastic resin containing a block copolymer that, when alloyed with a thermoplastic resin, acts as a compatibilizer to greatly improve the balance of physical properties such as impact resistance, transparency, flexibility and bending whitening resistance Composition.

[0002]

2. Description of the Related Art Conventionally, as a means for improving the thermal stability, weather resistance and ozone resistance of a diene-based block copolymer having an unsaturated double bond in a polymer, the unsaturated double bond has been converted to hydrogen. A method of adding (hereinafter, referred to as "hydrogenation") is known, for example, JP-B-36-3895, JP-B-42
No. 8933, Japanese Patent Publication No. 42-25304, Japanese Patent Publication No. 45-39274, etc. disclose a method for producing a hydrogenated butadiene polymer and a hydrogenated styrene-butadiene copolymer. The resulting hydrogenated polymer having excellent heat resistance, weather resistance and ozone resistance has been used for modifying various resins because of its excellent performance as a thermoplastic elastomer. Particularly, a hydrogenated styrene-butadiene copolymer having a styrene block has excellent compatibility with a styrene resin, and is therefore used as a modifier for these resins.

Further, in order to have excellent processability for pelletization and to enhance the effect of modifying the olefin resin, the microstructure (1,4-addition and 1,2-addition) of the polybutadiene block before hydrogenation is increased. ) Is proposed.

For example, Japanese Patent Publication No. 62-45883 discloses hydrogenation of a diblock copolymer comprising a polybutadiene block having a low vinyl content (less than 15%) and a polybutadiene block having a high vinyl content (85% or more). Discloses a hydrogenated copolymer consisting of a crystalline block and an amorphous block. However, a polybutadiene block containing a polystyrene block and having a moderate vinyl content (33% or more and less than 62%), which acts as a soft portion of the thermoplastic elastomer and has no crystallinity, is also amorphous and has a high vinyl content. (62% or more)
It does not disclose a hydrogenated product of a block copolymer having a polybutadiene block.

As examples of a hydrogenated block copolymer containing a polystyrene block, JP-A-2-133406 discloses a polystyrene block, a polyconjugated diene block having a vinyl content of 30 to 80%, and a polybutadiene block having a vinyl content of less than 30%. And hydrogenated block copolymers and compositions thereof. A block having a low vinyl content is hydrogenated to give polyethylene-like crystallinity to enhance resin properties. This brings out the performance as a thermoplastic elastomer. However, since this block copolymer does not have a polybutadiene block having a high vinyl content, even if hydrogenated, the effect of improving the flexibility of the composition with a specific thermoplastic resin was not sufficient.

JP-A-5-170844 discloses a hydrogenated block copolymer containing a polystyrene block and a polybutadiene block having a high vinyl content.
JP-A-7-118335 discloses a hydrogenated product of a block copolymer comprising a polystyrene block, a polyconjugated diene block having a vinyl content of more than 70%, and a polybutadiene block having a vinyl content of 30% or less. In each case, hydrogenation of a polybutadiene block having a high vinyl content enhances the effect of improving the flexibility of the composition with a specific thermoplastic resin, and hydrogenation of a block having a low vinyl content allows polyethylene-like crystallinity to be improved. To enhance the resin-like properties and suppress the occurrence of adhesion between the pellets.

However, in these hydrogenated block copolymers, the block acting as the soft part of the thermoplastic elastomer has a high glass transition temperature due to the hydrogenation of a polybutadiene block having a high vinyl content, and the rubber-like properties deteriorate. I do. Due to this, the modifying effect of the thermoplastic resin, particularly the improvement of impact resistance, was not sufficient.

[0008] Thus, a polystyrene block, which acts as a soft part of a thermoplastic elastomer, and has a low glass transition temperature and a medium content of vinyl (33% or more and less than 62%).
No block copolymer composed of a hydrogenated polybutadiene block, and a hydrogenated polybutadiene block which is also amorphous and has a high vinyl content (62% or more) is not disclosed.

Further, JP-A-8-208911 discloses a hydrogenated product of a block copolymer comprising a polystyrene block, a polyconjugated diene block having a vinyl content of 50% or more, and a polybutadiene block having a vinyl content of 25% or less, and the hydrogenated hydrogen. A PP-based film comprising an additive and PP is disclosed. However, when these hydrogenated block copolymers are blended with thermoplastics,
Or when alloyed with two or more thermoplastic resins,
It is not enough to obtain a balance of physical properties such as impact resistance, transparency, flexibility, and bending whitening resistance, and polymers having further performance as modifiers (compatibilizers, compatibilizers) are desired. I was

[0010]

DISCLOSURE OF THE INVENTION The present invention not only has excellent processability that can be pelletized by itself but also compatibilizes when blended with a thermoplastic resin, or has an alloy with two or more thermoplastic resins. Uses a block copolymer that has the characteristic of acting as a compatibilizer when it is converted, and contains a block copolymer that significantly improves the balance of physical properties such as impact resistance, transparency, flexibility and impact whitening resistance It is an object of the present invention to provide a thermoplastic resin composition to be used.

[0011]

DISCLOSURE OF THE INVENTION The present inventors have developed a polymer structure of a hydrogenated product of a vinyl aromatic compound block-conjugated diene compound block copolymer, its processability and its use as a modifier for a thermoplastic resin. The effects were studied diligently. As a result, a block copolymer containing a block that functions as a thermoplastic elastomer and a block that has a function of compatibilizing with a specific thermoplastic resin in the same polymer molecular chain not only has excellent processability, but also has a thermoplastic resin. By compatibilizing when blended with, or acting as a compatibilizer when alloyed with two or more thermoplastic resins, it balances physical properties such as impact resistance, transparency, flexibility and impact whitening resistance The present inventors have found a thermoplastic resin composition that greatly improves the above, and have completed the present invention.

That is, a first aspect of the present invention is a styrene block (S) comprising 99 to 1% by weight of one or more kinds of thermoplastic resins, and (1) 90% by mole or more of a styrene monomer component.
And the monomer component constituted by (2) is mainly composed of the 1-butene (a) component and the ethylene (b) component, and the component ratio of each component is 20 to 45 mol%. , One or more ethylene-1-butene random blocks (B1), in which the component (b) is 80 to 55 mol% and (a) + (b) ≧ 90 mol%, the same unit as (3) and (2). Component (a) is 45 to 100 mol%,
The component (b) is 55 to 0 mol%, and (a) + (b) ≧ 90
Mole% of ethylene-1-butene random block (B2), wherein (B1) block and / or (B2) block exists between (S) blocks and has a molecular weight of 20,000 to Block copolymer 1 having 1,000,000 molecular weight distribution Mw / Mn of 1 to 5
To 99% by weight of a thermoplastic resin composition.

A second aspect of the present invention is that the total content of the block (S) in the block copolymer is 5 to 80% by weight, the total content of the block (B1) is 10 to 70% by weight, and the block (B2) Is 10 to 70% by weight (however,
(S) + (B1) + (B2) = 100% by weight). The thermoplastic resin composition according to the first aspect of the present invention.

A third aspect of the present invention is the thermoplastic resin according to the first and second aspects, wherein the block copolymer has a structure of (S)-(B1)-(S)-(B2). Composition.

A fourth aspect of the present invention is the thermoplastic resin composition according to the first to third aspects, wherein one of the thermoplastic resins is a polypropylene resin.

A fifth aspect of the present invention is the thermoplastic resin composition according to the first to third aspects, wherein the thermoplastic resin is a polypropylene resin, a polystyrene resin and / or a polyphenylene ether resin.

The main feature of the present invention is that a block copolymer having two kinds of specific structures mainly composed of a 1-butene structure and an ethylene structure and having different composition ratios exists in the same polymer molecular chain. It is a thermoplastic resin composition that performs By adopting such a specific block structure, a block functioning as a thermoplastic elastomer and a block having a function of compatibilizing with a thermoplastic resin are included in the same polymer molecular chain.
The block copolymer not only has excellent processability, but also compatibilizes when blended with a thermoplastic resin or acts as a compatibilizer when alloyed with two or more thermoplastic resins. It has been found that a thermoplastic resin composition capable of greatly improving the balance of physical properties such as impact resistance, transparency, flexibility and impact whitening resistance can be obtained.

Hereinafter, the present invention will be described in detail. First, the characteristics of the block copolymer contained in the thermoplastic resin composition of the present invention will be described below. The block (S) is mainly composed of a styrene (s) component, and the (s) component is 90 mol% or more,
It is preferably at least 95 mol%. 1 other than the component (s)
A butene (a) component, an ethylene (b) component, a 1,4-added butadiene (c) component, and a 1,2-added butadiene (d) component may be contained, but the total of these components is 10 It is less than 5 mol%, preferably less than 5 mol%. If the styrene (s) component is less than 90 mol%, the cohesive force as a hard block is weakened, and the function as a thermoplastic elastomer is inferior. Further, two or more blocks (S) are contained in the block copolymer. The number is preferably 2 or more and 6 or less, and more preferably 2. When one block (S) is used, when blended with a thermoplastic resin or when alloyed with two or more kinds of thermoplastic resins, physical properties such as impact resistance are significantly deteriorated. Further, when the number is seven or more, the productivity is deteriorated.

The block (B1) is mainly composed of 1-butene (a)
Component and an ethylene (b) component, and is essentially an ethylene-1-butene random block. In addition to the component (a) and the component (b), a styrene (s) component, a 1,4-added butadiene (c) component, and a 1,2-added butadiene (d) component may be contained at random or in a taper. , The sum of these components is less than 10 mol%, preferably less than 5 mol%. When it is contained in an amount of 10 mol% or more, the heat resistance and weather resistance of the block copolymer or the low-temperature performance as a rubber decreases. The 1-butene (a) component in the block (B1) is 20 to 45 mol%, preferably 25 to 45 mol%, and the ethylene (b) component is 80 to 55 mol%.
Mol%, preferably 75 to 55 mol%. If the 1-butene (a) component is less than 20 mol%, ethylene units are continuous and polyethylene crystallization is likely to occur, so that rubber elasticity is reduced. Further, as the 1-butene (a) component increases, the glass transition point of the block (B1) increases, and the effect as a rubber component at low temperatures tends to decrease. When the content exceeds 45 mol%, the block (B1) increases. Has an excessively high glass transition point, resulting in insufficient low-temperature performance. Further, one or more blocks (B1) are contained in the block copolymer. Since the longer the block chain length is, the more easily the rubber elasticity is exerted, it is advantageous.
Or less, more preferably one. Block (B
If 1) is 4 or more, it is not preferable in terms of productivity.

As described above, the block (B1) functions as a soft block component having a low glass transition point in the block copolymer. For this purpose, the block (B1) exerts its maximum effect as a thermoplastic elastomer when sandwiched between two blocks (S) having a high glass transition point mainly composed of a styrene (s) component serving as a hard block component. .

The block (B2) is mainly composed of 1-butene (a)
Component and ethylene (b) component, and is substantially an ethylene-1-butene random block. In addition to the component (a) and the component (b), a styrene (s) component, a 1,4-added butadiene (c) component, and a 1,2-added butadiene (d) component may be randomly contained. Is less than 10 mol%, preferably less than 5 mol%. When the content is 10 mol% or more, the heat resistance and weather resistance of the block copolymer, the compatibility with the thermoplastic resin, and the function as a compatibilizer are reduced. The 1-butene (a) component in the block (B2) is 45 to 100 mol%, preferably 55 to 100 mol%, and the ethylene (b) component is 55 mol%.
０0 mol%, preferably 45 to 0 mol%. When the 1-butene (a) component is less than 45 mol%, the compatibilization when blended with a thermoplastic resin and the effect as a compatibilizer when alloyed with two or more thermoplastic resins are reduced,
Physical properties such as impact resistance, transparency, flexibility and impact whitening resistance cannot be improved. Further, one or more blocks (B2) are contained in the block copolymer. Since the longer the block chain length is, the more easily the thermoplastic resin becomes compatible with the thermoplastic resin, the number is preferably one or more and three or less, more preferably one. If the number of blocks (B2) is four or more, it is not preferable in terms of productivity.

As described above, the block (B2) has a function of compatibilizing with the thermoplastic resin in the block copolymer, and has a function as a compatibilizing agent in the polymer alloy containing the thermoplastic resin. Therefore, the higher the proportion of the block (B2) in the block copolymer and the higher the molecular weight of the block (B2), the higher the function of compatibilization and the function as a compatibilizer.

The proportion of each block is such that the total content of the block (S) is 5 to 80% by weight,
The total content of 1) is 10 to 70% by weight, and the block (B)
2) 10-70% by weight (however, (S) +
(B1) + (B2) = 100% by weight). Preferably, the total content of the block (S) is 5 to 50% by weight, the total content of the block (B1) is 25 to 60% by weight, and the total content of the block (B2) is 25 to 60% by weight.
(However, (S) + (B1) + (B2) = 100% by weight)
Range.

The block copolymer contained in the thermoplastic resin composition of the present invention has a number average molecular weight (Mn) in terms of polystyrene of 20,000 to 1,000, as measured by gel permeation chromatography (GPC).
000, and the molecular weight distribution Mw / Mn is 1 to 5. If Mn is less than 20,000, pelletization alone becomes difficult, and the strength and the effect as a modifier are significantly poor. On the other hand, when Mn exceeds 1,000,000, workability is remarkably deteriorated. If Mw / Mn is more than 5, the stickiness of the surface by the low molecular weight polymer becomes severe.

The block structure of the block copolymer contained in the thermoplastic resin composition of the present invention may be any block containing the above-mentioned block. For example, (S)-(B1)-(S)
-(B2), (S)-(B2)-(S)-(B1),
(B2)-(S)-(B1)-(S)-(B2),
(S)-(B1)-(S)-(B2)-(S), (S)
-(B1)-(B2)-(S), (S)-(B1)-
A linear polymer represented by (B2)-(S)-(B2), [(B2)-(S)-(B1)] nX, [(B1)
-(S)-(B2)] nX, [(S)-(B1)-(B
2)] nX, [(B2)-(S)-(B1)-(S)]
Sufficient effects can be obtained in any case such as a linear, branched, or radial polymer represented by nX (where n is an integer of 2 or more, and X is a residue of a coupling agent) or a combination thereof. A high effect can be obtained by a structure in which the (B1) block exists between the (S) blocks and the (B2) block is included at the molecular chain terminal, for example, (S)-(B)
1)-(S)-(B2), (B2)-(S)-(B1)
-(S)-(B2), [(B2)-(S)-(B1)]
nX, [(B2)-(S)-(B1)-(S)] nX, and has an excellent balance between the performance as a thermoplastic elastomer and the performance as a compatibilizing / compatibilizing agent. The most preferred block structure is a linear block (S)-(B1)
− (S) − (B2). When producing linear, branched, or radial polymers using a coupling agent, a small amount of uncoupled polymer may remain. An uncoupled polymer may be left to increase the flowability of the final polymer.

The block copolymer contained in the thermoplastic resin composition of the present invention is obtained by hydrogenating an olefinic double bond of a butadiene unit with a base block copolymer shown below in the presence of a hydrogenation catalyst. It can be obtained by:

(1) Two or more styrene blocks (S) comprising 90 mol% or more of a styrene monomer component,
(2) The monomer component is mainly composed of a 1,4-added butadiene (c) component and a 1,2-added butadiene (d) component, and the component ratio of each component is 38. ~ 6
7 mol%, component (d) is 62 to 33 mol%, and (c) +
(D) One or more random polybutadiene blocks (RB1) having ≧ 90 mol% and the same monomer components as in (3) and (2).
8 mol%, component (d) is 100 to 62 mol%, and (c)
(D) ≧ 90 mol% of one or more random polybutadiene blocks (RB2), wherein (RB1) blocks and / or (RB2) blocks are present between two or more (S) blocks; Molecular weight 20,000
１，1,000,000, molecular weight distribution Mw / Mn is 1-5
Is a block copolymer.

Here, the (S) block is the same as the (S) block in the block copolymer of the present invention. The block (RB1) is a block corresponding to the block (B1) in the copolymer of the present invention and mainly comprises a 1,4-added butadiene (c) component and a 1,2-added butadiene (d) component. The styrene (s) component may be contained randomly or in a taper.
Less than 5 mol%, preferably less than 5 mol%. Further, the 1,2-addition butadiene (d) component in the block (RB1) is 33 to 62 mol%, preferably 40 to 62 mol%.
And the 1,4-added butadiene (c) component is 67 to 38.
%, Preferably 60 to 38 mol%.

The block (RB2) is a block corresponding to the block (B2) in the copolymer of the present invention.
-It comprises an addition butadiene (c) component and a 1,2-addition butadiene (d) component, and the styrene (s) component may be included in a random or tapered manner, but the total of the (s) component is less than 10 mol%. , Preferably less than 5 mol%. The content of the 1,2-addition butadiene (d) component in the block (RB2) is 62 to 100 mol%, preferably 7 to 100 mol%.
The amount of the 1,4-added butadiene (c) component is 38 to 0 mol%, preferably 29 to 0 mol%.

The 1-butene structure and the ethylene structure constituting the block in the block copolymer contained in the thermoplastic resin composition of the present invention have a 1,2-added butadiene unit and a 1,4-added butadiene unit, respectively. Is hydrogenated. Therefore, 1,
When the 4-addition butadiene unit is hydrogenated, a (tetramethylene) structure in which two ethylene units are continuous. Therefore, the 1,4-added butadiene (c) is contained in the (RB1) block of the base block copolymer before hydrogenation.
When the component is 38% and the 1,2-added butadiene (d) component is contained at 62%, the (B1) block of the block copolymer after hydrogenation has a hydrogenation rate of 100% at 1-%. This means that the butene structure contains 45 mol% and the ethylene structure contains 55 mol%.

The process for producing the block copolymer before hydrogenation, which is the base of the block copolymer contained in the thermoplastic resin composition of the present invention, is described below. 1,3- as a monomer
Butadiene and styrene are prepared by using an anionic polymerization initiator such as an organic lithium compound in an inert hydrocarbon solvent such as hexane, cyclohexane and benzene, and using diethyl ether, tetrahydrofuran (THF) as a vinylating agent,
2,2-bis (2-oxolanyl) propane (BOP)
Ether compounds, such as triethylamine, N, N,
N ', N'-tetramethylethylenediamine (TMED
A) A tertiary amine compound such as dipiperidinoethane (DPE) is used. In addition, if necessary, epoxidized soybean oil as a coupling agent, diethyl carbonate, dimethyldichlorosilane, methylphenyldichlorosilane, dimethyldiphenylsilane, using a polyfunctional compound such as silicon tetrachloride, linear, branched, A radial block copolymer can also be obtained.

In the addition polymerization of 1,3-butadiene, three kinds of additions, trans 1,4-addition, cis 1,4-addition and 1,2-addition, can occur. This ratio can be controlled by the type and amount of the vinylating agent and the polymerization temperature. In order to increase the 1,2-addition, that is, the vinyl content, it is effective to lower the polymerization temperature or increase the amount of the vinylating agent added.

The block copolymer before hydrogenation may be prepared by a polymerization method other than using the above-mentioned organolithium compound as an initiator, for example, an organometallic compound such as nickel, cobalt or titanium, and lithium, magnesium or aluminum. It may be a method using a Ziegler-based catalyst composed of an organic metal compound such as the above or a radical polymerization method.

Regarding the reaction and conditions of the hydrogenation reaction, any methods and conditions can be used as long as a block copolymer having a hydrogenation ratio specified in the present invention can be obtained. Examples of such hydrogenation methods include a method using a catalyst mainly containing an organometallic compound of titanium as a hydrogenation catalyst, and a catalyst comprising an organic compound of iron, nickel, and cobalt and an organometallic compound such as alkylaluminum. How to use, ruthenium, method using a catalyst consisting of an organometallic compound such as rhodium, palladium, platinum, ruthenium, cobalt, nickel and other metals such as carbon, silica,
There is a method using a catalyst supported on a carrier such as alumina and diatomaceous earth. Among various methods, an organometallic compound of titanium alone or a homogeneous catalyst comprising the same and an organometallic compound of lithium, magnesium and aluminum (JP-B-63-4841 and JP-B-1-3797) is used. The method is preferred because it can be industrially hydrogenated under mild conditions of low pressure and low temperature, and has high hydrogenation selectivity to the olefinic double bond of the butadiene unit and does not hydrogenate the aromatic ring in the styrene unit. Suitable for the purpose of the present invention. A particularly preferred catalyst is a system using a titanocene compound represented by the following general formula and a reducing agent, which may be separately added to the reaction system, or a reaction product prepared in advance may be added to the reaction system. May be. When it is prepared in advance, an olefinically unsaturated double bond-containing polymer may be allowed to coexist as described in JP-B-7-25811.

[0035]

Embedded image

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ , R ⁹ and R ¹⁰ each represent hydrogen or a group having 1 to 8 carbon atoms.
Which may be the same or different, may form an aliphatic ring or an aromatic ring, or may be connected like a bridge between two substituted cyclopentadienyl groups. R ¹¹ and R ¹² are a hydrocarbon group having 1 to ¹² carbon atoms, a benzyl group, an aryloxy group, an alkoxy group,
It is a group selected from a halogen group and a carbonyl group. R ¹¹ and R ¹² may be the same or different, or may form a metallacycle containing titanium. Also,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ ,
R ¹⁰ , R ¹¹ , and R ¹² are groups mainly composed of carbon, and include atoms such as oxygen, nitrogen, boron, silicon, phosphorus, sulfur, and chlorine as long as they do not adversely affect hydrogenation activity. Is also good. Also, tetrahydrofuran, diethyl ether,
It may form a complex with trimethylphosphine, triphenylphosphine, or the like.

Among the titanocene compounds that can be used, examples of using the same (un) substituted cyclopentadienyl group include di-m-tolyl-bis (η ⁵ -cyclopentadienyl) titanium, di-m-tolyl - bis (eta ⁵ - pentamethylcyclopentadienyl) titanium, di -m- tolyl - bis (eta ⁵ - indenyl) titanium, di -m- tolyl - bis (eta ⁵ - tetrahydroindenyl) titanium, di -m - tolyl - bis (eta ⁵ - fluorenyl) titanium, di -p- tolyl - bis (eta ⁵ - cyclopentadienyl) titanium, di -p- tolyl - bis (eta ⁵ - di - trimethylsilyl cyclopentadienyl) titanium , Di-p-tolyl-bis (η
⁵ -trimethylcyclopentadienyl) titanium, di-p
-Tolyl-bis- (η ⁵ -tributylcyclopentadienyl) titanium, di-p-tolyl-bis (η ⁵ -tetramethylcyclopentadienyl) titanium, di-p-tolyl-
Bis (eta ⁵ - pentamethylcyclopentadienyl) titanium, di -p- tolyl - bis (eta ⁵ - indenyl) titanium, di -p- tolyl - bis (eta ⁵ - tetrahydroindenyl) titanium, di -p- tolyl - bis (eta ⁵ - fluorenyl) titanium, diphenyl bis (eta ⁵ - cyclopentadienyl) titanium, diphenyl bis (eta ⁵ - pentamethylcyclopentadienyl) titanium, dichlorobis (eta ⁵ -
Cyclopentadienyl) titanium, dichlorobis (η ⁵ −
Di-trimethylsilylcyclopentadienyl) titanium,
Dichlorobis (eta ⁵ - trimethyl cyclopentadienyl) titanium, dichlorobis (eta ⁵ - tri-butylcyclopentadienyl) titanium, dichlorobis (eta ⁵ - tetramethylcyclopentadienyl) titanium, dichlorobis (eta
⁵ - pentamethylcyclopentadienyl) titanium, dichlorobis (eta ⁵ - penta -n- butyl cyclopentadienyl) titanium, dichlorobis (eta ⁵ - indenyl) titanium, dichlorobis (eta ⁵ - tetrahydroindenyl) titanium, dichlorobis ( eta ⁵ - fluorenyl) titanium, dibromobis (eta ⁵ - cyclopentadienyl) titanium, dibromobis (eta ⁵ - pentamethylcyclopentadienyl) titanium, Jifurorobisu (eta ⁵ - cyclopentadienyl) titanium, diiodobis (eta ⁵ - cyclopentadienyl) titanium, dimethyl bis (eta ⁵ - cyclopentadienyl) titanium, dimethyl bis (eta ⁵ - di - trimethylsilyl cyclopentadienyl) titanium, dimethyl bis (eta ⁵
- trimethyl cyclopentadienyl) titanium, dimethyl bis (eta ⁵ - tri-butylcyclopentadienyl) titanium dimethyl bis (eta ⁵ - tetramethylcyclopentadienyl) titanium, dimethyl bis (eta ⁵ - pentamethylcyclopentadienyl ) titanium, Jiechirubisu (eta ⁵ - cyclopentadienyl) titanium, dihexyl bis (eta ⁵ -
Cyclopentadienyl) titanium, dioctylbis (η ⁵
-Cyclopentadienyl) titanium, di-trimethylsilylmethylbis (η ⁵ -cyclopentadienyl) titanium,
Di - trimethylsilylmethyl bis (eta ⁵ - pentamethylcyclopentadienyl) titanium, Jibenjirubisu (eta ⁵
-Cyclopentadienyl) titanium, dibenzylbis (η
⁵ - di - trimethylsilyl cyclopentadienyl) titanium, Jibenjirubisu (eta ⁵ - pentamethylcyclopentadienyl) titanium, dimethoxy bis (eta ⁵ - cyclopentadienyl) titanium, dimethoxy bis (eta ⁵ - pentamethylcyclopentadienyl enyl) titanium, Jietokishibisu (eta ⁵ - cyclopentadienyl) titanium, Jietokishibisu (eta ⁵ - pentamethylcyclopentadienyl) titanium, di -n- butoxybis (eta ⁵ - cyclopentadienyl) titanium, di -n- butoxybis (eta ⁵ - pentamethylcyclopentadienyl) titanium, Jifenokishibisu (eta ⁵ - cyclopentadienyl) titanium, Jifenokishibisu (eta ⁵ - pentamethylcyclopentadienyl) titanium, di (2,6 Di-tert-butylphenoxy) bis (η ⁵ -cyclopentadienyl ) Titanium, di (2, 6)
- di -tert- butyl) bis (eta ⁵ - pentamethylcyclopentadienyl) titanium, methyl bis (eta ⁵ - cyclopentadienyl) Chitankurorido, methyl bis (eta ⁵ - di - trimethylsilyl cyclopentadienyl) Chitankurorido , methyl bis (eta ⁵ - pentamethylcyclopentadienyl) Chitankurorido, trimethylsilylmethyl bis (eta ⁵ - cyclopentadienyl) Chitankurorido, trimethylsilylmethyl bis (eta ⁵ - pentamethylcyclopentadienyl) Chitankurorido, di ( trimethylsilyl) methyl (eta ⁵ - cyclopentadienyl) Chitankurorido, di (trimethylsilyl) methyl (eta ⁵ - pentamethylcyclopentadienyl) Chitankurorido, benzyl bis (eta ⁵ - cyclopentadienyl)
Chitankurorido, benzyl bis (eta ⁵ - pentamethylcyclopentadienyl) Chitankurorido, methoxybis (eta ⁵ - cyclopentadienyl) Chitankurorido, methoxybis (eta ⁵ - pentamethylcyclopentadienyl)
Chitankurorido, Fenokishibisu (eta ⁵ - cyclopentadienyl) Chitankurorido, Fenokishibisu (eta ⁵ - pentamethylcyclopentadienyl) Chitankurorido,
2,6-di-tert-butylphenoxybis (η ⁵ −
Cyclopentadienyl) titanium chloride, 2,6-di-
tert-butylphenoxybis (η ⁵ -pentamethylcyclopentadienyl) titanium chloride and the like.

Further, when two different cyclopentadienyl derivative groups are used, a cyclopentadienyl group, a di-trimethylsilylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group may be used. Enyl group, pentamethylcyclopentadienyl group, indenyl group, tetrahydroindenyl group,
It can be selected from a fluorenyl group, an octahydrofluorenyl group, or any combination of these derivatives.

In any combination of the two cyclopentadienyl derivative groups, two selected cyclopentadienyl derivative groups may be bridged by a dimethylsilyl group or a 1,2-ethylene group. .

R ¹¹ and R ¹² form a metallacycle containing titanium, which includes an o-xylidene group,
Examples thereof include a 1'-binaphthyl-2,2'-oxy group, a titanacyclobutane derivative represented by the following chemical formula, and a titanacyclopentane derivative.

[0041]

Embedded image

Here, m represents an integer of 3 or more, and R ¹³ ,
R ¹⁴ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms.
These may be the same or different, and may form an aliphatic ring or an aromatic ring.

R ¹¹ and R ¹² are groups mainly composed of carbon, but may contain atoms such as oxygen, nitrogen, boron, silicon, phosphorus, sulfur, chlorine and the like. For example, dimethylaminoalkyl group, diphenylphospho And a finoalkyl group.

Particularly preferred among these titanocene compounds are di-m-tolyl-bis (η ⁵ -cyclopentadienyl) titanium, di-p-tolyl-bis (η ⁵ -cyclopentadienyl) titanium, Di-p-tolyl-bis (η ⁵ -pentamethylcyclopentadienyl) titanium,
Dichlorobis (η ⁵ -cyclopentadienyl) titanium,
Dichlorobis (eta ⁵ - pentamethylcyclopentadienyl) titanium.

The reducing agent is preferably an organometallic compound or a hydride of an alkali metal, an alkaline earth metal, aluminum or zinc. Examples of the organometallic compound include a living anionic polymer having an activity and a living anionic polymer. An organic lithium compound, an organic sodium compound, an organic potassium compound, a diorganic substituted magnesium, an organic substituted magnesium halide, an organic trisubstituted aluminum, an organic substituted aluminum halogenide, an organic substituted aluminum hydride, an aluminum oxy compound, Organic substituted zinc and the like.

Specific examples of the organic lithium compound include methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium,
sec-butyllithium, tert-butyllithium,
Pentyl lithium, hexyl lithium, 2-ethylhexyl lithium, octyl lithium, phenyl lithium,
Tolyl lithium, xylyl lithium, methoxy lithium, ethoxy lithium, n-propoxy lithium, is
Examples thereof include o-propoxylithium, n-butoxylithium, pentyloxylithium, hexyloxylithium, octyloxylithium, phenoxylithium, 4-methylphenoxylithium, benzyloxylithium, and 4-methylbenzyloxylithium. Further, a lithium phenolate compound obtained by reacting an alkyllithium with a phenolic stabilizer, trimethylsilyllithium, diethylmethylsilyllithium, dimethylethylsilyllithium, triethylsilyllithium, triphenylsilyllithium, trimethylsiloxylithium, diethylmethylsiloxylithium Organosilicon lithium compounds such as lithium, triethylsiloxylithium, and triphenylsiloxylithium, and lithium amides such as di-isopropylamidolithium can also be used.

Examples of the organic sodium compounds include methyl sodium, ethyl sodium, n-propyl sodium, n-butyl sodium, sec-butyl sodium, tert-butyl sodium, hexyl sodium, octyl sodium, phenyl sodium, tolyl sodium, and sodium naphthalene. And the like. ,
Further, as the organic potassium compound, methyl potassium, ethyl potassium, n-propyl potassium, n-butyl potassium, sec-butyl potassium, tert-butyl potassium, hexyl potassium, octyl potassium, phenyl potassium, tolyl potassium, triphenylmethyl potassium, phenyl potassium Examples include ethyl potassium and potassium naphthalene.

As the diorganic substituted magnesium compound, dimethylmagnesium, cyethylmagnesium, di-n-
Butylmagnesium, n-butyl-sec-butylmagnesium, n-butylethylmagnesium and the like, and ate complexes such as tributylsodiummagnesium can also be used. Further, methyl magnesium bromide, ethyl magnesium bromide, ethyl magnesium chloride, t
Ert-butyl magnesium bromide, tert-butyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium chloride and the like can also be used.

Examples of the triorgano-substituted aluminum compound include trimethylaluminum, triethylaluminum, tri-iso-butylaluminum, tri (2-ethylhexyl) aluminum, triphenylaluminum and the like. Examples of the organosubstituted aluminum halide include diethylaluminum chloride, Methyl aluminum sesquichloride, ethyl aluminum sesquichloride,
iso-butylaluminum sesquichloride, ethylaluminum dichloride, iso-butylaluminum dichloride and the like. Further, examples of the organic substituted aluminum hydride compound include diethyl aluminum hydride and di-iso-butyl aluminum hydride, and examples of the aluminum oxy compound include methyl aluminoxane and ethyl aluminoxane. Examples of the diorganic substituted zinc compound include diethyl zinc, bis (η ⁵ -cyclopentadienyl) zinc, diphenyl zinc and the like.

In addition to these, sodium aluminum hydride, lithium aluminum hydride,
iso-butyl sodium aluminum hydride,
Tri (tert-butoxy) lithium aluminum hydride, triethyl sodium aluminum hydride, di-iso-butyl sodium aluminum hydride, iso-butyl sodium aluminum hydride, triethyl sodium aluminum hydride, triethoxy sodium aluminum hydride, triethyl lithium aluminum hydride, etc. A reducing agent containing the above metals may be used. Also,
These may be used as a mixture of two or more kinds.

The hydrogenation is carried out in a solvent which is inert to the catalyst and in which the copolymer is soluble. Preferred solvents include n-pentane, n-hexane, aliphatic hydrocarbons such as n-octane, cyclohexane, alicyclic hydrocarbons such as cycloheptane, benzene, aromatic hydrocarbons such as toluene, It is a single substance or a mixture mainly composed of ethers such as diethyl ether and tetrahydrofuran. Particularly, it is advantageous in terms of cost to use the copolymer solution obtained when producing the block copolymer as it is. In this case, it is generally preferable to completely inactivate the active terminal lithium with a compound having active hydrogen such as alcohol, but it is also possible to leave the active terminal lithium as part or all of the reducing agent. is there. Further, an organic compound such as a vinylating agent used during the production of the copolymer may be contained as it is.

The hydrogenation reaction is generally carried out by maintaining the copolymer at a predetermined temperature in a hydrogen or inert atmosphere, adding a hydrogenation catalyst with or without stirring, and then introducing hydrogen gas. This is performed by applying a predetermined pressure. The term "inert atmosphere" refers to an atmosphere such as helium, neon, or argon that does not hinder the hydrogenation reaction. Air and oxygen are not preferred because they oxidize the catalyst and cause deactivation of the catalyst.
Nitrogen may be present in the reaction system in a small amount, but is not preferred because it acts as a catalyst poison during the hydrogenation reaction and may reduce the hydrogenation activity. In particular, it is most preferable that the inside of the hydrogenation reactor be an atmosphere containing only hydrogen gas. Also,
The hydrogenation reaction process for obtaining the hydrogenated copolymer can be any of a batch process, a continuous process, and a combination thereof.

When a titanocene diaryl compound is used as a hydrogenation catalyst, it may be added alone to the reaction solution or as a solution dissolved in an inert organic solvent. As the inert organic solvent used when the catalyst is used as a solution, the above-mentioned various solvents which do not inhibit the hydrogenation reaction can be used. Preferably, it is the same solvent as the solvent used for the polymerization. The amount of the catalyst to be added is 0.02 to 20 mmol per 100 g of the block copolymer before hydrogenation.

The most preferred method for obtaining the block copolymer contained in the thermoplastic resin composition of the present invention is to convert the block copolymer before hydrogenation into an anion in solution using an organolithium initiator and a vinylating agent. After living polymerization, after the polymerization is completed, a coupling agent is added as necessary, or a reaction terminator containing active hydrogen such as alcohol is added, and the obtained polymer solution is used as it is in the next hydrogenation reaction. Yes, very industrially useful. Further, the block copolymer can be isolated and obtained by removing the solvent from the hydrogenated block copolymer solution.
Examples of the method for removing the solvent include, after coagulating the block copolymer solution with methanol or the like, heating or drying under reduced pressure, or pouring the block copolymer solution into boiling water, azeotropically removing the solvent, and then removing the solvent. , By heating or drying under reduced pressure.

The block copolymer contained in the thermoplastic resin composition of the present invention can be used singly, can be used alone for modifying thermoplastic resins, and can be used as a polymer alloy of two or more different thermoplastic resins. Used as a compatibilizer.

The thermoplastic resin may be a polyethylene resin such as polyethylene, high molecular weight polyethylene, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene (LLDPE), polyethylene produced by a metallocene polymerization catalyst, or homopolymer. Polypropylene-based resins such as polypropylene, block polypropylene and random polypropylene, polybutene, polyisobutylene, high impact polystyrene (HIPS),
Polystyrene resin such as polystyrene, poly-α-methylstyrene, ABS resin, polymethylene, poly-4-methyl-1-pentene, acrylic resin, polyacrylamide, polymethacrylamide, polyacrylic acid, polymethyl acrylate, polyacryl Polyacrylate alkyl esters such as ethyl acrylate, polymethacrylic acid, polymethyl methacrylate, polymethacrylate alkyl esters such as polyethyl methacrylate, polyacrylonitrile, polymethacrylonitrile, acetal resin, polyoxymethylene, chlorinated polyethylene, Coumarone-indene resin, cellulose, cellulose ester, cellulose ether,
Carboxymethyl cellulose, cellulose ether ester, fluororesin, polychlorotrifluoroethylene,
Polyvinylidene fluoride, polyvinyl fluoride, nylon 1
1, nylon 12, nylon 6, nylon 6,10, nylon 6,12, nylon 6,6, aliphatic polyamide such as nylon 4,6, polyphenylene isophthalamide,
Aromatic polyamides such as polyphenylene terephthalamide, polyimides, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether resins such as polyphenylene ether and modified polyphenylene ether, polyphenylene sulfide, polysulfone, polyether sulfone, polysulfonamide, polyether ether ketone, polyamide Examples include thermoplastic resins such as imide, polyarylate, polycarbonate, polyvinyl alcohol, polyvinyl ester, polyvinyl acetate, polymethyl vinyl ether, polyisobutylene vinyl ether, polyvinyl chloride, and polyvinylidene chloride. Preferred thermoplastic resins include polyethylene, polypropylene, polystyrene, polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyphenylene sulfide, polysulfone, and polycarbonate.

The polypropylene resin is most preferable because the block portion (B2) of the block copolymer is easily compatible with the polypropylene resin. By blending the block copolymer with the polypropylene resin, the polypropylene resin can be softened while maintaining its transparency. The amount required to soften the polypropylene resin depends on the desired softness, but a sufficient effect can be obtained by adding 10 parts by weight of the block copolymer to 90 parts by weight of the polypropylene resin. As the amount of the block copolymer increases, the degree of softening naturally increases.

On the other hand, whether or not the block portion (B2) of the polypropylene resin and the block copolymer are compatible can be evaluated by examining the impact whitening property. Impact whitening can be prevented by increasing the addition amount of the block copolymer. In the case of the block copolymer contained in the thermoplastic resin composition of the present invention, the impact whitening property can be improved by adding 5 to 80 parts by weight or more based on 100 parts by weight of the polypropylene resin. However, when the added amount of the block copolymer is too large, there is a disadvantage that the obtained composition becomes too soft. For the purpose of improving the characteristics of the block copolymer contained in the thermoplastic resin composition of the present invention, that is, to improve the impact whitening property without excessively softening, the addition of 10 to 45 parts by weight is preferred.

In recent years, soft PVC alternative materials have been demanded from the viewpoint of recyclability and environmental problems. Characteristics of soft PVC include moderate softness, transparency, and a balance of physical properties such that it does not whiten even when bent. A composition containing a polypropylene resin and the block copolymer has the characteristics of this soft PVC.

Further, the composition obtained by adding the block copolymer in an amount of 80 parts by weight or more with respect to 100 parts by weight of the polypropylene resin has improved whitening onset elongation at the time of tension. Particularly from the composition obtained by adding 200 parts by weight or more of the block copolymer, hardness,
It is possible to obtain a molded article having a good balance between elongation and elongation at start of whitening during tension.

The block copolymer also exhibits an effect as a compatibilizer of a polymer alloy made of two or more kinds of thermoplastic resins including a polypropylene resin. Since the block copolymer contained in the thermoplastic resin composition of the present invention has a styrene block, a thermoplastic resin having a styrene-like structure is preferable. Particularly suitable thermoplastic resins to be combined with the polypropylene-based resin include polystyrene-based resins and polyphenylene ether-based resins.

The thermoplastic resin composition of the present invention may contain auxiliary additives such as an antioxidant, a heat stabilizer, an ultraviolet absorber, a coloring agent, and a flame retardant. Furthermore, glass fiber, carbon fiber, metal fiber, glass beads, mica,
Fillers such as calcium carbonate, potassium titanate whiskers, talc, and aramid fibers, oils, plasticizers, and low molecular weight polymers can be used alone or in combination. Further, in order to prevent blocking of pellets or crumbs, various antiblocking agents used in the art may be added.

The method for producing these compositions is not particularly limited, but a known method, for example, a method of kneading the components with a variety of extruders, Banbury mixers, kneaders, rolls, Labo plast mills and the like can be used. No.

[0064]

EXAMPLES The present invention will now be described specifically with reference to Examples and Comparative Examples, but these do not limit the scope of the present invention.

-Method for measuring block copolymer-Styrene content in block copolymer Calculated by UV measurement.

The vinyl bond content of the polybutadiene block was calculated by the Hampton method using Fourier transform infrared spectroscopy (FT-IR). By measuring each time polybutadiene was polymerized, the vinyl bond content of each polybutadiene block was determined from the weight ratio of the charged butadiene monomers.

Hydrogenation rate of polybutadiene block Using deuterated chloroform as a solvent, 400 MHz,
It was calculated from the 1 H-NMR spectrum.

The number average molecular weight of the block copolymer was determined by gel permeation chromatography (GPC) at a column temperature of 43 ° C. using tetrahydrofuran (THF) as a solvent.

<Reference Example 1 for Polymerization> In a 100-liter autoclave purged with nitrogen, dried and purified 60 liters of cyclohexane and 605 of tetrahydrofuran (THF).
G (8.40 mol), n-butyllithium 9.69
A cyclohexane solution containing gram (0.151 mol) was charged and the temperature was raised to 60 ° C. 577 g of styrene was added thereto to carry out polymerization. Subsequently, 4.63 kg of 1,3-butadiene and 577 g of styrene were successively added to continue the polymerization. Here, the temperature is cooled to 40 ° C., and then tetramethylethylenediamine (TMEDA) 3
An additional 5.1 grams (0.302 mole) was added,
3.86 kg of 3-butadiene are polymerized at a polymerization temperature of 60 ° C.
, And polymerization was carried out by adding gradually so as not to exceed. After termination of the polymerization, 3.83 g (0.120 mol) of methanol was added to inactivate the living active terminal. The resulting block copolymer had a number average molecular weight of about 70,000, a styrene content of 12 wt%, a 1,2-vinyl bond content of the polybutadiene portion of 37% for the first polymerized polybutadiene block, and 1% for the final copolymer. Since the 2,2-vinyl bond content was 53%, the last polymerized polybutadiene block was an S-RB1-S-RB2 type block copolymer in which the 1,2-vinyl bond content was 72%. Was.

<Reference Example 2 for Polymerization> Instead of THF, TM
A block copolymer was prepared in the same manner as in Polymerization Reference Example 1, except that 4.54 g (39.1 mmol) of EDA and 8.94 g (0.140 mol) of n-butyllithium were used. The resulting block copolymer had a number average molecular weight of about 8
The styrene content was 12% by weight, the 1,2-vinyl bond content of the polybutadiene portion was 49% for the first polymerized polybutadiene block, and 62% for the 1,2-vinyl bond content of the final copolymer. From the above, it was found that the polybutadiene block finally polymerized was an S-RB1-S-RB2 type block copolymer having a 1,2-vinyl bond content of 77%.

<Reference Example 3 for Polymerization> n- as a polymerization initiator
7.89 g of butyllithium (0.123 mol)
3.87 g (33.3 mmol) of TMEDA, TM
Polymerization Reference Example 1 except that instead of EDA, 56.6 g (0.308 mol) of 2,2-bis (2-oxolanyl) propane (BOP) was used before the polymerization of the B2 block portion.
A block copolymer was prepared in the same manner as described above. The obtained block copolymer had a number average molecular weight of about 90,000 and a styrene content of 12
wt%, the 1,2-vinyl bond content of the polybutadiene portion is 40% for the first polymerized polybutadiene block,
Since the 1,2-vinyl bond content of the final copolymer was 57%, the 1,2-vinyl bond content of the finally polymerized polybutadiene block was 76%.
-S-RB2 type block copolymer.

<Polymerization Reference Example-4> 18 L of cyclohexane purified and dried in a 30 L autoclave purged with nitrogen, 1.76 g (15.1 mmol) of TMEDA instead of THF, and 3.7 parts of n-butyllithium
A cyclohexane solution containing 3 grams (58.3 mmol) was charged and heated to 60 ° C. There styrene 275
Grams were added to effect polymerization. Subsequently, 1.92 kg of 1,3-butadiene and 275 g of styrene were successively added, and polymerization was continued. Here, after cooling the temperature to 40 ° C., 26.8 g (0.146 mol) of BOP was further added, and a block copolymer was prepared in the same manner as in Polymerization Reference Example 1 except that 275 g of 1,3-butadiene was polymerized. Had made. The obtained block copolymer had a number average molecular weight of about 6
The styrene content was 20 wt%, the 1,2-vinyl bond content of the polybutadiene portion was 35% for the initially polymerized polybutadiene block, and 39% for the 1,2-vinyl bond content of the final copolymer. From the results, it was found that the polybutadiene block finally polymerized was an S-RB1-S-RB2 type block copolymer having a 1,2-vinyl bond content of 71%.

<Reference Example 5 for Polymerization> 3.34 g (52.3 mmol) of n-butyllithium polymerization initiator, TME
In the presence of 1.64 grams (14.1 mmol) of DA,
219 grams of styrene, 1.75 kilograms of 1,3-butadiene, and 219 grams of styrene were polymerized sequentially,
Same as in Polymerization Reference Example 4 except that 24.1 g (0.131 mol) was further added, and then 547 g of 1,3-butadiene was slowly added to carry out polymerization while controlling the polymerization temperature to 40 to 45 ° C. A block copolymer was prepared. The obtained block copolymer had a number average molecular weight of about 6
The styrene content was 16% by weight, the 1,2-vinyl bond content of the polybutadiene portion was 42% for the initially polymerized polybutadiene block and 52% for the 1,2-vinyl bond content of the final copolymer. From the results, it was found that the finally polymerized polybutadiene block was an S-RB1-S-RB2 type block copolymer in which the 1,2-vinyl bond content was 84%.

<Reference Example 6 for Polymerization> 2.47 g (38.5 mmol) of n-butyllithium polymerization initiator, TME
In the presence of 1.21 grams (10.4 mmol) of DA,
164 grams of styrene, 1.31 kilograms of 1,3-butadiene and 164 grams of styrene were sequentially polymerized and
Polymerization Reference Example 4 except that after addition of 17.7 g (0.096 mol), 1.09 kg of 1,3-butadiene was slowly added and polymerization was controlled at a polymerization temperature of 40 to 45 ° C. A block copolymer was prepared in the same manner as described above. The resulting block copolymer had a number-average molecular weight of about 70,000, a styrene content of 12 wt%, a 1,2-vinyl bond content of the polybutadiene portion of 35% for the first polymerized polybutadiene block, and 1 for the final copolymer. Since the 2,2-vinyl bond content was 57%, the last polymerized polybutadiene block was an S-RB1-S-RB2 type block copolymer having a 1,2-vinyl bond content of 83%. Was.

<Reference Example 7 for Polymerization> 7.13 g (0.111 mol) of n-butyllithium polymerization initiator, TMED
In the presence of 6.47 g (55.7 mmol) of A, 524 g of styrene, 3.76 kg of 1,3-butadiene, and 524 g of styrene were sequentially polymerized, and TMED
Polymerization Reference Example 1 except that 12.9 g (0.111 mol) of A was further added and then 3.93 kg of 1,3-butadiene was slowly added to control the polymerization temperature at 40 to 45 ° C. A block copolymer was prepared in the same manner as described above. The resulting block copolymer had a number average molecular weight of about 110,000, a styrene content of 12 wt%, a 1,2-vinyl bond content of the polybutadiene portion of 58% for the first polymerized polybutadiene block, and 1% for the final copolymer. , 2-
Since the vinyl bond content was 66%, the finally polymerized polybutadiene block was an S-RB1-S-RB2 type block copolymer in which the 1,2-vinyl bond content was 73%.

<Comparative Polymerization Reference Example-1> A cyclohexane solution containing 258 g (3.57 mol) of THF and 4.12 g (64.3 mmol) of n-butyllithium was charged and heated to 60 ° C. 275 g of styrene was added thereto to carry out polymerization. Subsequently, after sequentially polymerizing 2.06 kg of 1,3-butadiene and 275 g of styrene, 137 g of 1,3-butadiene was sequentially polymerized without adding an additive, and the block copolymerization was performed in the same manner as in Polymerization Reference Example 4. Made a union. The obtained block copolymer had a number average molecular weight of about 53,000, a styrene content of 20% by weight, a 1,2-vinyl bond content of the polybutadiene portion was 36% for the polybutadiene block polymerized first, and a final copolymer was obtained. Since the 1,2-vinyl bond content of the polybutadiene block finally polymerized was 36%,
S-RB1-S-RB having a vinyl bond content of 36%
It was a type 1 block copolymer.

Comparative Reference Polymerization Example 2 A block copolymer was prepared in the same manner as in Comparative Polymerization Reference Example 1 except that 2.09 g (18.0 mmol) of TMEDA was used instead of THF. The obtained block copolymer had a number average molecular weight of about 53,000, a styrene content of 20% by weight, a 1,2-vinyl bond content of the polybutadiene portion was 42% for the first polymerized polybutadiene block, and a final copolymer was obtained. 1,2
-Since the vinyl bond content was 42%, the S-RB1-S-RB1 type block copolymer in which the 1,2-vinyl bond content of the finally polymerized polybutadiene block was 42% was obtained.

<Comparative Polymerization Reference Example-3> Instead of THF, 9.07 g (78.0 mmol) of TMEDA was added, and 8.77 g (0.137 mol) of n-butyllithium was used as a polymerization initiator. 689 grams of styrene, 1,
8.02 kilograms of 3-butadiene, 689 grams of styrene, and 49% of 1,3-butadiene without additional additives.
A block copolymer was prepared in the same manner as in Polymerization Reference Example 1 except that 5 grams were sequentially polymerized. The obtained block copolymer had a number average molecular weight of about 95,000 and a styrene content of 15 wt.
%, The 1,2-vinyl bond content of the polybutadiene portion was 59% for the initially polymerized polybutadiene block and 59% for the 1,2-vinyl bond content of the final copolymer. The 1,2-vinyl bond content of the polybutadiene block is 59%.
It was an S-RB1 type block copolymer.

<Comparative Polymerization Reference Example-4> Nitrogen-substituted 10
In a 0 liter autoclave, 40 liters of dried and purified cyclohexane, 8.46 grams of TMEDA (73
Mmol), 15.5 grams of n-butyllithium (0.
243 mol) in a cyclohexane solution.
The temperature was raised to ° C. Thereto, 1233 g of styrene was added to carry out polymerization. Subsequently, 7.92 kg of 1,3-butadiene was added to obtain an AB2-type block polymer.
Dichlorodimethylsilane 7.05 as a coupling agent
Gram (54.6 mmol) was added to carry out the coupling reaction for about 30 minutes. After the coupling reaction is completed,
2.56 grams (80 mmol) of methanol were added to deactivate the remaining living active ends. The obtained block copolymer showed a bimodal GPC curve with peak molecular weights of about 40,000 and about 80,000, and a styrene content of 13 wt.
%, 1,2-vinyl bond content of polybutadiene part 4
The S-RB1 / S-RB1-RB1-S type block copolymer was 1% and was a 2/3 type block copolymer having a weight ratio of 30/70.

<Reference Example for Comparative Polymerization-5> Using 3.42 g (53.5 mmol) of n-butyllithium, 412 g of styrene, 1.79 kg of 1,3-butadiene, 412 g of styrene, 1,3- Butadiene 137
A block copolymer was prepared in the same manner as in Comparative Polymerization Reference Example 1 except that gram was sequentially polymerized. The obtained block copolymer had a number average molecular weight of about 67,000 and a styrene content of 30 wt.
%, The 1,2-vinyl bond content of the polybutadiene portion was 36% for the first polymerized polybutadiene block, and 36% for the 1,2-vinyl bond content of the final copolymer. S-RB1- wherein the 1,2-vinyl bond content of the polybutadiene block is also 36%.
It was an S-RB1 type block copolymer.

<Hydrogenated Reference Example-1> A nitrogen-substituted 20 liter autoclave was charged with 12 liters of the cyclohexane solution of the block copolymer obtained in Polymerization Reference Example 1, purged with hydrogen, and then subjected to a hydrogen pressure of 0.7 MPa ( (Gauge pressure), and the temperature was raised to 70 ° C. Then, 4 ml of a cyclohexane solution containing 254 mg (1.02 mmol) of dichlorobis (η ⁵ -cyclopentadienyl) titanium and 147 mg (2.04 mmol) of trimethylaluminum were added while stirring, and the hydrogen pressure was reduced to 0.7 MPa. (Gauge pressure) was maintained for 1 hour. After the absorption of hydrogen was completed, a small amount of this polymer was sampled and analyzed. The average hydrogenation rate of the polybutadiene block was 9%.
9%, and the aromatic ring of the polystyrene block was not hydrogenated.

<Hydrogenated Reference Example 2> 423 mg (1.70 mmol) of dichlorobis (η ⁵ -cyclopentadienyl) titanium and diethylaluminum chloride were added to a cyclohexane solution of the block copolymer obtained in Polymerization Reference Example 2. A hydrogenation reaction was carried out in the same manner as in Reference Example 1 except that 7 mL of a cyclohexane solution containing 1.23 g (10.2 mmol) was added. The average hydrogenation rate of the polybutadiene block of the obtained hydrogenated block copolymer was 98%, and the aromatic ring of the polystyrene block was not hydrogenated.

[0083] <hydrogenated Reference Example -3> Polymerization Example 3 with the resultant block copolymer cyclohexane solution of di -m- tolyl - bis (eta ⁵ - cyclopentadienyl) titanium 36
Hydrogenated Reference Example 1 except that 40 ml of a cyclohexane solution containing 8 mg (1.02 mmol) was added.
A hydrogenation reaction was performed in the same manner as described above. The average hydrogenation rate of the polybutadiene block of the obtained hydrogenated block copolymer was 99%, and the aromatic ring of the polystyrene block was not hydrogenated.

<Hydrogenated Reference Example-4> Di-m-tolyl-bis (η ⁵ -cyclopentadienyl) titanium was added to a cyclohexane solution of the block copolymer obtained in Polymerization Reference Example 4.
A hydrogenation reaction was carried out in the same manner as in Reference Example 1, except that a cyclohexane solution containing 5 mg (0.68 mmol) and 0.82 mmol of n-butyllithium was added.
The average hydrogenation rate of the polybutadiene block of the obtained hydrogenated block copolymer was 99%, and the aromatic ring of the polystyrene block was not hydrogenated.

<Hydrogenation Reference Example-5> Pd / C (5% by weight of Pd) was used as a hydrogenation catalyst in the cyclohexane solution of the block copolymer obtained in Polymerization Reference Example 5, and the hydrogen pressure was 3.5 P.
a, A hydrogenation reaction was performed at about 120 ° C. The average hydrogenation rate of the polybutadiene block of the obtained hydrogenated block copolymer was 96%, and the aromatic ring of the polystyrene block was not hydrogenated.

<Hydrogenated Reference Example-6> Nickel 2-ethylhexanoate and triethylaluminum (Al / Ni = 2/1) as a hydrogenation catalyst were added to a cyclohexane solution of the block copolymer obtained in Polymerization Reference Example 6. ) Was previously reacted in cyclohexane, Ni was added in an amount corresponding to about 900 ppm, and a hydrogen pressure of about 0.1 ppm was added.
The hydrogenation reaction was performed at 65 MPa and about 80 ° C. The average hydrogenation rate of the polybutadiene block of the obtained hydrogenated block copolymer was 98%, and the aromatic ring of the polystyrene block was not hydrogenated.

<Hydrogenated Reference Example-7> Except that the block copolymer obtained in Polymerization Reference Example 7 was used instead of the block copolymer obtained in Polymerization Reference Example 1, <Hydrogenated Reference Example- 1>
A hydrogenated block copolymer was obtained in the same manner as described above.

<Comparative Hydrogenated Reference Examples-1 to 5> Polymerization Reference Example 1
Comparative polymerization reference example 1 in place of the block copolymer obtained in
Except for using the block copolymer obtained in the above-mentioned,
A hydrogenated block copolymer was obtained in the same manner as in Hydrogenated Reference Example-1>.

Table 1 shows the structure and analysis results of the obtained block copolymer.

[0090]

[Table 1]

The physical properties of the compositions used in the examples were measured as follows.

-Preparation of the compound- Extrusion conditions: 220 ° C., 2 mm with a 30 mm twin screw extruder
The composition was adjusted at 50 rpm and a discharge pressure of 0.7 MPa.

[0093] The injection molded test piece was manufactured by using an injection molding machine FE-120 manufactured by Nissei Plastics Industrial Co., Ltd., with a rotation speed of 70 rpm, an injection speed of 50%, an injection pressure of 50%, an injection time of 7 seconds, and a cooling time of 30.
It was prepared at a molding temperature of 200 ° C. for seconds.

The polypropylene (PP) used was manufactured by Nippon Polyolefin Co., Ltd. under the trade name Joy Allomer FG46.
4 (random PP, cast film molding), MD
772H (random PP), M-8649 (block PP, for injection molding), M-7646 (block PP,
(For injection molding).

-Measurement of physical properties of blend-Measurement was performed using a hardness durometer D according to JIS K7215 or according to JIS K6253-93.

Bending elastic modulus 3.2 mm thick × 12.7 m prepared by injection molding machine
A test piece of m width × 127 mm was measured according to ASTM D790-9.

A business card prepared by an impact whitening injection molding machine (about 90 mm × 50 m
mx 2 mm thick) on a DuPont impact tester (temperature 23 ° C) with a 1/4 "radius of impacting core, 1 kg load and 50 height.
cm, and the impact whitening property of the sheet was evaluated by the following equation as a difference in transmittance before and after impact.

ΔT% = molded product T% −impact deformation portion T% Whitening limit that can be visually confirmed ΔT% = 4.5%, and a lower value indicates a lower degree of whitening.

Total light transmittance The sheet having a thickness of 2 mm was measured according to JIS K7105-81.

[0100] The haze above 2mm of thickness sheet was measured in accordance with JIS K7105-81.

Izod Impact Strength The notched Izod impact strength is −30 ° C. when measured at −30 ° C.
The measurement was performed after allowing the sample to stand in Drameta controlled at 30 ° C. for 5 minutes.

Tensile test According to JIS K6251-93, a tensile speed of 200
It was measured in mm / min.

At this time, the elongation (%) at the start of whitening was visually confirmed.

<Examples 1-4 and Comparative Examples 1-4>
Each composition was prepared at a blending weight composition ratio shown in Table 2 using random PP (trade name: Joy Allomer FG464) manufactured by Japan Polyolefin Co., Ltd. as polypropylene. Examples 1 to 4 show that the thermoplastic resin compositions containing the block copolymer of the present invention are excellent in transparency and greatly improved in impact whitening. Further, even in comparison with the same level of hardness and flexural modulus in Comparative Examples 1 to 3, the results show that the impact whitening property is significantly improved.

[0105]

[Table 2]

<Examples -5 to 7 and Comparative example -5> Block PP (trade name: Joy Allomer M-8649) manufactured by Nippon Polyolefin Co., Ltd. was used as the polypropylene, and the blending weight ratio shown in Table 3 was used. Each composition was prepared. Examples 5 to 7 show that the thermoplastic resin composition containing the block copolymer of the present invention is sufficiently softened. It also shows that the higher the content of the (B2) block in the block copolymer or the longer the (B2) block chain length, the more softened the composition can be obtained. In particular, as shown in Example 7, when the block copolymer of Polymerization Reference Example 6 was used, it was found that a composition having a good balance between the PP softening effect and the improvement in impact strength was obtained.

[0107]

[Table 3]

<Examples 8 to 9 and Comparative Examples 6 to 9>
Each composition was prepared at a blending weight composition ratio shown in Table 4 using random PP (trade name: Joy Allomer MD772H) manufactured by Japan Polyolefin Co., Ltd. as polypropylene. A sheet (90 × 120 × 2 mm) was prepared with an injection molding machine and punched out with a No. 3 dumbbell to obtain a sample piece. Examples 8 and 9 show that the composition containing the block copolymer of the present invention has excellent whitening onset elongation during stretching.

[0109]

[Table 4]

[0110]

As described above, the thermoplastic resin composition containing the specific block copolymer of the present invention has a high impact resistance, transparency, flexibility, impact whitening resistance, bending whitening resistance and the like. Excellent physical property balance.

Claims (6)

[Claims] 1. Two or more styrene blocks (S) comprising 99 to 1% by weight of one or more kinds of thermoplastic resins, (1) 90 mol% or more of a styrene monomer component, and (2) constituted The monomer component is mainly composed of a 1-butene (a) component and an ethylene (b) component, and the component ratio of each component is (a) 2%.
0 to 45 mol%, the component (b) is 80 to 55 mol%,
(A) + (b) at least one ethylene-1-butene random block (B1) satisfying ≧ 90 mol%, (3) (2)
And the constituent ratio of each component is (a)
Ethylene-1 having 45 to 100 mol% of the component, 55 to 0 mol% of the component (b), and (a) + (b) ≧ 90 mol%.
-One or more butene random blocks (B2), comprising (B1) blocks and / or (B2) blocks between two or more (S) blocks and having a molecular weight of 2
0.00-1,000,000, molecular weight distribution Mw / M
A thermoplastic resin composition comprising 1 to 99% by weight of a block copolymer in which n is 1 to 5. 2. The block copolymer has a total content of the block (S) of 5 to 80% by weight, a total content of the block (B1) of 10 to 70% by weight, and a total content of the block (B2) in the block copolymer. 10 to 70% by weight (however, (S) + (B1) +
The thermoplastic resin composition according to claim 1, wherein (B2) = 100% by weight). 3. The block copolymer has a total content of the block (S) of 5 to 50% by weight, a total content of the block (B1) of 25 to 60% by weight, and a total content of the block (B2) in the block copolymer. 25 to 60% by weight (however, (S) + (B1) +
The thermoplastic resin composition according to claim 1, wherein (B2) = 100% by weight). 4. The method according to claim 1, wherein the block copolymer is (S)-(B1)-
The thermoplastic resin composition according to any one of claims 1 to 3, having a structure of (S)-(B2). 5. The thermoplastic resin composition according to claim 1, wherein one of the thermoplastic resins is a polypropylene resin. 6. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is a polypropylene resin, a polystyrene resin and / or a polyphenylene ether resin.