JP3296921B2 - Hydrogenated block copolymer, and thermoplastic resin composition containing the hydrogenated block copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogenated block copolymer from which a molded article having excellent vibration damping performance can be obtained, and a thermoplastic resin composition containing the hydrogenated block copolymer.

[0002]

2. Description of the Related Art In recent years, noise and vibration have become major social problems due to the development of transportation. Also, in the field of precision machinery and electronics, the adverse effect of vibration has become a problem. As a result, there has been an increasing demand for molded articles having excellent characteristics of vibration damping and vibration damping performance.

Conventionally, metal springs, air springs, corks, felts, vibration-proof rubbers, and the like have been used as vibration-proof materials or vibration-damping materials. Since it has characteristics such as low vibration transmission force in the region and low cost, it is used in a wide range of fields.

As the vibration-proof rubber, diene rubber such as neoprene, styrene-butadiene copolymer (SBR), butyl rubber and the like are used.
Although the damping performance is insufficient, and butyl rubber is relatively excellent in the anti-vibration and damping properties, it is insufficient in strength, and neither can be satisfied.

[0005] Further, these rubbers must be compounded with various additives, vulcanizing agents and the like in order to exhibit strength.
There is a drawback that a vulcanization reaction needs to be performed, which requires a great deal of time and labor.

As a solution to this problem, a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising a vinyl aromatic monomer and a diene monomer having a specific structure is known.

However, conventional thermoplastic resin compositions containing a hydrogenated block copolymer have a problem in terms of moldability. For example, when injection molding is performed, there is a problem that the releasability from a metal mold is poor, and when performing sheet molding with a roll, adhesion to a roll occurs.

Further, when a molded article made of the thermoplastic resin composition containing the hydrogenated block copolymer is overlaid, the upper and lower molded articles may adhere to each other. The problem of sticking between molded products can be solved by using a lubricant, a release agent, or the like.However, a molded product using a lubricant or a release agent has a lubricant or a release agent on the surface of the molded product. This causes a problem that the mold agent bleeds out.

[0009]

According to the present invention, there can be obtained a molded article having good molding performance, excellent vibration proof and vibration damping properties, and which does not require a lubricant or a release agent. It is an object to provide a hydrogenated block copolymer and a thermoplastic resin composition containing the hydrogenated block copolymer.

[0010]

According to the present invention, the above-mentioned objects are attained in that the number of 1,2 bonds is 30% or less and the number average molecular weight is 25%.
A block (A) composed of a polybutadiene having a number of 100 to 100,000, a block (B) composed of a polyvinyl aromatic compound having a number average molecular weight of 2500 to 50,000, a vinyl bond content of 30% or more, and a number average molecular weight of 10,000 to 2;
And a block (C) composed of polyisoprene, polybutadiene or polyisoprene-butadiene having a number average molecular weight of 20,000 to 300,000
The problem can be solved by a hydrogenated block copolymer obtained by hydrogenating the (A)-(B)-(C)-(B) type block copolymer.

Further, according to the present invention, the above-mentioned object is to provide a compound having a 1,2 bond content of 30% or less and a number average molecular weight of 2,500 to 100
A block composed of a polybutadiene having a number average molecular weight of 2,500 to 50,000, a block composed of a polyvinyl aromatic compound having a number average molecular weight of 2500 to 50,000, and a block having a vinyl bond amount of 30
% Or more and a block (C) composed of polyisoprene, polybutadiene or polyisoprene-butadiene having a number average molecular weight of 10,000 to 200,000 and a number average molecular weight of 20,000 to 300,000 (A)-
The problem can be solved by a thermoplastic resin composition containing a hydrogenated block copolymer obtained by hydrogenating a (B)-(C)-(B) type block copolymer as one of the constituent components. .

Hereinafter, the hydrogenated block copolymer of the present invention and the thermoplastic resin composition containing the hydrogenated block copolymer will be described in more detail.

The block (A) in the (A)-(B)-(C)-(B) type block copolymer is a polybutadiene having 1,2 bonds of 30% or less. If the amount of the 1,2 bond of the polybutadiene constituting the block (A) exceeds 30%, the effect of improving the mold releasability at the time of molding and the sticking between molded products cannot be obtained.

The number average molecular weight of the block (A) is 2500
If it is less than the above, the mold releasability at the time of molding and the effect of improving the sticking between the molded articles cannot be obtained, and if it exceeds 100000, the (A)-(B)-(C)-(B) mold block When the hydrogenation reaction solution at the time of the hydrogenation reaction of the copolymer is waxed, its handling becomes difficult. From these, the number average molecular weight of the block (A) is 2,500 to 2,500.
It must be in the range of 100,000.

When the proportion of the block (A) in the (A)-(B)-(C)-(B) type block copolymer is less than 5%, the mold releasability at the time of molding and the moldings are not so large. Cannot be obtained, and if it exceeds 80%, it is impossible to obtain a molded article having sufficient vibration damping performance. For this reason,
The block (A) in the (A)-(B)-(C)-(B) type block copolymer is preferably in the range of 5 to 80%.

The block (B) in the (A)-(B)-(C)-(B) type block copolymer is a block composed of a polyvinyl aromatic compound.
-Vinylnaphthalene, 2-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-
It consists of a polymer of a vinyl aromatic compound capable of anion polymerization such as benzylstyrene and 4- (phenylbutyl) styrene, and is most preferably polystyrene.

The number average molecular weight of the block (B) is 2500
If less than, the strength of the obtained molded body becomes insufficient,
On the other hand, when it exceeds 50,000, the melt viscosity of the hydrogenated block copolymer becomes high and the processability deteriorates. From these, the number average molecular weight of the block (B) is 2500 to 500
It must be in the range of 00.

When the proportion of the block (B) in the (A)-(B)-(C)-(B) type block copolymer is less than 5%, the strength of the molded article becomes insufficient and the strength of the molded article becomes 80%. If it exceeds, a molded article having sufficient vibration damping performance cannot be obtained. For this reason, the block (B) in the (A)-(B)-(C)-(B) type block copolymer is preferably in the range of 5 to 80%.

The block (C) in the (A)-(B)-(C)-(B) type block copolymer is polyisoprene, polybutadiene or polyisoprene-butadiene. Two bonds and 3,
30% of total amount with 4 bonds (hereinafter referred to as vinyl bond amount)
If it is less than 30, a molded article having sufficient vibration damping performance near room temperature will not be obtained.

Therefore, the block (C) is made of polyisoprene, polybutadiene or polyisoprene-butadiene having a vinyl bond content of 30% or more.

When the block (C) is made of polyisoprene-butadiene obtained by using isoprene and butadiene, the block (C) has any of random and tapered structures of isoprene and butadiene.
May be I, their ratio of isoprene and butadiene emissions is arbitrary.

The number average molecular weight of the block (C) is 1000
If it is less than 0, the vibration damping performance of the molded body becomes insufficient,
On the other hand, if it exceeds 200,000, the melt viscosity of the hydrogenated block copolymer increases, and the processability decreases. From these, the number average molecular weight of the block (C) is 10,000 to 2
It must be in the range of 00000.

When the proportion of the block (C) in the (A)-(B)-(C)-(B) type block copolymer is less than 10%, the vibration-damping performance of the molded product becomes insufficient. 90
%, The strength of the molded body becomes insufficient. For this reason, the block (C) in the (A)-(B)-(C)-(B) type block copolymer is preferably in the range of 10 to 90%.

Further, when the number average molecular weight of the (A)-(B)-(C)-(B) type block copolymer is less than 20,000, the strength of the block copolymer itself is reduced, and when the composition is formed into a composition. However, sufficient strength cannot be obtained. 3
If it exceeds 00000, the melt viscosity of the block copolymer becomes too high and the processability of the composition decreases, which is not preferable. From these, (A)-(B)-(C)-
The number average molecular weight of the (B) type block copolymer is 2000
It must be in the range of 0 to 300,000.

When the hydrogenation rate of the hydrogenated block copolymer obtained by hydrogenating the (A)-(B)-(C)-(B) type block copolymer is less than 70%, the block ( Since the polybutadiene according to A) does not have crystallinity, the mold releasability at the time of molding and a sufficient improvement effect on sticking between molded products cannot be obtained, and the heat resistance and weather resistance are also insufficient. Become. From these, (A)-(B)-(C)-
The hydrogenation rate of the hydrogenated block copolymer obtained by hydrogenating the (B) type block copolymer is preferably 70% or more, and more preferably 80% or more.

The (A)-(B)-(C)-(B) type block copolymer uses an alkyllithium compound as a polymerization initiator and comprises butadiene, isoprene, butadiene-isoprene, a vinyl aromatic compound and the like. And by sequentially polymerizing the target copolymer in the order of the blocks.

The alkyl lithium compound is, for example, an alkyl compound having 1 to 10 carbon atoms in the alkyl residue, and particularly preferably methyl lithium, ethyl lithium, pentyl lithium and butyl lithium.

The amount of the alkyl lithium compound used is
It is determined by the molecular weight of the (A)-(B)-(C)-(B) type block copolymer.
It is generally used in the range of 0.01 to 0.2 parts by weight with respect to 00 parts by weight.

The block (C) polyisoprene,
In order to increase the vinyl bond content of polybutadiene or polyisoprene-butadiene to 30% or more, it is preferable to use a Lewis base as a co-catalyst at the time of polymerization.

Examples of Lewis bases include ethers such as dimethyl ether, diethyl ether, methyl ethyl ether and tetrahydrofuran, and glycol ethers such as ethylene glycol diethyl ether and ethylene glycol dimethyl ether. And tertiary amines such as N, N, N, N-tetramethylethylenediamine and triethylenediamine, and ether-containing amines such as N-methylmorpholine and N-ethylmorpholine.

The Lewis base is used in an amount of about 0.1 to 10,000 based on 1 mol of the alkyllithium compound as the polymerization initiator.
Used in the molar range.

At the time of the polymerization reaction, it is preferable to use a solvent in order to facilitate the control of the reaction, and an organic solvent inert to the polymerization initiator is used. In particular, hydrocarbons having 6 to 12 carbon atoms, for example, aliphatic hydrocarbons such as hexane, heptane, octane, and decane, and corresponding alicyclic hydrocarbons, and aromatic hydrocarbons such as toluene, benzene, and xylene Hydrogen or the like is used.

The polymerization reaction is carried out at -20 to 80 ° C. for about 0.5 to 50 hours in any of the polymerization methods.

The hydrogenation reaction of the (A)-(B)-(C)-(B) type block copolymer is carried out by a known method. That is, the hydrogenation catalyst and the solvent inert to the reaction,
It is preferable to use a method of dissolving the (A)-(B)-(C)-(B) type block copolymer and reacting hydrogen in a molecular state with a known hydrogenation catalyst.

As the hydrogenation catalyst, Raney nickel, a heterogeneous catalyst such as a metal such as Pt, Pd, Ru, Rh and Ni supported on a carrier such as carbon, alumina and diatomaceous earth, or a transition metal A Ziegler-based catalyst comprising a combination of an alkylaluminum compound and the like is used.

The hydrogenation reaction is carried out at a hydrogen pressure of normal pressure to 200 kg / cm ² , a reaction temperature of normal temperature to 250 ° C., and a reaction time of 0.1 to 100 hours.

The hydrogenated block copolymer after the hydrogenation reaction is coagulated by pouring the reaction solution into methanol or the like and then heating or drying under reduced pressure, or by pouring the reaction solution into boiling water and removing the solvent by azeotropic distillation. After that, it is obtained by heating or drying under reduced pressure.

The hydrogenated block copolymer of the present invention can be used alone as a raw material for forming a molded article, but can be used by blending with another polymer to the extent that the purpose of the present invention is not impaired. is there.

Other polymers that can be blended include N
Liquid rubber such as R, IR, BR, SBR, EPR, EPDM, butyl rubber, solid rubber such as 1,2-polybutadiene, polybutene, low molecular weight isoprene, butadiene rubber, isoprene-butadiene copolymer and hydrogenated product thereof Styrene-based thermoplastic elastomers such as styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-isobutylene block copolymer and hydrogenated products thereof, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate Copolymers, ethylene-based copolymers such as ethylene-methyl methacrylate copolymer, thermoplastic polyurethane elastomer, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, polyethylene, polyolefin such as polypropylene, polystyrene, S resins, ABS resins, styrene resins such as AES resin, polyamide resin, polyester resin, and the like.

Further, in the molecular chain of the above-mentioned polymer and / or
Alternatively, it is also possible to blend those having a functional group such as a carboxyl group, an epoxy group, or a hydroxyl group added to the molecular terminal.

The blending ratio of the other polymer varies depending on the purpose, but when the total of the hydrogenated block copolymer and the other polymer is 100 parts by weight, the other polymer is approximately 9 parts by weight.
5 parts by weight or less.

Further, (A)-(B)-(C)-(B)
The hydrogenated block copolymer obtained by hydrogenating the mold block copolymer, or the thermoplastic resin composition containing the hydrogenated block copolymer, various additions within a range that does not impair the object of the present invention An agent can be contained.

For example, (A)-(B)-(C)-(B)
5 to 250 parts by weight of an oil or the like based on 100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a mold block copolymer or a thermoplastic resin composition containing the hydrogenated block copolymer. Agent / softener, 5 to 300 parts by weight of car
Reinforcing agents or fillers such as Bon Black, silica, calcium carbonate, talc, mica, glass fiber, and 0.0
1 to 5 parts by weight of an antioxidant, an ultraviolet absorber, a coloring agent and the like can be added. In particular, the addition of mica is preferable from the viewpoint of improving the vibration damping performance of the obtained molded body.

(A)-(B)-(C)-(B) of the present invention
A hydrogenated block copolymer obtained by hydrogenating a mold block copolymer, or a thermoplastic resin composition containing the hydrogenated block copolymer is mixed by a kneader, a roll, an extruder, press-molded, and injected. It is molded into a molded body by a general molding method such as molding or extrusion molding.

(A)-(B)-(C)-(B) of the present invention
A hydrogenated block copolymer obtained by hydrogenating a mold block copolymer, or a thermoplastic resin composition containing the hydrogenated block copolymer, is used after crosslinking with a crosslinking agent such as sulfur or peroxide. Can also.

Crosslinking can be easily carried out using a general method and apparatus used for ordinary rubber crosslinking.

(A)-(B)-(C)-(B) of the present invention
Hydrogenated block copolymer obtained by hydrogenating a mold block copolymer, or a thermoplastic resin composition containing the hydrogenated block copolymer, for example, automobiles, railway vehicles, ships,
As a vibration damping material for aircraft, home appliances, OA equipment, flooring materials, wall materials, etc., or for automobile interior materials, exterior materials, sheets, films, hoses, tubes, medical materials, sporting goods, toys, household goods, textiles, Molded into shoes and the like.

In the present invention, (A)-(B)-(C)-
(B) A hydrogenated block copolymer obtained by hydrogenating a type block copolymer, or a thermoplastic resin composition containing the hydrogenated block copolymer is applied to a cloth or a thermoplastic resin plate. , A thermosetting resin plate, a steel plate, rubber, an elastomer or the like.

[0049]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples. In addition, each measured value in an Example and a comparative example was calculated | required by the following method. Molecular weight: determined by GPC. Vinyl bond content: determined by NMR spectrum. Hydrogenation rate: The iodine value of each block copolymer before and after the hydrogenation reaction was measured, and calculated by the ratio. Vibration suppression performance: 0, 20, determined by dynamic viscoelasticity measurement
It was evaluated by the tan δ value at 40 ° C.

Examples 1 and 2 In a 5-liter stirred autoclave purified with dry nitrogen, cyclohexane was used as a solvent, n-butyllithium was used as a polymerization initiator, and tetrahydrofuran was used as a vinylating agent. , Butadiene, styrene monomer, isoprene, and styrene monomer are polymerized in this order;
(B)-(C)-(B) type block copolymer was obtained.

Next, the obtained block copolymer was subjected to a hydrogenation reaction in cyclohexane using Pd—C as a hydrogenation catalyst at a hydrogen pressure of 20 kg / cm ² to obtain a hydrogenated block copolymer (a). And (b) were obtained. Table 1 shows these molecular properties.
Shown in

As an evaluation of the vibration damping performance of the hydrogenated block copolymer, tan δ was measured at 0, 20, and 40 ° C.

As an evaluation of the adhesiveness, a hydrogenated block was used.
3 mm thick, 10 c long, obtained by pressing the copolymer
m, two 10cm wide sheets are superimposed and 50g / cm
^After applying a load of ² and leaving the sheet at 25 ° C. for 24 hours, the sheet was easily peeled off, and the surface of the sheet after peeling was observed. Table 2 shows the evaluation results.

Comparative Examples 1 and 2 A polymerization reaction and a hydrogenation reaction were carried out in the same manner as in Example 1 except that butadiene was not used, and a hydrogenated block copolymer ( c) and (C) for comparison were used. d) was obtained. Table 1 shows their molecular characteristics.

Further, in the same manner as in Example 1, tan δ and adhesiveness of each of the hydrogenated block copolymers (c) and (d) were evaluated. Table 2 shows the evaluation results.

[0056]

[Table 1]

[0057]

[Table 2] Ease of peeling: ○ ·············································· Unchangeable Surface condition: ○ ······· No change, × ··· ..With change

Examples 3 to 4 The hydrogenated block copolymers (a) and (b) obtained in Examples 1 and 2 were used and consisted of the components shown in Table 3 (parts by weight). The composition was kneaded at 200 ° C. with a Brabender plastic coder and 3 m thick by press molding.
m, a sheet having a length of 10 cm and a width of 10 cm were prepared, and the adhesion was evaluated in the same manner as in Example 1. Also,
The measurement of tan δ at 0, 20, and 40 ° C. was performed. Table 3 shows the evaluation results of the adhesiveness and the measurement results of tan δ.

Comparative Examples 3 to 4 The hydrogenated block copolymers (c) and (d) obtained in Comparative Examples 1 and 2 were used and consisted of the components shown in Table 3 (parts by weight). The composition was kneaded and molded in the same manner as in Example 3, and the adhesiveness was evaluated in the same manner as in Example 1. Further, tan δ was measured at 0, 20, and 40 ° C. Table 3 shows the evaluation results of the adhesiveness and the measurement results of tan δ.
Shown in

[0060]

[Table 3] (* 1) ··· Mitsubishi Polypro MA3 (Mitsubishi Yuka Co., Ltd.) Ease of peeling: ○ · · · Easy peeling · · · · Can be peeled off using methanol as a mold release agent × · · ·・ ・ Surface condition which cannot be removed: ○ ・ ・ ・ ・ ・ ・ No change, × ・ ・ ・ ・ ・ ・ Change

Examples 5 to 6 The hydrogenated block copolymers (a) and (b) obtained in Examples 1 and 2 were used and consisted of the components shown in Table 4 (parts by weight). The composition was kneaded at 200 ° C. with a Brabender plastic coder and 3 m thick by press molding.
m, a sheet having a length of 10 cm and a width of 10 cm were prepared, and the adhesion was evaluated in the same manner as in Example 1.

Further, tan δ was measured at 0, 20, and 40 ° C. Table 4 shows the evaluation results of the adhesiveness and the measurement results of tan δ.

Comparative Examples 5 and 6 The hydrogenated block copolymers (c) and (d) obtained in Comparative Examples 1 and 2 were used and consisted of the components shown in Table 4 (parts by weight). The composition was kneaded and molded in the same manner as in Example 3, and the adhesiveness was evaluated in the same manner as in Example 1.

Further, tan δ was measured at 0, 20, and 40 ° C. Table 4 shows the evaluation results of the adhesiveness and the measurement results of tan δ.

[0065]

[Table 4] (* 1) ··· Mitsubishi Polypropylene MA3 (Mitsubishi Yuka Co., Ltd.) (* 2) ··· Hydrogenated styrene-isoprene block copolymer (Septon 4055: Kuraray Co., Ltd.) (* 3)・ ・ ・ Diana Process Oil PW-380 (Idemitsu Kosan Co., Ltd.) Ease of peeling: ○ ・ ・ ・ ・ Easily peelable △ ・ ・ ・ ・ Peelable when methanol is used as a mold release agent × ・ ・ ・ ・ Peel off No surface condition: ○ ・ ・ ・ ・ ・ ・ No change, × ・ ・ ・ ・ ・ ・ Change

From the results shown in Tables 2 to 4, the molded article made of the hydrogenated block copolymer of the present invention and the thermoplastic resin composition containing the hydrogenated block copolymer have excellent vibration damping performance. In addition, it can be seen that it has no sticking property.

[0067]

The hydrogenated block copolymer of the present invention and the thermoplastic resin composition containing the hydrogenated block copolymer have good mold releasability during molding using these as a molding material. In addition, the molded article has excellent vibration damping performance, has no sticking property, and has an excellent effect in practical use.

Continuation of the front page (56) References JP-A-4-255708 (JP, A) JP-A-3-188114 (JP, A) JP-A-3-146511 (JP, A) JP-A-2-133407 (JP) JP-A-2-133406 (JP, A) JP-A-61-155446 (JP, A) JP-A-61-34050 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C08F 8/00-8/50

Claims (2)

(57) [Claims] 1. A block (A) comprising a polybutadiene having a 1,2 bond amount of 30% or less and a number average molecular weight of 2,500 to 100,000, and a number average molecular weight of 2,500 to 500.
Block (B) comprising a polyvinyl aromatic compound of No. 00
And a vinyl bond content of 30% or more and a number average molecular weight of 10
And a block (C) composed of polyisoprene, polybutadiene or polyisoprene-butadiene having a number average molecular weight of 2,000 to 3,000.
A hydrogenated block copolymer obtained by hydrogenating the 00000 (A)-(B)-(C)-(B) type block copolymer. 2. A thermoplastic resin composition comprising the hydrogenated block copolymer according to claim 1 as one of the constituent components.