JP3357172B2 - Resin composition containing 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 resin having excellent properties such as solvent resistance and impact resistance, and, in addition to these properties, having flexibility and excellent transparency. The present invention relates to a resin composition capable of obtaining a molded article suitable for exterior parts, various industrial parts, and the like.

[0002]

2. Description of the Related Art A resin composition obtained by blending an EPR or styrene-based elastomer with a polypropylene resin is molded into a molded article having excellent properties such as mechanical strength, economy, and recyclability. Is used as a raw material for forming a molded article.

[0003]

However, a molded article made of a resin composition obtained by blending EPR or a styrene-based elastomer with a polypropylene resin has problems in terms of transparency and solvent resistance. It has been difficult to use as a raw material for forming films, medical materials, etc., or automotive exterior parts requiring solvent resistance.

On the other hand, the present invention relates to hydrogenated butadiene
By having a resin composition in which a vinyl isoprene block copolymer and a polypropylene resin, or a polyethylene resin is further mixed with the resin, it has excellent properties such as solvent resistance and impact resistance, or in addition to these properties,
It is an object of the present invention to provide a resin composition which is a raw material for molding a molded article having flexibility and excellent transparency.

[0005]

According to the present invention, the above object is achieved by (1) a polypropylene resin: 100 parts by weight ,
(2) The number average molecular weight is 2,500 to 100,000,
And hydrogenated poly-butadiene block A 2 bond content of 20% or less, hydrogenated polyisoprene or hydrogenated polyisoprene
Block B comprising butadiene, having a number average molecular weight of 10,000 to 200,000, 3,4 bonds and 1,2
5 to 1900 parts by weight of a hydrogenated block copolymer having a block B having a total amount of bonding of 30 to 60%
And (3) is achieved by providing a tree fat composition you characterized by comprising the polyethylene resin .... 0-1800 parts by weight.

[0006] The resin composition containing the hydrogenated block copolymer of the present invention is a raw material for forming a molded article having properties excellent in solvent resistance and impact resistance.

The resin composition containing the hydrogenated block copolymer of the present invention has properties excellent in solvent resistance and impact resistance by using a composition component containing a large amount of the hydrogenated block copolymer. In addition, it becomes a raw material for forming a molded body that is flexible and excellent in transparency.

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

In the resin composition containing the hydrogenated block copolymer of the present invention, there is no particular limitation on the polypropylene resin used as the component (1). It is preferable to use block polypropylene, and to obtain a molded article that emphasizes impact resistance, it is preferable to use block polypropylene.To obtain a molded article that emphasizes transparency, use random polypropylene. preferable. These polypropylenes may be used in combination as the polypropylene resin. Furthermore, polypropylene modified with an unsaturated carboxylic acid derivative or an anhydride thereof, or modified polypropylene having a functional group such as a hydroxyl group, a carboxyl group, or an epoxy group introduced at a molecular terminal may be used.

In the resin composition containing the hydrogenated block copolymer of the present invention, the block A of the hydrogenated block copolymer used as the component (2) is hydrogenated polybutadiene, and the 1,2 bond content is 20%. These are: If the amount of 1,2 bonds in the block A is more than 20%, a molded product having sufficient strength cannot be obtained.

The number average molecular weight of this block A is 25.
It needs to be in the range of 100 to 100,000. When the number average molecular weight of the block A is smaller than 2500, the mechanical performance of the obtained molded article is reduced, and
If it exceeds 0000, the melt viscosity becomes too high.
Mixing with other components in the composition cannot be performed uniformly.

Further, the block A needs to be hydrogenated, and the hydrogenation ratio is preferably 70% or more, more preferably 80% or more. When the hydrogenation ratio of the block A is lower than 70%, crystallinity cannot be obtained, the strength of the hydrogenated block copolymer becomes insufficient, and a molded article having high strength cannot be obtained.

The proportion of the block A in the hydrogenated block copolymer is preferably in the range of 5 to 95% by weight.
When the proportion of block A in the hydrogenated block copolymer is 5
If the amount is less than 10% by weight, the mechanical strength of the hydrogenated block copolymer becomes insufficient, and a molded article having sufficient mechanical strength cannot be obtained. If the amount exceeds 95% by weight, sufficient impact resistance is obtained. Cannot be obtained.

In the resin composition containing the hydrogenated block copolymer of the present invention, the block B of the hydrogenated block copolymer used as the component (2) is hydrogenated polyisoprene or hydrogenated polyisoprene-butadiene. . Content of 3,4 bond and 1,2 bond in block B (hereinafter, referred to as
These are sometimes collectively called vinyl bond content)
Should be in the range of 30-60%. If the vinyl bond content in the block B exceeds the above range, a molded article having sufficient impact resistance cannot be obtained.

The number average molecular weight of this block B is 1000
It must be in the range of 0 to 200,000. When the number average molecular weight of the block B is less than 10,000, a molded article having sufficient impact resistance cannot be obtained.
If it exceeds 000, the melt viscosity of the hydrogenated block copolymer becomes too high, so that mixing with other components in the composition cannot be performed uniformly.

Further, it is necessary that the block B is hydrogenated, and from the viewpoint of heat resistance and weather resistance of the obtained molded article, the hydrogenation ratio is preferably 70% or more, and 80% or more. % Is more preferable.

The proportion of the block B in the hydrogenated block copolymer is preferably in the range of 5 to 95% by weight. If the proportion of the block B in the block copolymer is less than 5% by weight, a molded article having sufficient impact resistance cannot be obtained. If the proportion is more than 95% by weight, the hydrogenated block copolymer is not obtained. Has insufficient mechanical strength, and a molded body having high mechanical strength cannot be obtained.

In the resin composition containing the hydrogenated block copolymer of the present invention, the hydrogenated block copolymer used as the component (2) has a number average molecular weight of 20,000 to 3,000.
It is preferably in the range of 00. When the number average molecular weight of this hydrogenated block copolymer is smaller than 20,000, the mechanical strength such as the breaking strength and elongation of the block copolymer itself decreases, and the breaking copolymer has excellent mechanical properties such as elongation. A molded article having properties cannot be obtained. On the other hand, when the number average molecular weight of the hydrogenated block copolymer exceeds 300,000, the processability deteriorates, and the mixing with other components of the composition is not uniform. From these viewpoints, the number average molecular weight of the block copolymer is more preferably in the range of 30,000 to 250,000.

In the resin composition containing the hydrogenated block copolymer of the present invention, the hydrogenated block copolymer used as the component (2) is modified with an unsaturated carboxylic acid derivative or an anhydride thereof. A hydrogenated block copolymer may be used.

The hydrogenated block copolymer used as the component (2) is obtained, for example, by the method described below.

First, the block copolymer is produced by a method in which an alkyllithium compound is used as a polymerization initiator and monomers are sequentially added to carry out polymerization.

Examples of the alkyl lithium compound include an alkyl compound having an alkyl residue having 1 to 10 carbon atoms, and methyl lithium, ethyl lithium, pentyl lithium and butyl lithium are particularly preferred. Examples of the dilithium compound include naphthalenedilithium and dilithiohexylbenzene. The amount of the polymerization initiator to be used is determined by the molecular weight of the block copolymer to be determined, and is generally 0.01 to 0.2 parts by weight based on 100 parts by weight of all monomers used for polymerization. As coupling agents, dichloromethane, dibromomethane, dichloroethane,
Dibromoethane, dibromobenzene and the like are used.

In order for the isoprene portion of the block B to have a microstructure having a vinyl bond content of 30 to 60%, a Lewis base is used as a cocatalyst in the polymerization of isoprene. Examples of Lewis bases include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran; glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; triethylamine; N, N, N ', N'-tetramethylethylenediamine (TMEDA); Examples include amine compounds such as methylmorpholine. These Lewis bases are used in an amount of about 0.1 to 1000 times the mole number of the lithium compound as the polymerization initiator.

In the polymerization, it is preferable to use a solvent in order to facilitate the control of the reaction. As the solvent, an organic solvent inert to the polymerization initiator is used. Particularly, an aliphatic hydrocarbon, an alicyclic hydrocarbon, and an aromatic hydrocarbon having 6 to 12 carbon atoms are preferable. Specific examples include hexane,
Heptane, cyclohexane, methylcyclohexane, benzene and the like can be mentioned.

The polymerization is carried out by using any polymerization method.
８０80 ° C. for about 0.5-50 hours.

The block copolymer is hydrogenated by a known method. The block copolymer and the hydrogenation catalyst are dissolved in a solvent inert to the reaction, and the hydrogenation in a molecular state is reacted with the known hydrogenation catalyst. The method is preferred. As a catalyst to be used, Raney nickel or Pt, Pd, Ru, R
h, a heterogeneous catalyst such as one in which a metal such as Ni is supported on a carrier such as carbon, alumina, or diatomaceous earth; or a Ziegler-based catalyst comprising a combination of a transition metal and an alkylaluminum compound or an alkyllithium compound. Used. The 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 0.1 to 10
Performed with a reaction time of 0 hours.

The block copolymer after the hydrogenation reaction is heated or dried under reduced pressure after coagulating the reaction solution with methanol or the like, or by pouring the reaction solution into boiling water and removing the solvent by azeotropic distillation, followed by heating. Alternatively, it is obtained by drying under reduced pressure.

Component (3) optionally used in the resin composition containing the hydrogenated block copolymer of the present invention.
The polyethylene is not particularly limited, but high density polyethylene, low density polyethylene, linear low density polyethylene and the like are preferable. Further, a polyethylene modified with an unsaturated carboxylic acid derivative or an anhydride thereof, a modified polyethylene having a functional group such as a hydroxyl group, a carboxyl group or an epoxy group introduced at a molecular terminal, or the like may be used.

The resin composition containing the hydrogenated block copolymer of the present invention may contain various additives as long as the properties are not impaired. For example, based on 100 parts by weight of the resin composition of the present invention containing a hydrogenated block copolymer, 5 to 250 parts by weight of carbon black, silica, calcium carbonate, talc, mica,
0.01 to 5 such as reinforcing material or filler such as glass fiber
Parts by weight of an antioxidant, an ultraviolet absorber, a coloring agent, and the like. In particular, by using a composition containing mica,
A molded article having excellent vibration damping properties can be obtained.

Further, other polymers can be blended with the resin composition containing the hydrogenated block copolymer of the present invention as long as the gist of the present invention is not impaired.

As the polymer to be blended, for example,
Styrene-butadiene block copolymer and its hydrogenated product,
Styrene-isoprene block copolymer and its hydrogenated product,
EPR, an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, and the like. The blending ratio of these polymers is preferably about 50% or less with respect to the resin composition containing the hydrogenated block copolymer of the present invention.

The resin composition containing the hydrogenated block copolymer of the present invention can be mixed and molded by a kneader, an extruder, an injection molding machine or the like to form, for example, an interior material, an exterior material, a sheet, a film, a hose, It is formed into tubes, medical materials, sporting goods, toys, household goods, etc.

[0033]

EXAMPLES Hereinafter, the specific constitution of the resin composition containing the hydrogenated block copolymer of the present invention will be described based on examples.

Each measured value was measured according to the following method. Molecular weight: determined by GPC. Vinyl bond amount: calculated from the NMR spectrum. Hydrogenation rate: The iodine value of the block copolymer before and after the hydrogenation reaction was measured and calculated from the ratio. Solvent resistance: Determined by measuring the state of the sheet when a 5 cm × 5 cm × 1 mm (thickness) press-formed sheet was immersed in 300 ml of toluene for 24 hours, and measuring the weight loss of the elastomer component. Transparency: Determined from the light transmittance at 800 nm of a press-formed sheet of 5 cm × 5 cm × 1 mm (thickness). Impact strength: A press-formed sheet of 5 cm × 5 cm × 1 mm (thickness) was determined by measuring with an Izod tester (JIS K7110).

REFERENCE EXAMPLE 1 (Preparation of hydrogenated block copolymer) In a pressure-resistant reactor purged with dry nitrogen, cyclohexane as a solvent, n-butyllithium as a polymerization catalyst, THF as a vinylating agent, butadiene, Isoprene was added in this order and polymerized to obtain two AB block copolymers (I) and (II).

The obtained AB type block copolymer (I)
And (II) were each 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 from AB type block copolymer (I). A hydrogenated block copolymer (ii) was obtained from the copolymer (i) and an AB type block copolymer (II).

The molecular characteristics of each hydrogenated block copolymer (i) and hydrogenated block copolymer (ii) are as shown in Table 1.

[0038]

[Table 1] ¹⁾ : molecular weight before hydrogenation reaction ²⁾ : 1,2 bond amount in polybutadiene ³⁾ : total amount of 3,4 and 1,2 bonds in polyisoprene

Examples 1 to 4 The proportions (parts by weight) of the hydrogenated block copolymer (i) or (ii) obtained in Reference Example 1 and a polypropylene resin or a polyethylene resin are shown in Table 2. ) And kneaded at 200 ° C. with a Brabender plastic coder to produce a composition. Each of the obtained compositions was press-molded at 210 ° C. to obtain a molded article. Transmittance) and impact resistance test (Izod)
Was performed.

The measurement results of the physical properties of the molded articles obtained from the compositions according to Examples 1 to 4 are shown in Table 3 respectively.

[0041]

[Table 2] ¹⁾ : Mitsubishi Yuka Co., Ltd., MA3 (homopolypropylene) ²⁾ : Mitsubishi Yuka Co., Ltd., UF240 (LLDPE)

[0042]

[Table 3] ¹⁾ ： Upper ・ ・ ・ ・ ○ -shape retention, no stickiness, △ －shape retention, stickiness, × -no shape retention Lower: ・ ・ ・ Elastomer component extraction rate (%)

Comparative Examples 1 to 5 A hydrogenated styrene-butadiene block copolymer, an ethylene-propylene rubber, a polypropylene resin and a polyethylene resin were blended in the blending ratio (parts by weight) shown in Table 4 to obtain a Brabender plastic coder. After kneading at 200 ° C. to prepare the compositions, each of the obtained compositions was press-molded at 210 ° C., and the molded articles were subjected to solvent resistance, transparency (light transmittance) and impact resistance test (Izo).
d) was performed.

Table 5 shows the measurement results of the physical properties of the molded articles obtained from the compositions according to Comparative Examples 1 to 5.

[0045]

[Table 4] ¹⁾ : MA3 (Homopolypropylene) manufactured by Mitsubishi Yuka Corporation ²⁾ : UF240 (LLDPE) manufactured by Mitsubishi Yuka Corporation ³⁾ : Esprene (ethylene content) manufactured by Sumitomo Chemical Co., Ltd. ⁴⁾ : Clayton G-1650, a styrene-based elastomer manufactured by Shell Chemical Co., Ltd.

[0046]

[Table 5] ¹⁾ ： Upper ・ ・ ・ ・ ○ -shape retention, no stickiness, △ －shape retention, stickiness, × -no shape retention Lower: ・ ・ ・ Elastomer component extraction rate (%)

[0047]

As is evident from the measurement results of the physical properties of the molded articles of the compositions shown in the examples, according to the resin composition containing the hydrogenated block copolymer of the present invention, the solvent resistance and the resistance to A molded article having excellent impact properties can be obtained.

Further, in the resin composition containing the hydrogenated block copolymer of the present invention, by making the composition component rich in the hydrogenated block copolymer, the resin composition is excellent in solvent resistance and impact resistance, and is transparent. A molded article having excellent properties can be obtained.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (1)

(57) [Claims] (1) Polypropylene resin... 10
0 parts by weight , (2) the number average molecular weight is 2,500 to 100,000,
And hydrogenated poly-butadiene block A 2 bond content of 20% or less, hydrogenated polyisoprene or hydrogenated polyisoprene
Block B comprising butadiene, having a number average molecular weight of 10,000 to 200,000, 3,4 bonds and 1,2
From 5 to 1900 parts by weight of a hydrogenated block copolymer having a block B having a total amount of bonding of 30 to 60% , (3) polyethylene resin ... from 0 to 1800 parts by weight A resin composition characterized by comprising: