JP2600295B2 - Cyclic olefin random copolymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to heat resistance, chemical resistance, solvent resistance, dielectric properties,
The present invention relates to a cyclic olefin-based random copolymer composition having excellent rigidity and impact resistance.

[Conventional technology]

Polycarbonate, ABS (acrylonitrile-butadiene-styrene copolymer) and the like are known as synthetic resins having an excellent balance between rigidity and impact strength. For example, polycarbonate is a resin excellent in heat resistance and impact resistance as well as rigidity. However, there is a problem that it is easily attacked by strong alkali, has poor chemical resistance, and has a high water absorption. In addition, ABS has a problem in that although it has excellent mechanical properties, it has poor chemical resistance and heat resistance.

On the other hand, crystalline general-purpose polyolefins, such as polyethylene and polypropylene, are excellent in chemical resistance and solvent resistance, but are often poor in heat resistance, and are poor in rigidity due to insufficiently high crystallinity. For this reason, in order to improve the rigidity and heat resistance of polyolefin, a method of adding a nucleating agent to accelerate the growth of crystals or performing slow cooling to promote the growth of crystals is generally employed. Is not enough. Rather, the addition of a third component such as a nucleating agent may impair the excellent properties inherent to polyolefins, and the slow cooling method has problems such as poor production efficiency.

In addition, a cyclic olefin-based random copolymer comprising ethylene and a specific noble cyclic olefin has been proposed as a synthetic resin having heat resistance, and also having chemical resistance, solvent resistance, dielectric properties, and rigidity ( JP-A-60-168708, JP-A-61-115912, JP-A-61-115916, JP-A-62-120816, etc.).

However, although these cyclic olefin-based random copolymers are resins having excellent heat resistance and rigidity despite being olefin-based polymers, there is a problem that impact resistance is not sufficient depending on the application. Was.

[Problems to be solved by the invention]

The object of the present invention is to solve these problems, and is excellent in heat resistance, chemical resistance, solvent resistance, dielectric properties, rigidity, etc., and also excellent in impact resistance, a cyclic olefin-based random copolymer composition. It is to provide things.

[Means for solving the problem]

The present invention comprises [A] an ethylene component and a cyclic olefin component represented by the following general formula [I] or [II], and has an intrinsic viscosity [η] measured in decalin at 135 ° C.
Is a cyclic olefin-based random copolymer having a softening temperature (TMA) of 70 ° C. or higher and 0.05 to 10 dl / g, [B] an amorphous or low-crystalline α-olefin formed from at least two α-olefins. An olefin-based copolymer and an amorphous or low-crystalline styrene-based copolymer in which [C] styrene or a derivative thereof is one of the monomer components and at least one of the glass transition temperatures is 0 ° C. or lower. With respect to 100 parts by weight of the component (A), (B)
The total amount of the component and the component (C) is 5 to 100 parts by weight, and the ratio of the component (B) to the component (C) is 95: 5 to 5:95 by weight.
It is a cyclic olefin random copolymer composition characterized by these.

General formula [In the formula, n and m are each 0 or a positive integer, is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group. The cyclic olefin random copolymer (A) constituting the cyclic olefin random copolymer composition of the present invention is
It is a cyclic olefin random copolymer composed of an ethylene component and a specific cyclic olefin component. The cyclic olefin component is a cyclic olefin represented by the general formula (I) or the general formula (II), and in the cyclic olefin random copolymer (A) of the present invention,
It forms a repeating unit having a structure represented by the following general formula [III] or general formula [IV].

[In the formula, n, m, and R ¹ to R ¹⁰ are the same as described above. The cyclic olefin of the cyclic olefin random copolymer [A] constituting the cyclic olefin random copolymer composition of the present invention is an unsaturated olefin represented by the general formulas [I] and [II]. It is at least one type of cyclic olefin selected from the group consisting of monomers. The cyclic olefin represented by the general formula [I] can be easily produced by condensing cyclopentadiene and a corresponding olefin by a Diels-Alder reaction. Similarly, the cyclic olefin represented by the general formula [II] can be easily produced by condensing a cyclopentadiene and a corresponding cyclic olefin by a Diels-Alder reaction.

Specific examples of the cyclic olefin represented by the general formula [I] include compounds described in Table 1 or 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Besides octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,
8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2-hexyl-1,4,
5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,
4a, 5,8,8a-octahydronaphthalene, 2-methyl-3
-Ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Bromo-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene,
2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8
a-octahydronaphthalene, 2-cyclohexyl-1,
4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,
3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, etc. Octahydronaphthalenes, the compounds described in Table 2, and the like.

Specific examples of the cyclic olefin represented by the general formula [II] include the compounds shown in Tables 3 and 4.

The cyclic olefin-based random copolymer [A] constituting the composition of the present invention contains an ethylene component and the above-mentioned cyclic olefin component as essential components. If necessary, other copolymerizable unsaturated monomer components may be contained within a range not impairing the above. Specific examples of the unsaturated monomer which may be optionally copolymerized include, for example, propylene, 1-butene, and 4-methyl-1 in a range of less than an equimolar amount to the ethylene component unit in the produced random copolymer. -Pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene,
Examples thereof include α-olefins having 3 to 20 carbon atoms such as 1-eicosene.

In the cyclic olefin random copolymer [A] constituting the composition of the present invention, the repeating unit (a) derived from the ethylene component is in the range of 40 to 85 mol%, preferably 50 to 75 mol%, and the cyclic olefin component The repeating unit (b) derived from the above is suitably in the range of 15 to 60 mol%, preferably 25 to 50 mol%, and the repeating unit (a) derived from an ethylene component and the repeating unit (b) derived from a cyclic olefin component ) Forms a substantially linear cyclic olefin-based random copolymer randomly arranged. The fact that the cyclic olefin-based random copolymer is substantially linear and does not have a gel-like crosslinked structure can be confirmed by completely dissolving the copolymer in decalin at 135 ° C.

The intrinsic viscosity [η] of the cyclic olefin random copolymer [A] constituting the composition of the present invention measured in decalin at 135 ° C. is 0.05 to 10 dl / g, preferably 0.08 to 5 dl / g. .

As the cyclic olefin random copolymer [A] constituting the composition of the present invention, the softening temperature (TMA) measured by a thermomechanical analyzer is 70 ° C or higher, preferably 90 to 250 ° C, more preferably 100 to 250 ° C. ~ 200 ° C range,
The glass transition temperature (Tg) of the cyclic olefin-based random copolymer [A] is usually 50 to 230 ° C, preferably 70 to 210 ° C. The crystallinity of the cyclic olefin random copolymer [A] measured by an X-ray diffraction method is from 0 to 10.
%, Preferably 0 to 7%, particularly preferably 0 to 5%.

As the cyclic olefin-based random copolymer [A] constituting the composition of the present invention, a copolymer consisting of only those having the properties in the above range may be used, but copolymers having physical properties outside the above range may be used. A part of coalescence may be included, and in this case, it is only necessary that the entire physical property value be included in the above range.

The cyclic olefin-based random copolymer [A] constituting the composition of the present invention is disclosed in JP-A-60-168708 and JP-A-61-168708.
JP-120816, JP-A-61-115912, JP-A-61-115912
No. 115916, JP-A-61-271308, JP-A-61-27
No. 2216, JP-A-62-252406, JP-A-62-2524
It can be produced by appropriately selecting conditions according to the method proposed by the present applicant in Japanese Patent Application Publication No. 07-2007 and the like.

The α-olefin copolymer [B] constituting the cyclic olefin random copolymer composition according to the present invention is an amorphous or low-crystalline copolymer formed from at least two kinds of α-olefins. Specifically, (i) an ethylene / α-olefin copolymer, (ii) propylene / α
-An olefin copolymer is used.

(I) The α-olefin constituting the ethylene / α-olefin copolymer is usually an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl- Examples thereof include 1-petene, 1-octene, 1-decene, and mixtures thereof. Among them, propylene or 1-
Butene is preferred.

And (ii) a propylene / α-olefin copolymer. As the α-olefin, an α-olefin having usually 4 to 20 carbon atoms, such as 1-butene, 1-petene,
Examples include -hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. Of these, 1-butene is particularly preferred.

In the above-mentioned (i) ethylene / α-olefin copolymer, the molar ratio of ethylene to α-olefin (ethylene / α-olefin) varies depending on the type of α-olefin, but generally 50/50. Preferably it is 50-95 / 5. The molar ratio is preferably 50/50 to 90/10 when the α-olefin is propylene, and 60/4 when the α-olefin has 4 or more carbon atoms.
It is preferably from 0 to 95/5.

In the above (ii) propylene / α-olefin copolymer, the molar ratio of propylene to α-olefin (propylene / α-olefin) varies depending on the type of α-olefin, but is generally 50/50. Preferably it is ~ 95/5.

It is desirable that such an α-olefin copolymer [B] has a crystallinity of 0 to 50%, preferably 0 to 25%, as measured by an X-ray diffraction method.

The intrinsic viscosity [η] of the α-olefin-based copolymer [B] measured in decalin at 135 ° C. is desirably 0.2 to 10 dl / g, preferably 1 to 7 dl / g.

The styrene-based copolymer [C] constituting the cyclic olefin-based random copolymer composition according to the present invention has styrene or a derivative thereof as one of the monomer components, and at least one of the glass transition temperatures is 0 ° C or lower. A non-crystalline or low-crystalline copolymer, specifically, a random copolymer of styrene or α-methylstyrene with butadiene or isoprene, a block copolymer, and a hydrogenated product thereof. .

The cyclic olefin-based random copolymer composition according to the present invention is based on 100 parts by weight of the cyclic olefin-based random copolymer [A], and the α-olefin-based copolymer [B] and the styrene-based copolymer [C Is present in an amount of 5 to 100 parts by weight, preferably 7 to 80 parts by weight, particularly preferably 10 to 70 parts by weight. When the total amount of the component (B) and the component (C) is less than 5 parts by weight based on 100 parts by weight of the component (A), the rigidity is excellent, but the impact resistance is inferior. Exceeding the weight part is not preferable because the impact resistance is excellent but the rigidity is low and the balance between the rigidity and the impact strength is poor. The ratio of the component (B) and the component (C) is 95: 5 to 5:95, preferably 90:10 to 10:90, in terms of the polymerization ratio.
Range. If the respective proportions are less than 5% by weight, the effect of improving the impact resistance is undesirably reduced.

The composition of the present invention comprises, in addition to the above components (A) to (C), a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent,
Anti-blocking agents, anti-fogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes and the like can be blended, and the blending ratio is an appropriate amount. For example, as a stabilizer blended as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-di- t-
Butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamidobis [ethyl-3 (3,5
Phenolic antioxidants such as -di-t-butyl-4-hydroxyphenyl) propionate; fatty acid metal salts such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; glycerin monostearate; glycerin monolaurate; glycerin Examples thereof include polyhydric alcohol fatty acid esters such as distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination, for example, tetrakis [methylene-3 (3,5-di-t-butyl-4-
[Hydroxyphenyl) propionate] methane with zinc stearate and glycerin monostearate.

As the method for producing the cyclic olefin-based random copolymer composition according to the present invention, known methods can be applied, and the cyclic olefin-based random copolymer [A], α-olefin-based copolymer [B], and styrene-based copolymer can be used. A method of mechanically blending the polymer [C] and other components to be added, if necessary, with an extruder, a kneader, or the like, or each component is a suitable good solvent, for example, hexane, heptane, decane, cyclohexane, benzene, toluene , Xylene and the like, or a method in which each is separately dissolved and then mixed and removed to remove the solvent, and a method in which these two methods are combined, and the like.

Since the cyclic olefin-based random copolymer composition obtained as described above contains the component [A] and the components [B] and [C], the cyclic olefin-based random copolymer [A] has heat resistance and chemical resistance. Impact resistance can be improved without impairing excellent properties such as solvent resistance and dielectric properties. In this case, by using the α-olefin-based copolymer [B] and the styrene-based copolymer [C] in combination, the performance is remarkably improved as compared with a composition in which these are used alone.

Due to the above properties, the cyclic olefin-based random copolymer composition of the present invention can be used for applications similar to polycarbonate, ABS, etc., for example, for interior materials of automobiles.

〔The invention's effect〕

The cyclic olefin-based random copolymer composition of the present invention is composed of a cyclic olefin-based random copolymer [A], an α-olefin-based copolymer [B], and a styrene-based copolymer [C]. In addition to being excellent in chemical resistance, solvent resistance, dielectric properties, rigidity, etc., it is also excellent in impact resistance.

〔Example〕

 Hereinafter, the present invention will be described specifically with reference to examples.

The methods for measuring and evaluating various physical properties in the present invention are described below.

(1) Melt flow index (MRF ₂₆₀ ° C.) Measured at a temperature of 260 ° C. and a load of 2.16 kg according to ASTM D1238.

(2) Preparation of test piece The test piece was molded under the following molding conditions using an injection molding machine IS-35 manufactured by Toshiba Machine Co., Ltd. and a predetermined test piece mold. The test pieces were left for 48 hours at room temperature after molding and then subjected to measurement.

Molding conditions: cylinder temperature 220 ° C, mold temperature 60 ° C, injection output primary / secondary = 1000 / 800kg / cm ² , injection speed (primary) 30mm
/ sec, screw rotation speed 150 rpm, cycle ([injection + holding pressure] / cooling) = 7/15 sec (3) Bending test The bending test was performed according to ASTM D790.

Test specimen shape: 5 x 1/2 x 1/8 ^t inch, distance between spans 51 mm Test speed: 20 mm / min Test temperature: 23 ° C (4) Izod impact test The test was performed according to ASTM D256.

Test specimen shape: 2 × 1/2 × 1/8 ^t inch (with notch) Test temperature: 23 ° C. (5) Heat deformation temperature (HDT) This was performed according to ASTM D648.

Specimen shape: 5 x 1/4 x 1/2 ^t inches Load: 264 psi (6) Glass transition temperature (Tg) Temperature rise rate using DSC-20 manufactured by SEIKO Electronic Industry Co., Ltd.
It was measured at ° C / min.

Example 1 Ethylene content measured by ¹³ C-NMR: 62 mol%, MFR: _{260 ° C.} 3
5g / 10min, intrinsic viscosity measured in decalin at 135 ° C [η]
0.47 dl / g ethylene, 1,4,5,8 with softening temperature (TMA) 148 ℃
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (structural formula: (Hereinafter abbreviated as DMON) 4 kg of random copolymer pellets,
Ethylene / propylene random copolymer (ethylene content 80 mol%, Tg-54 ° C, MFR _{230 ° C} 0.7g / 10min, [η] 2.2
dl / g) pellet, 1 kg, styrene-butadiene-styrene block copolymer (Califlex TR, manufactured by Shell Chemical Company)
After thoroughly mixing 1 kg of pellets of -1101, trademark, Tg-80 ° C and 95 ° C), a twin-screw extruder (PCM4 manufactured by Ikegai Iron Works Co., Ltd.)
The mixture was melt-blended at a cylinder temperature of 220 ° C according to 5) and pelletized with a pelletizer. A test piece was prepared from the obtained pellets by the method described above, and the physical properties were measured.

 Table 5 shows the results.

Examples 2 and 3 The same procedure as in Example 1 was carried out except that the amounts of the ethylene / propylene random copolymer and the styrene / butadiene / styrene block copolymer used in Example 1 were changed.

 Table 5 shows the results.

Examples 4 to 8 The same procedures as in Example 1 were carried out except that various styrene copolymers were used instead of the styrene / butadiene / styrene block copolymer used in Example 1.

 Table 6 shows the results.

Example 9 Instead of the ethylene / DMON random copolymer used in Example 1, an ethylene content of 71 mol%, MFR _{260 ° C.,} 20 g / 10 mi
n, [η] 0.60 dl / g, TMA Performed in the same manner as in Example 1 except that an ethylene / DMON random copolymer at 115 ° C. was used. MFR _{260 ° C} , Izod impact strength, flexural modulus, flexural strength, HDT of the obtained composition were 6.7 g / 10 min, 29 kgcm /
cm, 18000 kg / cm ² , 690 kg / cm ² , 93 ° C.

Comparative Example 1 The same procedure was performed as in Example 1, except that the styrene / butadiene / styrene block copolymer was not used and the amount of the ethylene / propylene random copolymer was changed to 2 kg.

 Table 7 shows the results.

Comparative Example 2 Example 1 was repeated except that the ethylene / propylene random copolymer was not used and the amount of the styrene / butadiene / styrene block copolymer was changed to 2 kg.

 Table 7 shows the results.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location C08L 25:04) (72) Inventor Kotaro Kishimura 6-1, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture No. 2 Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-61-115912 (JP, A) JP-A-61-115916 (JP, A)

Claims (1)

(57) [Claims] 1. An intrinsic viscosity [η] of [A] comprising an ethylene component and a cyclic olefin component represented by the following general formula [I] or [II] and measured in decalin at 135 ° C.
Is a cyclic olefin-based random copolymer having a softening temperature (TMA) of 70 ° C. or higher and 0.05 to 10 dl / g, [B] an amorphous or low-crystalline α-olefin formed from at least two α-olefins. An olefin-based copolymer and an amorphous or low-crystalline styrene-based copolymer in which [C] styrene or a derivative thereof is one of the monomer components and at least one of the glass transition temperatures is 0 ° C. or lower. With respect to 100 parts by weight of the component (A), (B)
The total amount of the component and the component (C) is 5 to 100 parts by weight, and the ratio of the component (B) to the component (C) is 95: 5 to 5:95 by weight.
A cyclic olefin-based random copolymer composition, characterized in that: General formula [In the formula, n and m are each 0 or a positive integer, is an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group. ]