JP3379810B2 - Polyolefin polymer alloy - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is an IC manufactured by injection molding or the like.
The present invention relates to a novel polyolefin-based polymer alloy that can be used as a tray molded product or the like, or as a sheet or film by extrusion molding or the like. More specifically, it is obtained by combining a specific amorphous polyolefin and a crystalline polyolefin, and further adding a radical initiator to melt-kneading to remarkably improve the compatibility, physical property balance and appearance, moldability, moisture resistance, Transparency, impact resistance,
The present invention relates to a novel polyolefin polymer alloy having excellent heat resistance.

[0002]

2. Description of the Related Art Amorphous polyolefins have excellent heat resistance, electrical properties, mechanical strength, moldability, transparency, moisture resistance, and dimensional stability. The molded article produced by the above method or the sheet or film produced by the extrusion method lacks impact resistance in practical use, and it is desired that the amorphous polyolefin is toughened without impairing the characteristics thereof. Further, the amorphous polyolefin has poor oil resistance because it is amorphous, and needs to be improved for use in applications such as foods requiring oil resistance. In order to improve these drawbacks, a method of forming a composite sheet in which a crystalline polymer and a hydride of a ring-opening polymer of dicyclopentadiene having a high glass transition point are combined is disclosed in JP-A-4-272.
Although the composite sheet of the present invention has an effect of improving impact resistance, it is merely a blend of two kinds of polymers, and the composite sheet of the present invention has mechanical properties, transparency, etc. It was insufficient.

[0003]

SUMMARY OF THE INVENTION In the present invention, a radical initiator is added to an amorphous polyolefin having good heat resistance, moldability, moisture resistance, transparency and dimensional stability and a crystalline polyolefin having good impact resistance. By further melt-kneading and remarkably improving the compatibility of both polymers, a new excellent balance of physical properties such as heat resistance, electrical properties, mechanical strength, moldability, transparency, moisture resistance, dimensional stability, etc. It is intended to provide a novel polyolefin-based polymer alloy.

[0004]

The present invention is directed to unsaturated groups and
Heat resistance obtained by adding a radical initiator to the amorphous polyolefin (A) and the crystalline polyolefin (B) having no double bond , and further melt-kneading to remarkably improve the compatibility of both polymers, The present invention relates to a novel polyolefin polymer alloy having an excellent balance of physical properties such as electrical properties, mechanical strength, moldability, transparency, moisture resistance, and dimensional stability. That is, the present invention has an unsaturated group and a double bond.
Amorphous polyolefin (A) not having 90% by weight to 10
% And crystalline polyolefin (B) 10% by weight to 90%
It is a polyolefin-based polymer alloy characterized in that 0.01 to 10 parts by weight of a radical initiator is added to 100 parts by weight of a mixture consisting of 1% by weight, and the mixture is melt-kneaded, and preferably the radical initiator is an organic compound. -Based peroxide, the crystalline polyolefin (B) is polyethylene, and the amorphous polyolefin (A) having no unsaturated group and double bond is cyclopentadiene or its derivative and norbornadiene or its derivative. Of the addition reaction product of ethylene with butadiene or one or more unsaturated monomers selected from styrene derivatives, hydrogenated products thereof, or addition of dicyclopentadiene or its derivatives with ethylene. Copolymerization of reactants with one or more unsaturated monomers selected from ethylene, butadiene, or styrene derivatives Or a hydrogenated product thereof, or a tetracyclo-3-dodecene or a polymer alloy which is a derivative thereof and Bishikuroheputo-2-ene or a hydrogenated product of a ring-opening polymer comprising a derivative thereof.

In general, when two or more resins are combined, they are rarely compatible with each other, and in most cases the resulting blends are inferior in properties to either polymer in most cases. In the case of the present invention, since the same polyolefin resin is used, the compatibility is quite good, but since the interfacial adhesion between both polymers is not sufficient by simply blending them, the mechanical properties, transparency, etc. Was insufficient. In order to improve this defect, it is necessary to improve the compatibility of both polymers and to improve the adhesion at the interface. As a result of various investigations, a radical initiator was added to both polymers and further melt kneading was performed. , The adhesive property of the interface is remarkably improved, and a novel polyolefin-based polymer alloy having excellent balance of physical properties such as heat resistance, electrical properties, mechanical strength, moldability, moisture resistance, transparency, and dimensional stability can be obtained. After finding out the above, the present invention has been completed.

The unsaturated groups and double bonds used in the present invention are
The non- crystalline amorphous polyolefin (A) is a polymer having a cyclic olefin structure, and can be said to be an amorphous polyolefin because of its structure and properties. Examples of the amorphous polyolefin include the following. For example, it is an amorphous polymer represented by the following general formula. (Wherein, n is a positive integer of 1 or more, m is a positive integer of 1 or more, R ₁ is a hydrogen atom, a halogen atom, CH ₃ CH
₂ groups or C ₆ H ₄ R ₂ groups are shown, and R ₂ represents a hydrogen atom, a hydrocarbon group, an alkoxy group, a halogenated hydrocarbon group or a halogen atom. X represents an addition reaction product of cyclopentadiene or its derivative with norbornadiene or its derivative or a hydrogenated product thereof, or an addition reaction product of dicyclopentadiene or its derivative with ethylene. )

The hydrogenation product of the addition reaction product of cyclopentadiene or its derivative with norbornadiene or its derivative, or the general formula of the addition reaction product of dicyclopentadiene or its derivative with ethylene is shown below.

[Chemical 1] (In the formula, n is a positive integer of 1 or more, and R _{1 to} R _1
12 independently represent an atom or a group selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and R _{9 to} R
₁₂ may combine with each other to form a monocycle or polycycle. )

Examples of the hydrogenation product of the addition reaction product of cyclopentadiene or its derivative with norbornadiene or its derivative, or the addition reaction product of dicyclopentadiene or its derivative with ethylene, include tetracyclo-3-dodecene, 8-methyltetracyclo-3
-Dodecene, 8-ethyltetracyclo-3-dodecene,
8-propyltetracyclo-3-dodecene, 8-butyltetracyclo-3-dodecene, 8-isobutyltetracyclo-3-dodecene, 8-hexyltetracyclo-3-
Dodecene, 8-stearyltetracyclo-3-dodecene, 5,10-dimethyltetracyclo-3-dodecene,
2,10-dimethyltetracyclo-3-dodecene, 8,
9-dimethyltetracyclo-3-dodecene, 8-ethyl-9-methyltetracyclo-3-dodecene, 11,12
-Dimethyltetracyclo-3-dodecene, 2,7,9-
Trimethyltetracyclo-3-dodecene, 9-ethyl-
2,7-Dimethyltetracyclo-3-dodecene, 9-isobutyl-2,7-dimethyltetracyclo-3-dodecene, 9,11,12-trimethyltetracyclo-3-dodecene, 9-ethyl-11,12- Dimethyltetracyclo-3-dodecene, 9-isobutyl-11,12-dimethyltetracyclo-3-dodecene, 5,8,9,10-
Tetramethyltetracyclo-3-dodecene, 8-chloro
Tetracyclo-3-dodecene , 8-bromotetracyclo-3-dodecene, 8-fluorotetracyclo-3-dodecene, 8,9-dichlorotetracyclo-3-dodecene,
Hexacyclo-4-heptadecene, 12-methylhexacyclo-4-heptadecene, 12-ethylhexacyclo-4-heptadecene, 12-isobutylhexacyclo-
4-heptadecene, 1,6,10-trimethyl-12-
Isobutylhexacyclo-4-heptadecene, octacyclo-5-dococene, 15-methyloctacyclo-5-
Docosene, 15-ethyloctacyclo-5-docosene,
Pentacyclo-4-hexadecene, 1,3-dimethylpentacyclo-4-hexadecene, 1,6-dimethylpentacyclo-4-hexadecene, 15,16-dimethylpentacyclo-4-hexadecene, heptacyclo-5-eicosene, heptacyclo- 5-heneicocene, pentacyclo-4-pentadecene, 1,3-dimethylpentacyclo-4-pentadecene, 1,6-dimethylpentacyclo-4-pentadecene, 14,15-dimethylpentacene
Chloro-4-pentadecene, etc. may be mentioned.

Examples of styrene derivatives include styrene, o-methylstyrene, m-methylstyrene and p.
-Methylstyrene, α-methylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o
-Ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-methoxystyrene, p-chloroethylstyrene, p-methyl-α-methylstyrene and the like are used. In addition, these can also be used as a mixture of 2 or more types.

Further, as another example of the amorphous polyolefin (A) having no unsaturated group and no double bond, those represented by the following general formula can also be mentioned.

[Chemical 2] (However, in the formula, n is 0 or a positive integer of 1 or more, m is a positive integer of 1 or more, and R _{1 to} R ₄ are hydrogen atoms or hydrocarbon groups.)

Examples of the above-mentioned tetracyclo-3-dodecene or its derivative are tetracyclo-3-dodecene, 5,10-dimethyltetracyclo-3-dodecene,
2,10-dimethyltetracyclo-3-dodecene, 1
1,12-dimethyltetracyclo-3-dodecene, 2,
7,9-Trimethyltetracyclo-3-dodecene, 9-
Ethyl-2,7-dimethyltetracyclo-3-dodecene, 9-isobutyl-2,7-dimethyltetracyclo-
3-dodecene, 9,11,12-trimethyltetracyclo-3-dodecene, 9-ethyl-11,12-dimethyltetracyclo-3-dodecene, 9-isobutyl-11,
12-dimethyltetracyclo-3-dodecene, 5,8,
9,10-tetramethyltetracyclo-3-dodecene,
8-methyltetracyclo-3-dodecene, 8-ethyltetracyclo-3-dodecene, 8-propyltetracyclo-3-dodecene, 8-hexyltetracyclo-3-dodecene, 8-stearyltetracyclo-3-dodecene,
8,9-Dimethyltetracyclo-3-dodecene, 8-methyl-9-ethyltetracyclo-3-dodecene, 8-cyclohexyltetracyclo-3-dodecene, 8-isobutyltetracyclo-3-dodecene, 8-butyltetracyne
Examples include cro-3-dodecene and the like . Examples of bicyclohept-2-ene and its derivatives include bicyclohept-2-ene and 6-methylbicyclohept-2.
-Ene, 5,6-dimethylbicyclohept-2-ene,
1-methylbicyclohept-2-ene, 6-ethylbicyclohept-2-ene, 6-n-butylbicyclohept-2-ene, 6-isobutylbicyclohept-2-ene, 7-methylbicyclo Hept-2-ene etc. are mentioned. In addition, these can also be used as a mixture of 2 or more types.

The amorphous polyolefin (A) having no unsaturated group or double bond has a heat distortion temperature in the range of 70 to 170 ° C., but for applications requiring heat resistance, It is preferable to use one having a heat distortion temperature of 100 ° C. or higher. Crystalline polyolefin (B) used in the present invention
Is not particularly limited and is generally used, and examples thereof include polyethylene and polypropylene, and among these, polyethylene having excellent impact resistance is more preferable. The radical initiator used in the present invention is
It is an important component which has the effect of remarkably improving the compatibility between the amorphous polyolefin (A) having no unsaturated group and the double bond and the crystalline polyolefin (B). The radical initiator of the present invention is not particularly limited and is commercially available, and includes organic peroxides, organic peresters, azo compounds and the like. Among these, the non-aromatic organic peroxides are transparent. Is preferred. The polyolefin-based polymer alloy of the present invention has an unsaturated group and a double bond.
It is obtained by adding the above-mentioned radical initiator to a mixture prepared by mixing the non-bonded amorphous polyolefin (A) and the crystalline polyolefin (B) in a predetermined ratio, and melt-kneading the mixture with a biaxial kneader or the like. . The polyolefin-based polymer alloy of the present invention has an unsaturated group and a double bond.
The amorphous polyolefin (A) must be mixed in the range of 90 to 10% by weight, and the crystalline polyolefin (B) in the range of 10 to 90% by weight. The content of component (A) is 10% by weight
If it is less than the above range, the moldability, dimensional stability and rigidity are not sufficient, and if it exceeds 90% by weight, favorable properties in impact resistance cannot be obtained. When heat resistance is important, the compounding ratio of the amorphous polyolefin (A) having no unsaturated group and double bond and the crystalline polyolefin (B) is 90% by weight: 10% by weight to 30% by weight. : 70% by weight
Is preferred, and more preferably 90% by weight: 10% by weight
60% by weight: 40% by weight. The radical initiator is a mixture 10 of an amorphous polyolefin (A) and a crystalline polyolefin (B) having no unsaturated group or double bond.
It should be blended in the range of 0.01 to 10 parts by weight with respect to 0 parts by weight. The amount of radical initiator compounded is 0.0
If it is less than 1 part by weight, the effect of improving the compatibility becomes insufficient, and if it exceeds 10 parts by weight, the cross-linking reaction of both polymers proceeds too much, and the impact resistance decreases.

As described above, an unsaturated group and a double bond are not contained.
The radical initiator is blended in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the mixture of the amorphous polyolefin (A) and the crystalline polyolefin (B), and the phase of both polymers is mixed by melt-kneading. The solubility was improved, and the adhesiveness at the interface, mechanical properties, transparency, etc. were remarkably improved. The reason is that when a radical initiator is added and melt kneading is performed,
A coupling reaction occurs between both polymers, and a reaction product containing the components of both polymers in the same molecule is produced. This acts as a surfactant, and a micro phase separation structure with good adhesion at the interface. It is thought that it is possible to take Further, if necessary, a compatibilizer, an additive such as a dye / pigment, a stabilizer, etc. within a range not impairing the basic properties
A plasticizer, an antistatic agent, an ultraviolet absorber, an antioxidant, a lubricant, a filler, an elastomer for imparting flexibility, and the like can also be added. The polyolefin-based polymer alloy of the present invention can be easily processed into a molded product, a film, a sheet or the like by a processing method used for ordinary thermoplastic resin molded products such as injection molding and extrusion molding.

[0014]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. First, examples and comparative examples examined for molding materials are shown below. The tensile test is ASTM-D638, the bending test is ASTM-D790, and the Izod impact test is AS.
It is the result measured by TM-D256. As for the warpage of the molded product, a flat plate having a length of 150 mm, a width of 300 mm and a thickness of 1 mm was measured and evaluated with a height master. The results of the blended composition and each characteristic value are shown in Table 1. (Examples 1 and 2) As the component (A) , the cyclic olefin structure of the chemical formula 1 was used.
To, Appel 150R [APO; thermal deformation temperature of 150
C. (ASTM D648 18.6 Kg / cm ² ) manufactured by Mitsui Petrochemical Co., Ltd.] is used as the component (B). Ace Polyeth HDF6080V [PO; Showa Denko KK
Was used as the radical initiator, and dicumyl peroxide [peroxide; Perkmill D Nippon Oil & Fats Co., Ltd.] was used as a radical initiator. (Examples 3 to 4) As the component (A) , the cyclic olefin structure of the chemical formula 1 was used.
Yes , Apel APL6011 [APO; heat distortion temperature 9
5 ° C. (ASTM D648 18.6 Kg / cm ² ) manufactured by Mitsui Petrochemical Industry Co., Ltd.] is used as the component (B).
Ace Polyech HD S6002 [PO; Showa Denko
Co., Ltd.] and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane [peroxide; Perhexa 25B NOF CORPORATION] as a radical initiator. Comparative Example 1 As the component (A), Apel 150R [APO; heat distortion temperature 150 ° C., manufactured by Mitsui Petrochemical Industry Co., Ltd.] was used. (Comparative Example 2) As the component (A), Apel APL6011 [APO
Heat distortion temperature 95 ° C (ASTM D648 18.6K
g / cm ² ) manufactured by Mitsui Petrochemical Industry Co., Ltd.] was used. (Comparative Example 3) As the component (A), Apel 150R [APO; heat distortion temperature 150 ° C (ASTM D648 18.6 Kg / c
m ² ) manufactured by Mitsui Petrochemical Industry Co., Ltd.], and as the component (B), Ace Polyethylene HD F6080V (PO
Showa Denko KK) was used.

[0015]

Next, examples and comparative examples examined for sheet materials are shown below. In addition, a 0.25 mm T-die sheet was used to measure the characteristics of the sheet, and the light transmittance,
And Haze is ASTM-D1003, and is moisture proof and has a moisture permeability (unit: g / m ² · 24hr / 0.25mm) JI
It is a measurement value based on S-Z0208 under condition A, that is, a temperature of 25 ° C. and a relative humidity of 90%, and the appearance was visually determined. Regarding the oil resistance, a sheet of 5 mm square and a thickness of about 250 μ was immersed in n-heptane, and the appearance change (swelling etc.) after leaving at 23 ° C. for 3 days, the degree of softening, the change in transparency, etc. were evaluated. The thing which did not change was marked with ◯, the thing which changed a little was marked with Δ, and the thing which changed was marked with x. The tensile test is ASTM-D63.
8. The bending test is a result measured by ASTM-D790, and the Izod impact test is a result measured by ASTM-D256.
The results of the blended composition and each characteristic value are shown in Table 2. (Examples 5 to 6) As the component (A), Apel APL6509 [APO
Heat distortion temperature 72 ° C. (ASTM D648 18.6
Kg / cm ² ) manufactured by Mitsui Petrochemical Industry Co., Ltd.]
As the component (B), Ace Polyethylene HD F6080
V [HDPE; Density 0.961 g / cm ³ (JIS
K6760) Showa Denko KK] and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane [peroxide; Perhexa 25B NOF CORPORATION] as a radical initiator. (Examples 7 to 8) As the component (A), Apel APL6011 [APO
Heat distortion temperature 95 ° C. (ASTM D648 18.6
Kg / cm ² ) manufactured by Mitsui Petrochemical Industry Co., Ltd.]
As the component (B), Ace Polyethylene HD S6002
[HDPE; density 0.954 g / cm ³ (JIS K
6760) Showa Denko KK] and dicumyl peroxide [peroxide; Park Mill D as a radical initiator]
Nippon Oil & Fats Co., Ltd.] was used. (Comparative Example 4) As the component (A), Apel APL6509 [APO;
Manufactured by Mitsui Petrochemical Industry Co., Ltd.] was used. (Comparative Example 5) As the component (A), Apel APL6509 [APO
Heat distortion temperature 72 ° C. (ASTM D648 18.6
Kg / cm ² ) manufactured by Mitsui Petrochemical Industry Co., Ltd.]
As the component (B), Ace Polyethylene HD F6080
V [HDPE; Density 0.961 g / cm ³ (JIS
K6760) Showa Denko KK] was used. (Comparative Example 6) As the component (A), Apel APL6515 [APO
Heat distortion temperature 125 ° C. (ASTM D648 18.
6 Kg / cm ² ) manufactured by Mitsui Petrochemical Industry Co., Ltd.]
As the component (B), Ace Polyethylene HD F6080
V [HDPE; Density 0.961 g / cm ³ (JIS
K6760) Showa Denko KK] was used.

[0017]

[0018]

The polyolefin-based polymer alloy according to the present invention is easily processed into a molded product, film or sheet by a processing method used for ordinary thermoplastic molding materials, such as injection molding or extrusion molding, and is heat-resistant. The product has an excellent balance of physical properties such as properties, electrical properties, mechanical strength, moldability, moisture resistance, transparency, and dimensional stability.

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Claims (6)

(57) [Claims] 1. A compounding ratio of an amorphous polyolefin (A) having no unsaturated group and a double bond and a crystalline polyolefin (B) is 90% by weight: 10% by weight to 10% by weight: 90% by weight.
The radical initiator is 0.0
A polyolefin-based polymer alloy, which is obtained by adding 1 to 10 parts by weight and melt-kneading. 2. The polyolefin-based polymer alloy according to claim 1, wherein the radical initiator is an organic peroxide. 3. The polyolefin polymer alloy according to claim 1 or 2, wherein the crystalline polyolefin (B) is polyethylene. 4. An amorphous polyolefin (A) having no unsaturated group or double bond is obtained from an addition reaction product of cyclopentadiene or its derivative and norbornadiene or its derivative, and an ethylene, butadiene, or styrene derivative. The polyolefin polymer alloy according to claim 1, 2, or 3, which is a copolymer with one or more selected unsaturated monomers or a hydrogenated product thereof. 5. The amorphous polyolefin (A) having no unsaturated group and double bond is selected from the addition reaction product of dicyclopentadiene or its derivative with ethylene, and ethylene, butadiene, or styrene derivative. 4. A copolymer with one or more unsaturated monomers.
The polyolefin-based polymer alloy described. 6. A hydrogen of a ring-opening polymer in which the amorphous polyolefin (A) having no unsaturated group or double bond is tetracyclo-3-dodecene or its derivative and bicyclohept-2-ene or its derivative. The polyolefin-based polymer alloy according to claim 1, which is an additive.