JPH0618952B2 - Poly-4-methyl-1-pentene composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a poly-4-methyl-1-pentene composition containing a silicone oil, which is excellent in mold releasability, heat resistance and chemical resistance, and uniformly. The manufacturing method is related.

[Conventional technology]

Poly 4-methyl-1-pentene has its transparency, heat resistance,
Utilizing its chemical resistance, it is used for chemical experiments such as beakers and graduated cylinders, syringes for syringes, cells for optical measurement, trays for microwave ovens or papers coated with paper for baking cartons. Poly 4-methyl-1-pentene does not cause a problem when it is used for injection molding of a molded product having a simple shape, and it is not a problem, but it is used for a mold with a draft close to 0 degrees. May cause defects,
Further, when a poly-4-methyl-1-pentene film was used as a release film for crosslinking polyurethane, there were cases where the polyurethane could not be released after passing through a high temperature and high pressure roll.

It is known to add silicone oil or the like in order to improve the releasability and anti-sticking property of the thermoplastic resin (for example, JP-A-48-28542). However, in order to mix the silicone oil with the poly-4-methyl-1-pentene, the silicone oil and the poly-4-methyl-1-pentene are simply stirred by a conventional Henschel mixer, a tumbler or the like, and a single-screw or multi-screw extruder is used. Even if an attempt is made to knead the mixture into a uniform composition or a molded product by mixing, the silicone oil is present between the extruder screw and the poly-4-methyl-1-pentene, and the screw causes co-rotation. Under the present circumstances, molding cannot be performed, and even if a molded product is obtained, the composition has poor dispersibility of silicone oil and is not practical.

[Problems to be solved by the invention]

In view of such a situation, the present inventors have conducted various studies to obtain a poly-4-methyl-1-pentene composition having excellent dispersibility of silicone oil, and as a result, have identified poly-4-methyl-1-pentene and silicone oil. It was found that the object of the present invention can be achieved by mixing for a certain time in a heated state and then melt-kneading, and the present invention has been completed.

[Means for solving problems]

That is, the present invention provides poly-4-methyl-1-pentene (A) in an amount of 50 to 99.5% by weight, and a viscosity at 25 ° C. of 50 to 8 × 10 ⁶ cp and a general formula: [In the formula, R represents a hydrogen atom, an aromatic organic group, or an atom or a group of the same or different types selected from an aliphatic saturated or unsaturated organic group. However, when the aliphatic organic group has 3 or more carbon atoms, the group may contain a hetero ring or a hetero atom. n is a positive integer], and the average maximum projected area of the silicone oil (B) is 3.0 × 10 ³ μm ² or less. The present invention provides a poly-4-methyl-1-pentene composition characterized by the above.

The present invention also provides a method for producing the poly-4-methyl-1-pentene composition, wherein the poly-4-methyl-1-pentene (A) is 50 to 99.5% by weight, and the viscosity at 25 ° C. is 50 to 8 ×. General formula at 10 ⁶ cp: [In the formula, R represents a hydrogen atom, an aromatic organic group, or an atom or a group of the same or different types selected from an aliphatic saturated or unsaturated organic group. However, when the aliphatic organic group has 3 or more carbon atoms, the group may contain a hetero ring or a hetero atom. n is a positive integer] and the silicone oil (B) is added in an amount of 0.5 to 50% by weight, and the silicone oil (B) is added to the poly-4-methyl-1-pentene at a temperature of 60 to 230 ° C. The present invention also provides a method for producing a poly-4-methyl-1-pentene composition, which comprises impregnating (A) for 5 minutes or more and then performing melt mixing.

The poly-4-methyl-1-pentene (A) used in the present invention is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and other α-olefins such as ethylene, propylene and 1-. It is a copolymer with butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like α-olefin having 2 to 20 carbon atoms, and usually 4-methyl-1-pentene is 85 mol%. It is a polymer mainly containing 4-methyl-1-pentene.
The melt flow rate (MFR, load: 5 kg, temperature: 260 ° C.) of poly-4-methyl-1-pentene (A) is preferably
It is in the range of 0.5 to 200 g / 10 min. MFR is
Those having a MFR of less than 0.5 g / 10 min have a high melt viscosity and poor moldability, and those having a MFR of more than 200 g / 10 min have a low melt viscosity and poor moldability and low mechanical strength.

Incidentally, the silicone oil (B) described below is poly-4-methyl-1-
In order to increase the impregnation effect on the pentene (A), it is more preferable that the poly-4-methyl-1-pentene (A) is in powder form.

The silicone oil (B) used in the present invention has a viscosity at 25 ° C. of 50 to 8 × 10 ⁶ cp, preferably 5 × 10 ² to 5 cp.
It is in the range of × 10 ⁶ cp. Such silicone oil has the general formula (In the formula, R is a hydrogen atom, an aromatic organic group, or the same or different atom or group selected from an aliphatic saturated or unsaturated organic group, provided that the aliphatic organic group has 3 carbon atoms.
In the above cases, the group may contain a hetero ring or a hetero atom. n is a positive integer. ), Which is also referred to as an organopolysiloxane that is liquid at room temperature.

The poly-4-methyl-1-pentene composition of the present invention comprises the poly-4-methyl-1-pentene (A) in an amount of 50 to 99.5% by weight, preferably 80 to 98% by weight, and the silicone oil (B) in an amount of 0.5 to 50%. % By weight, preferably 2 to 20% by weight, and the dispersion state of the silicone oil (B) has an average maximum projected area of 3.0 × 10 ³ μm ² or less, preferably 2.0 × 10 ² μm ^2. And the maximum projected area is
It is characterized in that those having a size of 3.0 × 10 ⁴ μm ² or more are 10% or less, and more preferably those having a maximum projected area of 1.0 × 10 ⁴ μm ² or more are 10% or less.

In the composition of the present invention, the average maximum projected area of the silicone oil (B) is an index showing the dispersed state of the silicone oil (B) in the composition, and is measured by the following method.

A test piece (1 × 3 × 0.05 mm) molded from the composition is immersed in methyl ethyl ketone (MEK) at room temperature for 30 minutes or more to elute the silicone oil (B) from the test piece.

Several pieces of the test piece in which the silicone oil (B) is eluted are sliced to prepare a thin piece sample having a thickness of 10 μm.

Gold is vacuum-deposited on the cross section of the thin sample.

A cross section of a thin sample randomly selected from 10 or more is observed using a scanning electron microscope, and a cross-sectional photograph is taken.

The cross-sectional area of the holes seen in the cross-sectional photograph is measured, the maximum cross-sectional area of each thin piece sample is determined, and the average value is taken as the average maximum projected area.

In order to obtain the poly-4-methyl-1-pentene composition of the present invention, the poly-4-methyl-1-pentene (A) and the silicone oil (B) are each added in an amount within the range of 60 to 230.
It can be produced by a method of impregnating poly (4-methyl-1-pentene (A)) with silicone oil (B) at a temperature of 80 ° C., preferably 80 to 150 ° C., and then melt mixing.

When the temperature of the impregnation treatment is less than 60 ° C, the silicone oil (B) is not impregnated in the poly-4-methyl-1-pentene (A) at all,
A composition having good dispersibility cannot be obtained. On the other hand, when the temperature exceeds 230 ° C, poly-4-methyl-1-pentene (A) softens and the temperature rises to 240 ° C.
Therefore, it cannot be melted and mixed uniformly with an ordinary extruder.

Poly 4-methyl-1-pentene (A) and silicone oil
When the (B) and (B) are impregnated at a predetermined temperature, stirring is preferable because the impregnation can be effectively performed in a short time. Further, the impregnation time varies depending on the amount of poly-4-methyl-1-pentene (A) and the like, but when impregnation is carried out for 5 minutes or longer, preferably 20 minutes or longer, the impregnation can be carried out to such an extent that melt mixing is possible.

Poly 4-methyl-1-pentene (A) and silicone oil
The impregnation treatment with (B) can be carried out using a Henschel mixer, a tumbler blender, a V-blender, a ribbon blender or the like heated to a predetermined temperature. The melt mixing after impregnation is usually performed using a single-screw extruder, a multi-screw extruder, etc.
To 340 ° C., preferably 280 to 300 ° C., by melt extrusion.

Silicone oil (B) poly-4-methyl-1-pentene
To confirm the impregnation state in (A), the pellet or powder of poly-4-methyl-1-pentene (A) should be silicone oil (B).
It can be carried out by visual observation such as a state in which the gloss due to the silicone oil (B) is reduced by absorbing the oil or the fluidity of the mixture is improved (a smooth state).

The poly-4-methyl-1-pentene composition of the present invention is added to ordinary polyolefins such as weather resistance stabilizers, heat resistance stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, pigments, dyes and inorganic fillers. Various compounding agents used as described above may be compounded within a range not impairing the object of the present invention.

〔The invention's effect〕

The poly-4-methyl-1-pentene composition containing the silicone oil of the present invention is excellent in retention of silicone oil, heat resistance, and mold release property as compared with other polyolefins such as polyethylene and polypropylene, and is aged. The release of silicone oil due to (aging) is small (change over time), and the effect can be maintained over a long period of time, so a release film when curing polyurethane for artificial leather, a separator for adhesive labels (labels with pressure-sensitive adhesive) (Backing paper), a substrate of an adhesive tape, or an injection-molded product having a complicated shape can be suitably used.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded.

Example 1 MFR: 5 g / 10 min of poly-4-methyl-1-pentene powder (hereinafter abbreviated as PMP) and silicone oil having a viscosity of 3 × 10 ³ cp (trade name: Toray Silicone SH200, 3000CS: manufactured by Toray Silicone Co., Ltd.) (Hereinafter abbreviated as S0-I) were separately left in an oven at 100 ° C. for 2 hours for preheating. Next, after measuring PMP / S0-I = 90/10 (wt%), put it into a Hensiel mixer (50) kept at 80 ° C and mix it under conditions of low speed for 5 minutes and high speed for 5 minutes to PMP S0-I.
Was impregnated in. Subsequently, the mixture was kneaded and granulated with a twin-screw extruder (PCM45, resin temperature: 270 ° C., manufactured by Ikegai Tekko KK) to obtain a composition-I. Then, a film was formed using the composition-I under the following conditions.

40 mmφ extruder (set temperature: 280 ° C.) T-die (set temperature: 280 ° C.) chill roll (cooling temperature: 40 ° C.) Film thickness (50 μ) The performance of the obtained film was evaluated by the following method.

Average maximum projected area of silicone oil: A thin sample was prepared according to the above method, and a cross-sectional photograph was taken at a magnification of 1000 times using a scanning electron microscope (MSM-2 type, manufactured by Akashi Seisakusho Co., Ltd.). The projected area was calculated.

Peel strength with cellophane tape: After attaching cellophane tape (trade name: Cellophane Nichiban Co., Ltd.) to the sample, use an Instron tensile tester (Instron) to pull the cellophane tape side 180 at a pulling speed of 200 mm / min. After peeling, the peel strength (g / 15 m) was measured.

Dynamic wear coefficient (μk): ASTM D 1894 Table 1 shows the results.

Examples 2 and 3 The mixing ratio of PMP and S0-I used in Example 1 was set to 1st, respectively.
The same procedure as in Example 1 was carried out except that the ratios shown in the table were used. The results are shown in Table 1.

Example 4 Instead of S0-I used in Example 1, a silicone oil having a viscosity of 1 × 10 ⁵ cp (trade name Toray Silicone SH200, 100,000 C) was used.
The same procedure as in Example 1 was performed except that S, manufactured by Toray Silicone Co., Ltd., abbreviated as S0-II hereinafter) was used. The results are shown in Table 1.

Example 5 The composition-I obtained in Example 1 was applied to an injection molding machine (Meiki Seisakusho Co., Ltd., M100: cylinder temperature 300 ° C.) to obtain 10 cm × 10 cm.
A 2 mm thick square plate was formed. The performance was then evaluated by the method described in Example 1. The results are shown in Table 1.

Example 6 The composition-I obtained in Example 1 was aged (aged) in a gear oven at 60 ° C. for 3 days, and then the performance was evaluated by the method described in Example 1. The results are shown in Table 1.

Example 7 The composition-I obtained in Example 1 was aged (aged) in a gear oven at 60 ° C. for 7 days, and then the performance was evaluated by the method described in Example 1. The results are shown in Table 1.

Comparative Example 1 PMP and S0-I in Example 1 were not preheated and charged into a Hensiel mixer at room temperature and mixed. The resulting mixture is
S0-I was not impregnated into PMP and the surface of PMP was sticky. Then, the mixture was made into a composition by the method described in Example 1 below, and then the performance was evaluated. The results are shown in Table 1.

Comparative Example 2 In Example 2, PMP and S0-I were not preheated and charged into a Hensiel mixer at room temperature and mixed. The resulting mixture is
S0-I was not impregnated into PMP and the surface of PMP was sticky. Then, the mixture was tried to be kneaded by the method described in Example 1. However, S0-I slipped between the screw and the cylinder of the extruder and could not be extruded.

Comparative Examples 3 and 4 The same procedures as in Examples 3 and 4 were carried out except that PMP and S0-I and S0-II were not preheated in Examples 3 and 4 and that they were mixed in a Henschel mixer at room temperature. First result
Shown in the table.

Comparative Example 5 The mixing ratio of PMP and S0-I used in Example 1 was set to the first
The same procedure as in Example 1 was carried out except that the ratios shown in the table were used. The results are shown in Table 1.

Claims (2)

[Claims] 1. Poly-4-methyl-1-pentene (A) 5
General formula: 0 to 99.5% by weight, and a viscosity at 25 ° C. of 50 to 8 × 10 ⁶ cp: [In the formula, R represents a hydrogen atom, an aromatic organic group, or an atom or a group of the same or different types selected from an aliphatic saturated or unsaturated organic group. However, when the aliphatic organic group has 3 or more carbon atoms, the group may contain a hetero ring or a hetero atom. n is a positive integer], and the average maximum projected area of the silicone oil (B) is 3.0 × 10 ³ μm ² or less. A poly-4-methyl-1-pentene composition comprising: 2. Poly-4-methyl-1-pentene (A) 5
0 to 99.5% by weight and a viscosity at 25 ° C of 50
To 8 × 10 ⁶ cp in the general formula: [In the formula, R represents a hydrogen atom, an aromatic organic group, or an atom or a group of the same or different types selected from an aliphatic saturated or unsaturated organic group. However, when the aliphatic organic group has 3 or more carbon atoms, the group may contain a hetero ring or a hetero atom. n is a positive integer] and the silicone oil (B) is added in an amount of 0.5 to 50% by weight, and the silicone oil (B) is added to the poly-4-methyl-1-pentene at a temperature of 60 to 230 ° C. A method for producing a poly-4-methyl-1-pentene composition, which comprises impregnating (A) for 5 minutes or more and then performing melt mixing.