JPS60229941A - Glass-reinforced poly-4-methyl-1-pentene - Google Patents

Abstract

PURPOSE:To produce the titled composition having improved mechanical properties, etc. without deteriorating the transparency, by compounding a glass reinforcing material composed mainly of silicon dioxide to the base resin. CONSTITUTION:Poly-4-methyl-1-pentene is compounded with 5-40wt% glass reinforcing material containing >=95% silicon dioxide. The base resin may contain a modified poly-4-methyl-1-pentene grafted with an unsaturated carboxylic acid or its derivative. The modified resin is the one grafted with 0.1-15%, preferably 1-10% unsaturated carboxylic acid or its derivative (e.g. maleic acid, nadic acid, their anhydride, etc.) and having a melt flow rate of 1-500g/10min.

Description

[Detailed Description of the Invention] [Object of the Invention] The present invention provides a glass-reinforced poly(4-methyl-1) with excellent transparency.
- B to bebutene.

[Problems with conventional technology]

It is known that glass reinforcing materials are added to polyolefins to improve mechanical properties such as tensile strength, bending strength, impact strength, and surface hardness, melt properties such as melt tension, and heat deformation resistance. Among polyolefins, poly(4-methyl-1-pentene) has exceptional transparency and heat deformation resistance compared to other polyolefins such as polyethylene, polypropylene, and poly-1-butene, so glass reinforcement is added to it. If the above-mentioned mechanical properties are improved, the resin will be useful in a wide range of fields. However, even if a glass reinforcing material is simply added to poly-4-methyl-1-pentene, the glass reinforcing material and poly-4-pentene
Due to the difference in refractive index from methyl-1-pentene, poly-4
-Methyl-1-pentene Light scattering occurs inside the resin, and only a cloudy glass-reinforced poly-4-methyl-1-pentene is obtained. This will impair the transparency, which is a major feature of poly-4-methyl-1-pentene, and its value as a product will decrease.

In view of the above situation, the inventors of the present invention have continued to investigate whether it is possible to obtain glass-reinforced poly-4-methyl-1-pentene that does not impair transparency, and have decided to use a glass reinforcing material with a specific composition. I found out that I can achieve my goal.

[Structure of the invention]

That is, the present invention uses a glass reinforcing material containing 95% or more of silicon dioxide in poly-4-methyl-1-pentene.
This is glass-reinforced poly-4-methyl-1-pentene characterized by containing ~40% by weight.

Poly4-methyl-1-pentene used in the present invention is 4-methyl-1-pentene.
- Homopolymer of methyl-1-pentene or 4-methyl-1-pentene in a molar ratio of 15 or less, preferably 9
Other α-olefins below molti, e.g. evaporation ethylene,
It is a copolymer with an α-olefin having 27 carbon atoms and L20, such as propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, and 1-octadecene. Melt flow of poly-4-methyl-1-pentene!
-Rate (load 5 losses, temperature 260℃, below IV'fFR
) is preferably 1 to 500 f/10 [,
Particularly preferably 5 to 600 l/10. It belongs to i. If the MFR exceeds 500f/10111, the mechanical strength is low, and if the MFR is less than "/10ain, the moldability is poor.

The glass reinforcing material may be in any shape such as glass fiber, glass strand, glass roving, glass chopped strand, glass milled fiber, glass powder, glass tape, glass cloth, glass flake, etc., but it is preferably in the primary shape of the glass reinforcing material. In the case of powder, it is better to have a diameter of 100μ or less and 1μ or more, in the case of fibers, the diameter is 50μ or less and 1μ or more, and in the case of flakes, the thickness is 20μ or less and 1μ or more, which provides a good balance between transparency and mechanical strength. In good condition. At least 95% by weight of the glass component must be silicon dioxide. silicon dioxide (
If a glass reinforcing material having a Sin2) of less than 95% by weight is used, only a cloudy material with impaired transparency will be obtained when mixed with poly4-methyl-1-bentene.

However, if a weight coefficient of 95 or more is used, a composition with excellent transparency can be obtained, and in particular, if a powder-form one is used, a composition with even better transparency can be obtained.

As a method for producing a glass reinforcing material containing 95% by weight or more of silicon dioxide, a dry method is advantageous, for example, when glass powder is used. That is, crow powder obtained by thermal decomposition of silicon halides, thermal decomposition of silicic acid-containing substances, thermal decomposition of organosilicon compounds, etc. has a high purity silicon dioxide content and is suitable for the present invention. It is suitable for use as a crow reinforcing material. On the other hand, glass powder produced by a wet method has a silicon dioxide content of approximately 90% by weight or less, and is therefore unsuitable for use in the present invention.

In the present invention, poly4-methyl-1-pentene +
In order to strengthen the glass, the above-mentioned glass reinforcing material is added, but in order to further improve the glass reinforcing effect, the base material poly-4-methyl-1-pentene and the glass reinforcing material are bonded more firmly. It is preferable to use modified poly-4-methyl-1-pentene grafted with an unsaturated carboxylic acid or a derivative thereof, or to use it in combination. -Pentene is in the same category as the poly-4-methyl-1-pentene described above, but preferably has a melt flow in the range of 0.3 to 100 f/10 sin. If the melt flow rate is outside the above range, it is difficult to obtain a melt flow rate after graft modification of 0 within the range of 1 to 5 Q Q t An.

As unsaturated carboxylic acid or its derivative component unit,
Acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid, (endocys-vinchroC2)
, 2,1] hept-5-ene-2,3-dicarboxylic acid), or derivatives thereof, such as acid halides, amides, imides, anhydrides, esters, etc. , maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate,
Examples include dimethyl maleate and glycidyl maleate. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, or their acid anhydrides are particularly preferred.

The modified poly-4-methyl-1-pentene that may be used in the present invention is obtained by graft-copolymerizing the poly-4-methyl-1-pentene with an unsaturated carboxylic acid or a derivative thereof, and its base structure is preferably It is substantially linear and does not have a three-dimensional crosslinked structure, and this can be confirmed by the fact that it dissolves in an organic solvent such as P-xylene and the absence of a gel-like substance.○ Modified poly-4-methyl-1- Pentene is an unsaturated carboxylic acid or a derivative component thereof, preferably in a grafting amount of 0.1 to 15% by weight, particularly preferably 1 to 1% by weight.
The melt flow rate is preferably in the range of 1 to 500 f/1:n, and particularly preferably in the range of 1 to 5 to OOy/10w1n. Even if the graft amount is less than 0.1 weight φ, the thermal deformation density,
The effect of improving tensile strength, bending strength, impact strength, etc. is not sufficient, and on the other hand, if 15% by weight is used, the water resistance of the composition becomes poor.

Even when modified poly-4-methyl-1-pentene having a melt flow rate exceeding 500 f/10 units is used in the composition of the present invention, it is not possible to improve heat distortion temperature, tensile strength, bending strength, impact strength, etc. Not enough, on the other hand, ”/10m1n
If it is less than that, the melt viscosity is too thick and the wetting with the glass reinforcing material is poor, so that the effect of improving the mechanical properties of the composition will not be sufficient.

The modified poly-4-methyl-1-pentene used in the present invention may be within the above range, but by using one having the following properties, a composition with further improved heat resistance and mechanical strength can be obtained. I can do it. That is, it is preferably a modified poly-4-methyl-1-pentene having a molecular weight distribution (Mw/Mn) of 1 to 8, a melting point of 170 to 245 DEG C., and a crystallinity of 1 to 45.

Molecular weight distribution (Mw/M n
) (fl) The molecular weight distribution was determined by Kölpermeation chromatography (GPC). The molecular weight distribution was measured by GPC according to the following method.

That is, 0-dichlorobenzene was used as a solvent, and 0.04F of polymer was added to 100 parts by weight of the solvent (0.05F of 2.6-tert-butyl-p-cresol was added as a stabilizer to 100 parts by weight of the polymer). Add
After making a solution, it is passed through a 1μ filter to remove insoluble matter such as dust. after that.

Column temperature: 1 to 5°C; flow rate: 1. Measurements were made using a G'PC measuring device set at Omt/min, and numerical ratios were converted on a polystyrene basis.

The melting point of modified poly-4-methyl-1-pentene is a value measured by a differential scanning calorimeter (DSC). Note that the melting point here is measured as follows. First, the material was placed in a differential scanning calorimeter (duPout 990 model), which raised the temperature from room temperature at a rate of 20°C/l1fl 250
Once it reaches ℃, the temperature is lowered at a rate of 20℃/win to 25℃, then the temperature is raised again at a rate of 20"C/sin, and the melting point is read from the melting peak at this time (in many cases (In this case, the value on the higher melting point side was adopted because multiple melting points appeared.) The degree of crystallinity was measured by the following method. That is, the chart for measuring the melting point by DSC described above was The melting surface 1 (sl) of the measurement sample per unit amount is compared with the melting surface @ (So) on the recording paper corresponding to the melting energy (P o ) of the control sample of indium per unit amount.Indium P of
o is a known amount, and on the other hand, the melting energy 0 per unit amount of the crystalline part of poly-4-methyl-1-pentene is also known as shown below, so the crystallinity of the measuring needle can be determined by the following formula. .

Here, Po: 27J'oul/g (at 156±0
．． 5°C) P: 141.7 Joul/g [F, C,
Frank etal, Ph1losophical
Magazine.

4.200 (1959)] The glass reinforced poly-4-methyl-1-pentene of the present invention is
A glass reinforcing material of 5 to 40 M is added to 95 to 60% by weight of the poly-4-methyl-1-pentene. In addition, when using modified poly-4-methyl-1-pentene, the balance of 5 to 50% by weight of the glass reinforcing material is modified poly-4-methyl-1-pentene alone or poly-4-methyl-1-pentene.
It is a mixture with marten. If the blending amount is outside the above range, only products with poor mechanical properties, heat resistance, and moldability can be obtained.

The compositions of the present invention can be obtained by mixing the above-mentioned components within the above-mentioned proportions in various known ways, such as in a V-blender, ribbon blender, Henschel mixer, tumbler blender, or in an Ail bush blender.
Examples include a method of granulating with an extruder, a method of melting and mixing with a single-screw extruder, a multi-screw extruder, a Nigu, a Banbury mixer, etc., and then granulating or pulverizing.

Furthermore, in order to carry out graft modification, poly4-methyl-1-pentene, an unsaturated carboxylic acid or its derivative, and a glass reinforcing material can be simultaneously mixed and reacted and mixed in an extruder.

In addition, we also introduce other well-known ingredients such as weather-resistant stabilizers, heat-resistant stabilizers, lubricants, slip agents, antistatic agents, antifogging agents, nucleating agents, pigments, dyes, etc., which are usually added to polyolefins. They may be blended within a range that does not impair the purpose of the invention.

〔Effect of the invention〕

The glass reinforced poly-4-methyl-1-pentene of the present invention is
Without impairing the unique transparency of poly-4-methyl-1-pentene,
Rather, depending on the case, it can be made with excellent transparency, and can also improve mechanical properties and heat resistance.
Therefore, these products can be used in fields where transparency and heat resistance are required, such as home appliances such as microwave trays, fans, lamp covers, and laboratory equipment such as beakers and test tubes. It can be molded by various molding methods such as injection molding, blow molding, sheet molding, film molding, and lamic coat molding.

〔Example〕

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

The method for preparing the test pieces and the method for evaluating the properties of the test pieces used in the Examples and Comparative Examples are as follows.

Preparation of test pieces (A composition consisting of a predetermined ratio was mixed and mixed and granulated at 290°C using a 3Q mmφ vented-screw extruder. Using this pellet, physical property tests were performed using an injection molding machine under the following conditions. Create a piece.

Cylinder temperature = 290℃ Injection pressure: 350 dazzle/d Injection speed: 4. Oy/sec Mold temperature: 50℃ Also, the 1 m:rn thickness sheet for haze measurement is 2
Press molding was performed at 60°C.

■ MFR Based on ASTM-D-1238, at a temperature of 260℃,
Measurement was performed under a load of 5.0 K.

(2) [V] (Intrinsic viscosity) Measurement was carried out using a decalin solution at a temperature of 135° C. using an Ubbelod viscometer in the usual manner.

■ Haze: Based on ASTM-1746, 1 mrn Thickness L
/Measured by sheet.

■ Bending elastic modulus Method described in ASTM-D790 ■ Izod impact strength Method described in ASTM-IJ-256 ■ Crushing point strength Method described in ASTM-Ll-638 ■ Heat distortion temperature ASTM-D-648 Load 4.6 using the method described in
Using Ky/cJ ■ Method based on pencil hardness JIS K5400 ■ Measurement using a Sheartube refractometer using a 5 mm press sheet with refractive index Q Example 1 4-Methyl-1-pentene copolymer 1:R) (1- Decene content: 3 molar, intrinsic viscosity [η) = 2.3 d/V, M
FR=36, Mw/Mn=4. Q, melting point -235°C, crystallinity 34%, refractive index -1,465) with silica powder (Aerosil≠300■ manufactured by Nippon Aerosil Co., Ltd., 5iO2
= 99.5 wt%) was mixed with 10 wt%, and oxidation stabilizer Irganox 1010 (manufactured by Ciba Geigy) 0, 2
wt%, calcium stearate 0.3 wt%
290 mrn under nitrogen atmosphere in a 30 mrn extruder.
A granular sample was prepared at t. After drying this sample at 100° C. for 8 hours, it was injection molded and press molded into test soap pieces for physical property evaluation. The results are shown in Table 1.

Example 2 Same 4-methyl-1-pentene copolymer as Example 1 [R
] and silica powder, and the mixing amount was changed. The results are shown in Table 1.

Example 3 4-methyl-1-pentene copolymer [M] (1-decene content: 9 molar ratio, intrinsic viscosity [η): 2.4 d13/y,
M Ii' Bth-30, Mw/M n = 4.2
, melting point = 230°C, crystallinity 28%, refractive index -1,46
6) was mixed with the silica powder described in Example 1, and the same procedure as in Example 1 was carried out. The results are shown in Table 1.

Examples 4 and 5 Silica fiber (Alph
A predetermined amount of a-Quartz Izumi KK, 5in2=99%, diameter 10μ, length 6mrn) was mixed and the same procedure as in Example 1 was carried out. The silica fibers were surface treated with r-aminopropyltrimethoxysilane.

The results are shown in Table 1.

Example 6 Maleic acid graft modified 4-methyl-1-pentene copolymer [XR] obtained by grafting maleic anhydride in a toluene solution (1-decene content: 6 mol, maleic acid graft i: 1.5 wt%) , intrinsic viscosity -2,6dJ3/
f, Mw/Mn=4.7, melting point 234°C, crystallinity 62
The same procedure as in Example 1 was carried out except that the silica fiber described in Example 4 was mixed with the silica fiber having a refractive index of 1,467). The results are shown in Table 1.

Example 7 The same procedure as in Example 1 was conducted except that the copolymer (XR) described in Example 6 and the silica powder described in Example 1 were used.

The results are shown in Table 1.

Comparative Examples 1 to 3 Using the copolymers shown in Table 1, granulation was performed in the same manner as in Example 1 using a 30 mmφ extruder. The results are shown in Table 1.

Comparative Example 4 White carbon (■
Tokuseal UR manufactured by Tokuyama Soda KK, 5 in 2 = 86 pieces was mixed and the same procedure as in Example 1 was carried out.

The results are shown in Table 1.

Comparative Example 5 Copolymer [R) described in Example 1, white carbon, Tsubu Seal VN3: Nippon Silica KK [,5i02=86%
) and the same procedure as in Example 1 was carried out. The results are shown in Table 1.

In particular, the samples of Comparative Examples 4 and 5 exhibited a foaming phenomenon during molding.

Comparative example 6

Claims (1)

[Claims] (1) Glass-reinforced poly-4-methyl-1-pentene characterized by blending 5 to 40 polymers of glass reinforcing material containing 95% by weight or more of silicon dioxide to poly-4-methyl-1-pentene. . (2J;'r: The glass-reinforced poly-4-methyl-1-pentene according to claim 1, which is used in combination with a modified poly-4-methyl-1-pentene grafted with a saturated carboxylic acid or a derivative thereof.