JPS60177052A - Fiber-reinforced poly-4-methyl-1-pentene composition - Google Patents

Abstract

PURPOSE:To produce the titled composition having excellent heat-resistance, mechanical strength and impact resistance of the base resin and suppressed deformation caused by the warpage of the molded article, by compounding poly-4- methyl-1-pentene with a specific modified poly-4-methyl-1-pentene, a reinforcing fiber and a specific alpha-olefin copolymer. CONSTITUTION:The objective composition is produced by compounding (A) 80- 99.99pts.(wt.) of poly-4-methyl-1-pentene, (B) 0.01-20pts. of a graft-modified poly-4-methyl-1-pentene having an intrinsic viscosity [eta] of 0.3-10dl/g and grafted with 0.5-15wt% unsaturated carboxylic acid or its derivative, (C) a reinforcing fiber material (1-300pts. per 100pts. of the components A+B), (D) an alpha-olefin copolymer having a crystallinity of <=35% measured by X-ray (10- 300pts. per 100pts. of A+B), and (E) a radical initiator (0-2pts. based on the component D).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fiber-reinforced poly-4-methyl-1-pentene composition in which deformation due to warping after molding is suppressed. More specifically, unsaturated carboxylic acid or its derivative modified poly-4-
Methyl-1-pentene and low crystalline or amorphous α
-Fiber-reinforced poly-4-methyl containing olefin copolymer-
1-Pentene compositions.

It is known to improve the mechanical properties and heat resistance of polyolefins, such as tensile strength, bending strength, and impact strength, by blending glass fibers with polyolefins. However, if glass fiber is simply mixed with polyolefin, there is no bonding force between the polyolefin and glass fiber, so there is a limit to the effect of improving the mechanical properties and heat resistance of polyolefin. The improvement effect cannot be compared to that of saturated polyester or epoxy resin. On the other hand, many methods have been proposed for improving the bonding strength between polyolefin and glass fiber. For example, a method in which maleic acid or maleic anhydride is reacted with polyolefin and glass fiber whose surface has been treated with an aminosilane compound in the presence of an organic peroxide at a temperature higher than the melting point of the polyolefin (Japanese Patent Publication No. 49-41096), polyolefin and a modified polyolefin having an aromatic carboxylic acid anhydride unit, and glass fibers surface-treated with an aminosilane compound (Japanese Patent Publication No. 31895/1989), in which a polyolefin and maleic anhydride are mixed in the presence of an organic peroxide. Methods for producing modified polyolefins obtained by melt-kneading in a nitrogen atmosphere and glass-based reinforcing materials, or compositions consisting of these and unmodified polyolefins (Japanese Patent Publication No. 51-10265), etc., have been proposed, and have some effectiveness. are listed.

However, the method of Japanese Patent Publication No. 49-41096 in which maleic anhydride, polyolefin, and glass fiber are treated simultaneously, or by melt-kneading polyolefin and maleic anhydride in a nitrogen atmosphere in the presence of an organic peroxide. Special Publication No. 51-10 using modified polyolefin
Even if the method of No. 265 is applied to poly-4-methyl-1-pentene, sufficient effects cannot be obtained because poly-4-methyl-1-pentene is easily thermally decomposed unlike other polyolefins such as polyethylene and polypropylene. do not have.

Although the heat resistance and mechanical strength of poly4-methyl-1-pentene can be improved to some extent by applying the method used in Japanese Patent Publication No. 31895/1989, which uses aromatic carboxylic acid anhydride-modified polyolefin, the heat resistance and mechanical strength are still not sufficient depending on the application. There wasn't.

In view of the current situation, the present applicant has previously developed a specific modified poly-4-
It was found that a composition with excellent heat resistance and mechanical strength could be obtained by adding methyl-1-pentene to glass fiber-reinforced poly-4-methyl-1-pentene. did.

The present invention further adds a low crystallinity or amorphous α-olefin copolymer to such a composition, thereby maintaining heat resistance and improving impact resistance, g, and deformation due to warpage after molding. It has been discovered that a composition can be obtained.

That is, the present invention provides poly4-methyl-1-pentene (I
): 80 to 99.99 parts by weight, the amount of grafting of unsaturated carboxylic acid or its derivative component unit is 0.5 to 1
5% by weight and intrinsic viscosity [η] of 0.3 to 10
d! /g of graft-modified poly-4-methyl-1-pentene (n): o, ot to 20 parts by weight, (1)
+ (II) = 100 parts by weight of fiber reinforcement (
I[[); 1 to 300 parts by weight, also [I]+
(I[) = α-olefin copolymer with a crystallinity of 35% or less by X-rays based on 100 parts by weight [■]: 1
Provided is a fiber-reinforced poly-4-methyl-1-pentef composition characterized in that it comprises from 1 to 100 parts by weight and (IV) to 2 parts by weight of a radical initiator (V): O to 100 parts by weight. It is something.

Poly 4-methyl-1-pentene [I] used in the present invention refers to a homopolymer of 4-methyl-1-pentene or a 4-methyl-1-pentene homopolymer
- Methyl-1-pentene and usually up to 15 mol%, preferably up to 9 mol% of other α-olefins, such as ethylene, propylene, 1-butene, l-hexene, 1-octene, 1-decene, -tetradecene , 1-octadecene and other α-olefins having 2 to 20 carbon atoms. The melt flow rate of poly-4-methyl-1-pentene (load 5 kg, temperature 260°C, hereinafter abbreviated as MFR) is preferably 5 to 500 g/10 m1n,
Particularly preferred is 25 to 150 g/10 m1. If the MFR exceeds 500 g/10 m1n, the mechanical strength is low, and if the MFR is less than 5 g/10 m1n, the moldability is poor.

The poly-4-methyl-1-pentene grafted with unsaturated carboxylic acid or its derivative is the aforementioned poly-4-methyl-1-pentene.
- intrinsic viscosity [η] of the same range as pentene (I), but preferably measured at 135°C in decalin solvent;
is in the range of 0.5 to 25 a/g. [η]
However, for those outside the above range, the intrinsic viscosity after graft modification is 0.3 to 10 d! / g is difficult to obtain.

The graft-modified poly-4-methyl-1-pentene (II) used in the present invention is obtained by graft-copolymerizing the poly-4-methyl-l-pentene with an unsaturated carboxylic acid or a derivative thereof, and its base structure is essentially It is superlinear, meaning that it 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 that no gel-like substance is present.

The graft-modified poly-4-methyl-1-pentene (II) used in the present invention has a grafting amount of unsaturated carboxylic acid or its derivative component units in the range of 0.5 to 15% by weight, preferably 1 to 10% by weight. and limiting viscosity [η]
(value measured in decalin solvent at 135° C.) is in the range of 0.3 to 10 d17 g, preferably 0.5 to 5 dl/H. Even if a grafting amount of less than 0.5% by weight is used in the composition of the present invention, the effect of improving heat deformation temperature, tensile strength, bending strength, impact strength, etc. will not be sufficient, whereas if it exceeds 15% by weight, , the water resistance of the composition becomes poor.

Even if graft-modified poly-4-methyl-1-pentene (Il) with [η] of less than 0.3 dl/g is used in the composition of the present invention, the heat distortion temperature, tensile strength, bending strength, impact strength, etc. On the other hand, if it exceeds 10 aj/g, the melt viscosity is too large and the wetting with glass fibers is poor, so that the effect of improving the mechanical properties of the composition is not sufficient.

The purpose of the present invention can be achieved if the graft-modified poly-4-methyl-1-pentene [■] used in the present invention is within the above range. A composition with improved optical strength can be obtained. That is, preferably the molecular weight distribution (Miv
/'i'tn) is a graft-modified poly-4-methyl-1-pentene (II) having a property of 1 to .

Molecular weight distribution (weight average molecular weight/number average molecular weight) of graft modified poly(4-methyl-1-pentene CI+)
Mw/Mn) is measured by gel permeation chromatography (GPC).

Measurement of molecular weight distribution by GPC was carried out according to the following method. That is, using 0-dichlorohenzene as a solvent, 0.04 g of polymer per 100 parts by weight of solvent.
(Add 0.05 g of 2,6-tert-butyl-p-cresol as a stabilizer per 100 parts by weight of the polymer) to form a solution, and then pass through a 1 μm filter to remove insoluble matter such as dust. After that, column temperature 13
Measurements were made using a GP'C measuring device set at 5° C. and a flow rate of 1.0 ml/min, and numerical ratios were converted using polystyrene haze.

The melting point of the graft-modified poly-4-methyl-1-pentene (II) is a value measured by a differential scanning calorimeter (DSC). Note that the melting point here is measured as follows. In other words, the sample is passed through a differential scanning calorimetric needle (du Pou
t 990 type), the temperature was raised from room temperature at a rate of 20°C/min, and when it reached 250°C, the temperature was lowered at a rate of 20°C/min, once lowered to 25°C, and then raised again to 20°C/min.
The temperature is increased at a rate of in, and the melting point is read from the melting peak at this time (in many cases, multiple melting peaks appear, so in this case, the value on the higher melting point side was adopted). Further, the degree of crystallinity was measured by the following method. That is, using the chart for measuring the melting point by DSC described above, calculate the melting area (S) of the measurement sample per unit amount and the melting energy (Po) of the control sample on the recording paper corresponding to the melting energy per unit amount of indium. Compare the area (So). Po of indium is a known amount, while poly-4-methyl-1-
Melting energy per unit M of crystal part of pentene (1)
) is also known as below, so the crystallinity of the measurement sample is determined by the following formula.

Here, Po: 27 Joul/g (at 15
G±0.5℃)P: 141.7 Joul/g
(F, C, Frank etal, Ph1losop
hical Magazine.

Sat., 200 (1959)) In addition, graft-modified poly-4-methyl-1-pentene (I
The DSC parameter that is a parameter of the composition distribution of I) is the melting surface M (S
) divided by the peak height at the melting point (fWJ, maximum peak). Therefore, it is estimated that the smaller the DSC parameter, the sharper the DSC curve and the narrower the composition distribution.

The unsaturated carboxylic acid or its derivative component units constituting the graft-modified poly-4-methyl-1-pentene (II) used in the present invention include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, and citraconic acid. , unsaturated carboxylic acids such as crotonic acid, isocrotonic acid, nadic acid (endocys-bicyclo' (2,2,1)hept-5-ene-2,3-dicarboxylic acid),
or its derivatives, such as acid halides, amides, imides, anhydrides, esters, etc., specifically malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate. Examples include. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid (2), and their acid anhydrides are particularly preferred.

A preferred method for obtaining graft-modified poly-4-methyl-1-pentene (II) used in the present invention is shown below. That is, poly-4-methyl-1-pentene is graft-modified by adding an unsaturated carboxylic acid or a derivative thereof and a radical initiator in a solution state in the presence of a medium and heating the mixture. The ratio of radical initiator used is poly-4-methyl-1
- ranging from 0.1 to 100 parts by weight, preferably from 1 to 50 parts by weight, based on 100 parts by weight of pentene. The proportion of solvent used when carrying out the modification reaction in a solution state is:
The amount is generally 100 to 100.000 parts by weight, preferably 200 to 10,000 parts by weight, per 100 parts by weight of the poly-4-methyl-1-pentene. The temperature during the modification reaction is usually in the range of 100 to 250°C, preferably 110 to 200°C, and the reaction time is usually in the range of 15 to 600 minutes, preferably 30 to 36 minutes.
The range is 0 minutes. The solvent used for the modification reaction is
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, tetradecane, kerosene, methylcyclopenkune, cyclohexane, methylcyclohexane,
Alicyclic hydrocarbons such as cyclooctane, cyclododecane, benzene, toluene, xylene, ethylbenzene,
Aromatic hydrocarbons such as cumene, ethyltoluene, trimethylbenzene, cymene, diisopropylbenzene, chlorobenzene, bromobenzene, o-'; halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride, trichloroethane, trichloroethylene, tetrachloroethane, tetrachloroethylene For example, Among these, alkyl aromatic hydrocarbons are particularly preferred.

Typical radical initiators used in the graft modification reaction are organic peroxides, and more specifically, alkyl peroxides, rubber oxides, acyl peroxides, aroyl peroxides, ketone peroxides, and peroxycarbonates. , peroxycarboxylate, hydroperoxide, etc. As the alkyl peroxide, diisopropyl peroxide,
Diter t-butyl peroxide, 2,5-dimethyl-2,5-diter t-butylperoxy-hexyne-3, etc.; aryl peroxides such as dicumyl peroxide; acyl peroxides such as dilauroyl peroxide; aroyl peroxide; Examples of the hydroperoxide include dibenzoyl peroxide, ketone peroxides include methyl ethyl ketone hydroperoxide and cyclohexanone peroxide, and examples of the hydroperoxide include tert-butyl hydroperoxide and cumene hydroperoxide. Among these are di-tert-butyl peroxide, 2,
Preferred are 5-dimethyl-2,5-di-tert-butylperoxy-hexyne-3, dicumyl peroxide, dibenzoyl peroxide, and the like. - The proportion of unsaturated carboxylic acid or its derivative used is usually 1/100 parts by weight of poly-4-methyl-1-pentene.
The amount is from 2 to 500 parts by weight, preferably from 2 to 100 parts by weight. If the amount of unsaturated carboxylic acid or its derivative added is less than 1 part by weight, the amount of grafted unsaturated carboxylic acid or its derivative in the obtained graft-modified poly-4-methyl-1-pentene will be lower than 0.5% by weight. The improvement effect is not sufficient, and if the amount of unsaturated carboxylic acid or its derivative added exceeds 500 parts by weight, the amount of grafted unsaturated carboxylic acid or its derivative becomes greater than 15% by weight, so the improvement effect is not sufficient. do not have.

The graft-modified poly-4-methyl-1-pentene (II) used in the present invention can be obtained by the solution method as described above. Even if a mixture consisting of poly-4-methyl-1-pentene, an unsaturated carboxylic acid or its derivative, and a radical initiator is grafted by melt-kneading in an extruder, thermal decomposition of poly-4-methyl-1-pentene occurs. , the graft-modified 4-methyl-1-pentene having [η] and the grafting amount of the unsaturated carboxylic acid or its derivative in the above range used in the present invention cannot be obtained, and the grafting amount of the unsaturated carboxylic acid or its derivative is 0. Even if it is .5% by weight [η
] is 0.3 a/g or less, and even when used in the composition of the present invention, the effect of improving heat distortion temperature is poor.

The fiber reinforcement material (III) used in the present invention includes inorganic fibers such as glass fiber, potassium titanate fiber, metal-coated glass fiber, ceramic fiber, wollastonite, carbon fiber, metal carbide fiber, and metal cured fiber, and aramid fiber. It is a fibrous material such as organic fiber such as fiber. Further, the surface of these fiber reinforcing materials may be treated with a silane compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, etc. Among these, inorganic fibers and glass fibers are preferred because they have excellent reinforcing effects and heat resistance improvement effects.

The α-olefin copolymer (IV) used in the present invention is
It is a copolymer with an X-ray crystallinity of 35% or less, preferably 30% or less, and usually has a melt flow rate (MFR) of 35% or less, preferably 30% or less.
: ASTM D 123B, L) 0.01 to 1
00g/10mln, preferably 0.5 to 50g
/10m1n. α-olefin copolymer (IV) refers to α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, ■-octene, 1-decene, 1-dodecene, l - It is obtained by copolymerizing two or more types of α-olefins such as tetradecene and 1-octadecene. Specifically, ethylene-propylene copolymer, ethylene-1
-Butene copolymer, ethylene/4-methyl-1-pentene copolymer, propylene/ethylene copolymer, propylene/l-butene copolymer, propylene/4-methyl-1
-Pentene copolymers and the like can be exemplified. The α-olefin copolymer (IV) also contains a small amount of diene monomer, such as dicyclopentadiene, ethylidenenorbornene, 1.
4-hexadiene or the like may be copolymerized.

The composition of the present invention comprises 80 to 99.99 parts by weight of the poly(4-methyl-1-pentene CI), preferably 90 parts by weight.
from 9,969 parts by weight, graft-modified poly-4-methyl-
1-pentene (n): o, ol to 20 parts by weight, preferably 0.1 to 10 parts by weight, [I]+(II)
= 100 parts by weight, fiber reinforcement [■]: 1 to 300 parts by weight, preferably 10 to 100 parts by weight,
Same < (1) + (II3 = α-olefin copolymer (IV): 1 to 100 with respect to 100 parts by weight
Parts by weight, preferably 5 to 50 parts by weight, and [■]=
The radical initiator (V): 0 to 2 parts by weight, preferably O to 1 part by weight, per 100 parts by weight.

If the amount of graft-modified poly-4-methyl-1-pentene (U) is less than 0.01 parts by weight, the effect of improving heat distortion temperature and mechanical strength will be small, while if it exceeds 20 parts by weight, bending strength, tensile strength, There is little improvement effect on mechanical strength such as impact strength. Furthermore, if the amount of fiber reinforcing material (III) is less than 1 part by weight, the effect of improving heat distortion temperature and mechanical strength will be small, while if it exceeds 300 parts by weight, the fiber reinforcing material will emboss on the surface of the molded product. There is a significant deterioration in appearance due to If the amount of α-olefin copolymer (IV) is less than 1 part by weight, impact resistance and warpage after molding will not be improved, while if it exceeds 100 parts by weight, rigidity and heat distortion temperature will decrease.

When the radical initiator (V) is added to the composition of the present invention, 2 parts by weight or less, preferably O to 1.0 parts by weight, based on 100 parts by weight of the α-olefin copolymer (IV), the bending strength is increased. , heat distortion temperature, warpage after molding, etc. are further improved. However, the amount of radical initiator (V) added is 2
If the amount exceeds parts by weight, the mechanical strength will drop significantly. The radical initiator [■] is in the same category as the radical initiator used in producing the above-mentioned graft-modified poly-4-methyl-1-pentene.

The content of the grafted unsaturated carboxylic acid or its derivative component unit is preferably in the range of 0.001 to 2% by weight based on 100 parts by weight of the entire composition.

As a method for obtaining the composition of the present invention, each of the above components (1)
, [11), (III), (IV) and (V) in the above range. As for the mixing method, various known methods such as a Henschel mixer, a blender, a ribbon blender, a tumbler blender, etc. are used as necessary, and a screw extruder, a twin screw extruder, a kneader, etc. are used.
Examples include a method of melt-kneading using a Banbury mixer or the like, followed by granulation or pulverization.

The composition of the present invention includes a heat stabilizer, a weather stabilizer, a nucleating agent,
Various compounding agents, such as pigments, dyes, lubricants, rust inhibitors, etc., which can be added and mixed with the polyolefin, may be added to the extent that the purpose of the present invention is not impaired.

The composition of the present invention has a significantly higher heat distortion temperature than conventional glass fiber-reinforced poly-4-methyl-1-pentene, has improved mechanical strength, and is less deformed due to warping after molding, so it can be used as a connector. It is suitable for use in precision molded products that require strict dimensional accuracy, such as electrical and electronic parts such as tuners and switches.

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

Experimental example 1 4-methyl-1-pentene homopolymer ([η] 1.7
di/g, Mw/Mn 7.5, melting point 241°C,
Crystallinity 42%, DSC parameters 3. O;hereinafter referred to as TPX
(1)), a grafting reaction of maleic anhydride was carried out at 145°C in a toluene solvent with a dicumylperonsite catalyst. By adding a large excess of acetone to the obtained reaction product, the polymer was precipitated, collected by filtration, and the precipitate was repeatedly washed with acetone to obtain maleic anhydride graft-modified poly-4-methyl-1-pentene A (
(hereinafter abbreviated as MAH-TPX(A)) was obtained.

The grafting ratio of maleic anhydride units in this modified polymer was 4.0% by weight, [η) 0.95 dl/g, melting point 210°C, crystallinity 18%, Mw/Hn 4.5, D
The SC parameter was 2.8.

Example 1 Glass fiber (6PA-437C3, Nitto Boseki Co., Ltd. i
! ! , hereinafter abbreviated as GF), and an ethylene-propylene random copolymer (hereinafter abbreviated as EPR) with an ethylene content of 81 mol%, V F Ro, 6 g/10 m1n, and a crystallinity of 5% by X-rays, were TPX (1) H-TP to 10M
X (A) = 30 parts by weight and 23 parts by weight each in 100 parts by weight
After adding and mixing parts by weight, use a normal extruder (resin temperature 290
℃) to obtain pellets. Next, a test piece was made from this pellet using an injection molding machine, and the following items were measured.

(11 bending strength was conducted based on ASTM D790. The thickness of the test piece was 1
/8 inches.

(2) IZOD impact strength Tested based on ASTM D256. The thickness of the test piece is l
/8 inches.

(3) Heat distortion temperature was determined based on ASTM0648. The thickness of the test piece is 1
/4 inch and a load pressure of 18.56 kg and 10 a.

(4) Mold a square root (130 x 130 mm) with a warp thickness of 2 mm using an injection molding machine, press one side parallel to the flow direction on a surface plate, and from the two corners on the other side, from the surface plate of the corner with the largest upheaval. The height was measured and considered as warp.

The results are shown in Table 1.

Example 2 Instead of the EPR used in Example 1, a propylene-1-butene random copolymer (hereinafter abbreviated as PBR) with a propylene content of 70 mol%, M F R of 8 g/10 m1n, and a crystallinity of 25% by X-rays was used. ) Example 1 except that
I did the same thing. The results are shown in Table 1.

Example 3 The same procedure as in Example 2 was carried out except that GF and PBR were changed to 60 parts by weight and 40 parts by weight, respectively.

The results are shown in Table 1.

Example 4 2,5-dimethyl-2,5-di(
tert-butylperoxy)hexane (hereinafter abbreviated as peroxide) to EPR: 0.2 parts per 100 parts by weight.
The same procedure as in Example 1 was carried out except that 8 parts by weight was added. The results are shown in Table 1.

Example 5 In Example 4, 2,5-dimethyl-2,5-di(tert-
The same procedure as in Example 1 was carried out except that 0.08 part by weight of butylperoxy)hexane was added. The results are shown in Table 1.

Comparative example 1

Claims (1)

[Claims] (11 Poly-4-methyl-1-pentene (1): 80 to 99.99 parts by weight, the amount of grafting of unsaturated carboxylic acid or its derivative component unit ranges from 0.5 to 15% by weight) and graft-modified poly-174-methyl-1-pentene (I) having an intrinsic viscosity [η] of 0.3 to 10 dl/g.
I): o, ox to 20 parts by weight, (1) + (I
I) = 100 parts by weight of fiber reinforcement (ITI)
: 1 to 300 parts by weight, same < (1) + (II
) = X-ray crystallinity of 3 for 100 parts by weight
A fiber characterized by comprising 5% or less of α-olefin copolymer (IV): 1 to 100 parts by weight, and radical initiator (V) jO to 2 parts by weight per (IV) = 100 parts by weight. Reinforced poly-4-methyl-1-pentene composition.