JPS647621B2 - - Google Patents

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, the present invention relates to a fiber-reinforced poly-4-methyl-1-pentene composition containing unsaturated carboxylic acid or its derivative-modified poly-4-methyl-1-pentene, glass flakes, and/or mica. 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 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 at a temperature higher than the melting point of the polyolefin in the presence of an organic peroxide
41096), a composition consisting of a polyolefin, 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), A method for producing a modified polyolefin obtained by melt-kneading under a nitrogen atmosphere in the presence of an oxide and a glass-based reinforcing material, or a composition consisting of these and an unmodified polyolefin (Japanese Patent Publication No. 10265/1983), etc. has been proposed. It has been done and has been reasonably effective. However, the method of Japanese Patent Publication No. 49-41096, in which maleic anhydride, polyolefin, and glass fiber are treated simultaneously, or
Japanese Patent Publication No. 1989-1997- Using a modified polyolefin obtained by melt-kneading polyolefin and maleic anhydride in the presence of an organic peroxide in a nitrogen atmosphere.
Even if the method of No. 10265 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. In addition, Patent Publication No. 52-31895 using aromatic carboxylic acid anhydride-modified polyolefin was used as Poly4.
Even when applied to -methyl-1-pentene, the heat resistance and mechanical strength were improved to some extent, but it was still not sufficient for some uses. In view of this current situation, the applicant has developed a composition with excellent heat resistance and mechanical strength by first adding a specific modified poly-4-methyl-1-pentene to glass fiber-reinforced poly-4-methyl-1-pentene. It was discovered that a product could be obtained, and an application was filed as Japanese Patent Application No. 57-226948. The present invention further improves heat resistance by adding glass flakes and/or mica to such a composition.
It has been discovered that a composition that maintains mechanical strength and is suppressed from deformation due to warpage after molding can be obtained. That is, the present invention provides 80 to 99.99 parts by weight of poly-4-methyl-1-pentene, which is obtained by modifying poly-4-methyl-1-pentene in a solution state with an unsaturated carboxylic acid or a derivative thereof. Grafting amount of saturated carboxylic acid or its derivative component unit ranges from 0.5 to 15% by weight and intrinsic viscosity [η]
Graft-modified poly-4-methyl-1-pentene [] with a range of 0.3 to 10 dl/g: 0.01 to 20
Parts by weight, [] + [] = 100 parts by weight, fiber reinforcement []: 1 to 300 parts by weight, same [] +
[] = 100 parts by weight, glass flakes []
and/or mica: 1 to 200 parts by weight. Poly 4-methyl-1-pentene [] used in the present invention refers to a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and usually 15
mol% or less, preferably 9 mol% or less of other α-
Olefins, such as ethylene, propylene, 1-
It is a copolymer with an α-olefin having 2 to 20 carbon atoms such as butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, etc. The melt flow rate of poly4-methyl-1-pentene (load 5 kg, temperature 260°C, hereinafter abbreviated as MFR) is preferably 5 to 500 g/10 min,
Particularly preferred is 25 to 150 g/10 min. Items with MFR exceeding 500g/10min,
The mechanical strength is low, and if it is less than 5 g/10 min, the moldability is poor. The poly-4-methyl-1-pentene grafted with an unsaturated carboxylic acid or its derivative is in the same category as the poly-4-methyl-1-pentene described above, but is preferably heated at 135°C in a delicane solvent.
Intrinsic viscosity [η] measured at 0.5 to 25 dl/g
It is within the range of . If [η] is outside the above range, the intrinsic viscosity after graft modification will be 0.3 or more.
It is difficult to obtain one within the range of 10 dl/g. Graft-modified poly-4-methyl- used in the present invention
1-pentene [] is the poly-4-methyl-1
- It is obtained by graft copolymerizing pentene with an unsaturated carboxylic acid or its derivative, and its base structure is substantially linear, meaning that it does not have a three-dimensional crosslinked structure, which means that organic solvents such as p-
It can be confirmed by dissolving in xylene and by the absence of gel-like substances. Graft-modified poly-4-methyl- used in the present invention
1-Pentene [] means a compound in which the amount of grafting of unsaturated carboxylic acid or its derivative component unit is 0.5 to
15% by weight, preferably in the range of 1 to 10% by weight, and the intrinsic viscosity [η] (measured in decalin solvent at 135° C.) is in the range of 0.3 to 10 dl/g, preferably 0.5 to 5 dl/g. 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. is not sufficient, whereas if it exceeds 15% by weight,
The water resistance of the composition becomes poor. Even when graft-modified poly-4-methyl-1-pentene [ ] with [η] of less than 0.3 dl/g is used in the composition of the present invention, improvements in heat distortion temperature, tensile strength, bending strength, impact strength, etc. On the other hand, if it exceeds 10 dl/g, the melt viscosity is too high and wetting with glass fibers is poor, so that the effect of improving the mechanical properties of the composition is not sufficient. Graft-modified poly-4-methyl- used in the present invention
If 1-pentene [] falls within the above range, it is possible to achieve the object of the present invention, or it is possible to obtain a composition with further improved heat resistance and mechanical strength by using one having the following properties. can. That is, the graft-modified poly(4-methyl-) preferably has a molecular weight distribution (w/n) of 1 to 8, a melting point of 170 to 245°C, a crystallinity of 1 to 45%, and a DSC parameter of 4.0 or less.
1-pentene [ ]. The molecular weight distribution (w/n) expressed as weight average molecular weight/number average molecular weight of the graft-modified poly-4-methyl-1-pentene [] 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 o-dichlorobenzene as a solvent, for 100 parts by weight of the solvent,
0.04 g of polymer (2,6-di-tert as a stabilizer)
- Add 0.05g of butyl-p-cresol to 100 parts by weight of polymer) to form a solution, and then
Insoluble matter such as dust is removed through a filter. Thereafter, measurement was performed using a GPC measuring device set at a column temperature of 135°C and a flow rate of 1.0 ml/min, and the numerical ratio was converted to a polystyrene base. The melting point of the graft-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. In other words, the sample was placed in a differential scanning calorimeter (du Pout990 model) and heated from room temperature to 20
The temperature is increased at a rate of ℃/min, and when it reaches 250℃,
After lowering the temperature to 25℃ at a rate of ℃/min, increase the temperature again at a rate of 20℃/min and read the melting point from the melting peak at this time (in many cases, multiple melting peaks will appear). (in this case, the value on the high melting point side was adopted). Further, the degree of crystallinity was measured by the following method. That is, the above
Using a chart when measuring the melting point by DSC, the melting area (S) of the measurement sample per unit amount and the melting area (So) on the recording paper corresponding to the melting energy (Po) per unit amount of the control sample indium.
Compare. The amount of Po in indium is known, and the melting energy (P) per unit amount of the crystalline part of poly-4-methyl-1-pentene is also known as shown below, so the crystallinity of the sample to be measured is determined by the following formula: It is determined by Crystallinity (%) = S / So × Po / P × 100 where, po: 27 Joul/g (at 156 ± 0.5°C) P: 141.7 Joul/g [FCFrank etal.,
Philosophical Magazine, 4, 200
(1959)] Also serves as a parameter for the composition distribution of graft-modified poly-4-methyl-1-pentene []
The DSC parameter is the melting area (S) of the sample measured by DSC as described above, and the melting point (i.e. maximum peak).
divided by the peak height at . Therefore, it is estimated that the smaller the DSC parameter, the sharper the DSC curve and the narrower the composition distribution. Graft-modified poly-4-methyl- used in the present invention
Examples of the unsaturated carboxylic acid or its derivative component unit constituting 1-pentene are acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid,
Isocrotonic acid, nadic acid (endocys-bicyclo[2,2,1]hept-5-ene-2,3
- dicarboxylic acids), or derivatives thereof, such as acid halides, amides, imides, anhydrides, esters, etc. Specifically, examples include 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, and their acid anhydrides are particularly preferred. Graft-modified poly-4-methyl- used in the present invention
A preferred method for obtaining 1-pentene 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 solvent and heating the mixture. The ratio of radical initiator used is poly4-methyl-1-pentene.
The amount ranges from 0.1 to 100 parts by weight, preferably from 1 to 50 parts by weight, per 100 parts by weight. When carrying out the modification reaction in a solution state, the proportion of the solvent used is usually 100 to 100,000 parts by weight, preferably 200,000 parts by weight, based on 100 parts by weight of the poly-4-methyl-1-pentene.
and 10,000 parts by weight. The temperature during the modification reaction is usually 100 to 250°C, preferably 110°C.
The temperature range is from 200°C to 200°C, and the reaction time is usually from 15 to 600 minutes, preferably from 30 to 360 minutes. Solvents used in the modification reaction include aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, tetradecane, and kerosene, and alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and cyclododecane. Hydrocarbons, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, ethyltoluene, trimethylbenzene, cymene, diisopropylbenzene, chlorobenzene, bromobenzene, o-dichlorobenzene, carbon tetrachloride, trichloroethane, trichloroethylene, tetrachloroethane , halogenated hydrocarbons such as tetrachloroethylene, and the like. Among these, alkyl aromatic hydrocarbons are particularly preferred. Typical radical initiators used in the graft modification reaction are organic peroxides, more specifically alkyl peroxides,
These include aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, peroxycarboxylates, hydroperoxides, and the like. As the alkyl peroxide, diisopropyl peroxide,
Di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxy-hexyne-3, etc. Aryl peroxides include dicumyl peroxide, acyl peroxides include dilauroyl peroxide, aroyl Peroxides include dibenzoyl peroxide, ketone peroxides include methyl ethyl ketone hydroperoxide and cyclohexanone peroxide, and hydroperoxides include
Examples 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 the unsaturated carboxylic acid or its derivative used is usually 1 to 500 parts by weight, preferably 2 to 100 parts by weight, per 100 parts by weight of poly-4-methyl-1-pentene. 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 graft-modified poly-4-methyl-1-pentene obtained will be lower than 0.5% by weight, resulting in an improvement effect. Moreover, 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 that the improvement effect is not sufficient. Graft-modified poly-4-methyl- used in the present invention
As described above, 1-pentene [] is obtained by the solution method. Poly4-methyl-1-pentene can also be grafted by melt-kneading a mixture of poly-4-methyl-1-pentene, an unsaturated carboxylic acid or its derivative, and a radical initiator using an extruder.
Thermal decomposition of 1-pentene occurs and the graft-modified 4-pentene has [η] in the above range and the amount of grafting of the unsaturated carboxylic acid or its derivative used in the present invention.
Methyl-1-pentene was not obtained, and the amount of grafting of unsaturated carboxylic acid or its derivative was 0.5% by weight.
Even if it is used, [η] is 0.3 dl/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 used in the present invention [ ] refers to inorganic fibers such as glass fibers, potassium titanate fibers, metal-coated glass fibers, ceramic fibers, wollastonite, carbon fibers, metal carbide fibers, and cured metal fibers, and aramid fibers. It is a fibrous material such as organic fiber such as. 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, particularly glass fibers, are preferred because they have excellent reinforcing effects and heat resistance improving effects. The glass flakes [] and mica [] used in the present invention are not particularly limited as long as they are flaky, but usually have an aspect ratio (average diameter/average thickness of flakes) in the range of 10 to 500, and even 20.
The range is preferably from 300 to 300. Further, the size is preferably in the range of 20 to 2000 μm, more preferably 100 to 1000 μm, since it is effective in improving mechanical strength, appearance, dispersibility, etc. The composition of the present invention comprises the poly-4-methyl-1-
Pentene []: 80 to 99.99 parts by weight, preferably 90 to 99.9 parts by weight, graft-modified poly4-methyl-1-pentene []: 0.01 to 20 parts by weight,
Preferably 0.1 to 10 parts by weight, [ ] + [ ] = 100
Fiber reinforcement []: 1 to 300 parts by weight, preferably 10 to 100 parts by weight, glass flakes [] and/or mica [] to parts by weight [] + [] = 100 parts by weight: 1 200 parts by weight, preferably 5 to 150 parts by weight. If the amount of graft-modified poly-4-methyl-1-pentene [] is less than 0.01 parts by weight, there will be little effect on improving heat distortion temperature and mechanical strength, while if it exceeds 20 parts by weight, bending strength, tensile strength, impact strength, etc. The improvement effect on mechanical strength is small. In addition, if the amount of fiber reinforcement [] 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 reinforcement [] will stand out on the surface of the molded product, resulting in significant Appearance deteriorates. If the amount of glass flakes [] and/or mica [] is less than 1 part by weight, warpage after molding will not be improved;
If it exceeds 200 parts by weight, the decrease in mechanical strength (particularly the decrease in impact strength) will be significant. In addition, the content of the grafted unsaturated carboxylic acid or its derivative component unit is based on the entire composition (100 parts by weight).
It is preferably in the range of 0.001 to 2% by weight. The composition of the present invention can be obtained by mixing each of the above-mentioned components [ ], [ ], [ ], [ ], and/or [ ] within the above-mentioned ranges. As a mixing method, various known methods such as Henschel mixer, V-blender, ribbon blender, tumbler blender, etc. are used to mix as necessary, and after melt-kneading using a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, etc., Examples include granulation or pulverization methods. The composition of the present invention contains various compounding agents that can be added and mixed with ordinary polyolefins, such as heat stabilizers, weather stabilizers, nucleating agents, pigments, dyes, lubricants, and rust inhibitors. may be added as long as it does not impair it. 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. ,
Suitable for use in precision molded products such as tuners, switches, etc. that require strict dimensional accuracy, such as electrical and electronic parts. Next, the present invention will be further explained 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]
1.7dl/g, w/n7.5, melting point 241℃, crystallinity
42%, DSC parameter 3.0; hereinafter abbreviated as TPX(I)), a grafting reaction of maleic anhydride was carried out with a dicumylperoneside catalyst in a toluene solvent at 145°C. By adding a large excess of acetone to the resulting reaction product, the polymer is precipitated,
By filtering and repeatedly washing the precipitate with acetone, maleic anhydride graft modified poly-4-methyl-1-pentene A (hereinafter referred to as MAH-TPX (A)) was obtained.
) was obtained. The grafting ratio of maleic anhydride units in this modified polymer was 4.0% by weight, [η] 0.95dl/g,
Melting point 210℃, crystallinity 18%, w/n 4.5, DSC
The parameter was 2.8. Example 1 Glass fiber (6PA-473CS Nitto Boseki Co., Ltd.) was added to 95 parts by weight of TPX (I) used in Experiment 1 and 5 parts by weight of MAH-TPX (A), which was also produced in Experiment 1.
(hereinafter abbreviated as GF) and mica (white mica, P-80K manufactured by Harris Mining Corporation) were added to 100 parts by weight of TPX (I) + MAH - TPX (A) = 12.5 parts by weight. After mixing, Pellets were obtained by granulation using a conventional extruder. Next, test pieces were made from the pellets using an injection molding machine, and the following items were measured. (1) Bending strength Based on ASTMD790. The thickness of the specimen is 1/8 inch. (2) IZOD impact strength Based on ASTMD265. The thickness of the specimen is 1/8 inch. (3) Heat distortion temperature Based on ASTMD648. The thickness of the test piece was 1/4 inch, and the test was carried out under conditions of a load pressure of 18.56 kg/cm ² . (4) Warpage A square plate (130 x 130 mm) with a thickness of 2 mm is molded using an injection molding machine, and one side parallel to the flow direction is pressed on a surface plate, and of the two corners on the other side, the corner with the largest upheaval is determined. The height from the board was measured and considered as warpage. The results are shown in Table 1. Example 2 Glass flakes (CEF-048A manufactured by Nippon Sheet Glass Co., Ltd.) were used instead of the mica used in Example 1, and GF
The same procedure as in Example 1 was conducted except that the amounts of glass flakes and glass flakes were 14 parts by weight and 28 parts by weight, respectively. The results are shown in Table 1. Example 3 The amounts of GF and glass flakes in Example 2 were each 33
The same procedure as in Example 2 was carried out except that parts by weight were used. The results are shown in Table 1. Comparative Example 1 The same procedure as in Example 1 was conducted except that 11 parts by weight of GF alone was added without adding mica. The results are shown in Table 1. Comparative Example 2 The same procedure as Comparative Example 1 was carried out except that GF was changed to 25 parts by weight. The results are shown in Table 1. 【table】

Claims (1)

[Claims] 1 Poly-4-methyl-1-pentene []: 80 to 99.99 parts by weight, obtained by modifying poly-4-methyl-1-pentene in a solution state with an unsaturated carboxylic acid or a derivative thereof. , a graft-modified poly-4-methyl-1-pentene [ ] having a grafting amount of unsaturated carboxylic acid or its derivative component units in the range of 0.5 to 15% by weight and an intrinsic viscosity [η] of 0.3 to 10 dl/g: 0.01 to 20 parts by weight, [] + [] = 100 parts by weight, fiber reinforcement []: 1 to 300 parts by weight, also [] + [] = 100 parts by weight, glass flakes [] and/or Mica []: 1 to 200 parts by weight of a fiber-reinforced poly-4-methyl-1-pentene composition.