JPS647625B2 - - 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 an unsaturated carboxylic acid or its derivative-modified poly-4-methyl-1-pentene and a low-crystalline or amorphous α-olefin copolymer. 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 provides a composition that maintains heat resistance and improves impact resistance and deformation due to warpage after molding by further adding a low crystallinity or amorphous α-olefin copolymer to such a composition. It was discovered that something could be obtained. That is, the present invention comprises poly4-methyl-1-pentene [ ]: 80 to 99.99 parts by weight, and the amount of grafting of unsaturated carboxylic acid or its derivative component unit is
The range of 0.5 to 15% by weight and the intrinsic viscosity [η]
Graft modified poly 4 in the range 0.3 to 10 dl/g
-Methyl-1-pentene []: 0.01 to 20 parts by weight, [] + [] = 100 parts by weight, and fiber reinforcement []: 1 to 300 parts by weight, also [] +
[ ] = Crystallinity by X-ray for 100 parts by weight
A fiber-reinforced polyester comprising 1 to 100 parts by weight of an α-olefin copolymer [ ] of 35% or less and 0 to 2 parts by weight of a radical initiator [ ] to 100 parts by weight [ ]. 4-methyl-1
- Provides a pentene composition. Poly4-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 are
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 unsaturated carboxylic acid or its derivatives is in the same category as the poly-4-methyl-1-pentene described above, but preferably at 135°C in a decalin 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-
This can be confirmed by the fact that it dissolves in xylene and that no gel-like substance is present. 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
The purpose of the present invention can be achieved if 1-pentene falls within the above range, but by using one having the following properties, it is possible to obtain a composition with further improved heat resistance and mechanical strength. 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 on a polystyrene basis. 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 degree of crystallinity of the measurement sample can be determined by the following formula: . Crystallinity (%) = S / So × Po / P × 100 Here, Po: 27 Joul/g (at 156 ± 0.5°C) P: 141.7 Joul/g [FCFrank et al.,
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, peroxycarruboxylates, hydroperoxides, and the like. As the alkyl peroxide, diisopropyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butyl peroxide
Aryl peroxides such as dicumyl peroxide, acyl peroxides such as dilauroyl peroxide, aroyl peroxides such as dibenzoyl peroxide, ketone peroxides such as methyl ethyl ketone hydroperoxide and cyclohexanone peroxide, and hydroperoxides such as tert -butyl hydroperoxide, cumene hydroperoxide and the like. Among these are di-tert-butyl peroxide,
2,5-dimethyl-2,5-di-tert-butylperoxy-hexyne-3, dicumyl peroxide, dibenzoyl peroxide and the like are preferred. 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, or the like. Among these, inorganic fibers, particularly glass fibers, are preferred because they have excellent reinforcing effects and heat resistance improving effects. α-olefin copolymer used in the present invention []
is a copolymer with an X-ray crystallinity of 35% or less, preferably 30% or less, and usually has a melt flow rate (MFR: ASTM D 1238, L) of 0.01 to 100g/10min, preferably 0.5 to 100g/10min. 50g/
It is in the range of 10min. α-olefin copolymer [] refers to α-olefin, such as ethylene, propylene, 1-butene, 1-hexene, 4
- It is obtained by copolymerizing two or more α-olefins such as methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-octadecene. Specifically, ethylene・
Propylene copolymer, ethylene/1-butene copolymer, ethylene/4-methyl-1-pentene copolymer, propylene/ethylene copolymer, propylene/1-butene copolymer, propylene/4-methyl-1 -Pentene copolymers and the like can be exemplified. Further, the α-olefin copolymer [] may be copolymerized with a small amount of a diene monomer such as dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, or the like. 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 reinforcing material []: 1 to 300 parts by weight, preferably 10 to 100 parts by weight, α-olefin copolymer []: 1 to 100 parts by weight [] + [] = 100 parts by weight Parts by weight, preferably 5 to 50 parts by weight, and [ ] = 100 parts by weight, radical initiator []: 0 to 2 parts by weight, preferably 0 to 1 part 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 is small, while if it exceeds 300 parts by weight, the fiber reinforcement may emboss on the surface of the molded product. Significant deterioration in appearance. If the amount of α-olefin copolymer [ ] 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. The composition of the present invention contains a radical initiator [ ],
When 2 parts by weight or less, preferably 0 to 1.0 parts by weight, are added to 100 parts by weight of α-olefin copolymer [ ], bending strength, heat distortion temperature, warping after molding, etc. are further improved. However, when the amount of the radical initiator [] added exceeds 2 parts by weight, the mechanical strength is significantly reduced. Incidentally, the radical initiator [] is the aforementioned graft-modified poly-4-methyl-
It is in the same category as the radical initiator used in producing 1-pentene. In addition, the content of the grafted unsaturated carboxylic acid or its derivative component unit is determined by the total composition (100
The amount is preferably in the range of 0.001 to 2% by weight based on the total weight (parts by weight). The composition of the present invention can be obtained by mixing the above-mentioned components [], [], [], [] and [] within the above-mentioned ranges. There are various known mixing methods such as Henschel mixer,
Examples include a method of mixing as necessary with a V-blender, ribbon blender, tumbler blender, etc., melt-kneading with a single-screw extruder, twin-screw extruder, kneader, Banbury mixer, etc., and then granulating or pulverizing. 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 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. Experimental example 1 4-methyl-1-pentene homopolymer ([η]
17dl/g, w/n7.5, melting point 241℃, crystallinity
42%, DSC parameter 3.0; hereinafter abbreviated as TPX()), a graft 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 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 MAH-TPX(A))
) 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-437CS, Nitto Boseki Co., Ltd.) was added to 95 parts by weight of TPX () used in Experimental Example 1 and 5 parts by weight of MAH-TPX(A), which was also produced in Experimental Example 1.
(hereinafter abbreviated as GF), ethylene content 81 mol%, MFR 0.6 g/10 min, X-ray crystallinity 5
% of ethylene-propylene random copolymer (hereinafter abbreviated as EPR) is TPX () + MAH − TPX (A) =
After adding and mixing 30 parts by weight and 23 parts by weight to 100 parts by weight, they were granulated using an ordinary extruder (resin temperature 290°C) to obtain pellets. Next, test pieces were made from the pellets using an injection molding machine, and the following items were measured. (1) Bending strength Based on ASTM D790. The thickness of the specimen is 1/8 inch. (2) IZOD impact strength Based on ASTM D256. The thickness of the specimen is 1/8 inch. (3) Heat distortion temperature Based on ASTM D648. 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 onto a surface plate, and of the two corners on the other side, the surface plate is placed at the corner with the largest upheaval. The height was measured and considered the 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%, an MFR of 8 g/10 min, and a crystallinity of 25% by X-rays was used. The procedure was carried out in the same manner as in Example 1 except for using. The results are shown in Table 1. Example 3 The same procedure as in Example 2 was carried out except that GF was changed to 60 parts by weight and PBR was changed to 40 parts by weight. The results are shown in Table 1. Example 4 In addition to the composition of Example 1, 2,5-dimethyl-2,
The same procedure as in Example 1 was conducted except that 0.28 parts by weight of 5-di(tert-butylperoxy)hexane (hereinafter abbreviated as peroxide) was added to 100 parts by weight of EPR. The results are shown in Table 1. Example 5 The procedure of Example 1 was repeated except that 0.08 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane was added. The results are shown in Table 1. Comparative Example 1 95 parts by weight of TPX () used in Example 1 and
After adding and mixing 11 parts by weight of GF to 5 parts by weight of MAH-TPX(A), the mixture was granulated in the same manner as in Example 1 to obtain pellets. Performance evaluation was the same as in Example 1.

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Claims (1)

[Scope of Claims] 1. Poly4-methyl-1-pentene [ ]: 80 to 99.99 parts by weight, a grafting amount of unsaturated carboxylic acid or its derivative component unit in the range of 0.5 to 15% by weight, and intrinsic viscosity [η] is 0.3 to 10dl/
Graft-modified poly-4-methyl-1-pentene in the range of g []: 0.01 to 20 parts by weight, [] + []
= 100 parts by weight of fiber reinforcement [ ]: 1 or
300 parts by weight, also [] + [] = 100 parts by weight, α-olefin copolymer with a crystallinity of 35% or less by X-ray []: 1 to 100 parts by weight and [] = 100 parts by weight On the other hand, radical initiator []:
0 to 2 parts by weight of a fiber-reinforced poly-4-methyl-1-pentene composition.