JPH0216931B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to inorganic fiber reinforced poly-4-methyl-1-pentene compositions. More specifically, unsaturated carboxylic acid or its derivative graft-modified poly-4-
Inorganic fiber-reinforced poly(4-) containing methyl-1-pentene and nylon 66 with excellent heat resistance and mechanical strength.
The present invention relates to methyl-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 adding reinforcing materials such as glass fibers to polyolefins. However, simply mixing glass fibers with polyolefins will naturally limit the effect of improving the mechanical properties and heat resistance of polyolefins because there is no bonding force between the polyolefins and glass fibers. Saturated polyester does not have the same improvement effect as 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 Publication), a composition comprising a polyolefin, a modified polyolefin having an aromatic carboxylic acid anhydride unit, and a glass fiber surface-treated with an aminosilane compound (Japanese Patent Publication No. 52-31895), a polyolefin and maleic anhydride A process for producing a composition comprising a modified polyolefin and a glass reinforcing material obtained by melt-kneading the above in the presence of an organic peroxide in a nitrogen atmosphere, or a composition comprising these and an unmodified polyolefin (Japanese Patent Publication No. 51-10265) Public bulletin), etc. have been proposed, and have shown some effectiveness. However, recently, there has been an increasing demand for thermoplastic resins that have even better heat resistance, mechanical strength, and moldability, so-called engineering plastics. Both of these have insufficient heat resistance and mechanical strength, and further improvements are desired. As one of the improvement methods,
Japanese Patent Publication No. 56-9943 describes a polyolefin resin composition consisting of (A) an unsaturated carboxylic acid-added polyolefin resin or an unsaturated carboxylic acid-added polyolefin resin diluted with the polyolefin resin, (B) a nitrogen-containing resin, and (C) a filler. It is said that by mixing a nitrogen-containing resin, a composition with excellent mechanical strength, heat resistance, paintability, etc. can be obtained.
However, among polyolefins, poly4-methyl-1-pentene, which has particularly excellent heat resistance, has ABS and nylon 6, which are specifically described in this publication.
Even if ABS was added, the heat resistance was not improved at all, and ABS
It has been found that when mixed with other materials, the heat resistance actually decreases. In view of this situation, the present inventors conducted various studies in order to obtain an inorganic fiber-reinforced poly-4-methyl-1-pentene composition with improved heat resistance and mechanical strength, and as a result, they arrived at the present invention. That is, the present invention comprises poly4-methyl-1-pentene (A): 10 to 90% by weight, a graft amount of unsaturated carboxylic acid or its derivative component unit from 0.5 to 15% by weight (based on the graft modified product), and Graft-modified poly-4-methyl-1-pentene (B) with an intrinsic viscosity [η] in the range of 0.3 to 10 dl/g: 0.1 to 40% by weight, nylon 66: 5 to 85% by weight,
and inorganic fiber (C): 2 to 80% by weight, and provides an inorganic fiber-reinforced poly-4-methyl-1-pentene composition having excellent heat resistance and mechanical strength. Poly4-methyl-1-pentene used in the present invention
(A) is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and other α-olefins, such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1- Desen,
4-Methyl-1 is a copolymer with an α-olefin having 2 to 20 carbon atoms such as 1-tetradecene and 1-octadecene, and usually contains 4-methyl-1-pentene in an amount of 85 mol% or more, preferably 91 mol% or more. - It is a polymer mainly composed of pentene. Poly 4-methyl-
1- Melt flow rate of pentene (A) (load: 5
kg, temperature: 260℃) is preferably 5 to 500g/
10min, preferably 25 to 150/10min
It is within the range of . Melt flow rate is 5
Those with a melt flow rate of less than 500 g/10 min have a high melt viscosity and poor moldability, and those with a melt flow rate of more than 500 g/10 min have a low melt viscosity and are inferior to molds, and also have low mechanical strength. Poly-4-methyl-1-pentene grafted with unsaturated carboxylic acids or derivatives thereof is in the same category as poly-4-methyl-1-pentene (A) described above, but preferably in a decalin solvent at 135°C. The measured intrinsic viscosity [η] is in the range of 0.5 to 25 dl/g. If [η] is outside the above range, the intrinsic viscosity after graft modification will be 0.3 to 10.
It is difficult to obtain one within the dl/g range. Graft-modified poly-4-methyl- used in the present invention
1-Pentene (B) 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 substantially linear and has a three-dimensional crosslinked structure. This can be confirmed by the absence of gel-like substances when dissolved in organic solvents such as p-xylene. Graft-modified poly-4-methyl- used in the present invention
1-Pentene (B) has a grafting amount of unsaturated carboxylic acid or its derivative component unit in the range of 0.5 to 15% by weight, preferably 1 to 10% by weight, and an intrinsic viscosity [η] (decalin solvent at 135°C). The measured value) is in the range of 0.3 to 10 dl/g, preferably 0.5 to 5 dl/g. Graft amount is 0.5% by weight
Even if less than 15% by weight is used in the composition of the present invention, the effect of improving heat denaturation temperature, tensile strength, bending strength, impact strength, etc. will not be sufficient, while if it exceeds 15% by weight, the water resistance of the composition will be poor. It becomes like this. Graft modified poly-4-methyl-1-pentene (B)
Even if a composition with [η] of less than 0.3 dl/g is used in the composition of the present invention, the effect of improving heat distortion temperature, tensile strength, bending strength, impact strength, etc. is not sufficient;
If it exceeds 10 dl/g, the melt viscosity is too high and wettability with glass fibers is poor, so that the effect of improving the mechanical properties of the composition will not be sufficient. Graft-modified poly-4-methyl- used in the present invention
The purpose of the present invention can be achieved if 1-pentene (B) is 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. Can be done. That is, it preferably has a molecular weight distribution (w/n) of 1 to 8, a melting point of 170 to 245°C, and a crystallinity of 1 to 8.
45% and a DSC parameter of 4.0 or less.
It is pentene (B). Graft modified poly-4-methyl-1-pentene (B)
The molecular weight distribution (w/n) expressed as weight average molecular weight/number average molecular weight 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, 0.04 g of polymer per 100 parts by weight of solvent (2,6-di-tert-butyl-p-cresol as a stabilizer per 100 parts by weight of polymer)
Add 0.05 parts by weight) to form a solution, and then pass through a 1μ filter to remove insoluble matter such as dust. 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. Graft modified poly-4-methyl-1-pentene (B)
The melting point of is the value measured by 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 (do Pout990 type) and heated from room temperature to 20℃/
The temperature increases at a rate of min, and when it reaches 250℃, the temperature increases by 20℃/min.
After lowering the temperature to 25°C at a rate of 20°C/min, the temperature is raised again at a rate of 20°C/min, and the melting point is read from the melting peak at this time (in many cases, multiple melting peaks appear, so (in cases where the value on the high melting point side was adopted). Further, the degree of crystallinity was measured by the following method. In other words, using the chart used to measure the melting point by DSC described above, the melting area (S) of the measurement sample per unit amount and the melting energy (Po) of the control sample indium per unit amount on the recording paper are calculated. Compare the area (So). 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 Here, Po: 27 Joul/g (at156±0.5
℃) P: 141.7Joul/g [FCFrank, etal,
Philosophical Magazine, 4, 200
(1959)] In addition, the DSC parameter, which is a parameter of the composition distribution of graft-modified poly-4-methyl-1-pentene (B), is the melting area (S) of the sample measured by DSC described above at the melting point (i.e., the maximum peak). divided by the peak height. 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
The unsaturated carboxylic acid or its derivative component units constituting 1-pentene (B) are acrylic acid, methacrylic acid, α-methylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid. Acid, endocys-bicyclo[2.2.1]hept-5-2,3-
dicarboxylic acid (nadic acid), methyl-endocys-bicyclo[2.2.1]hept-5-ene-2,
Examples include unsaturated carboxylic acids such as 3-dicarboxylic acid (methylnadzic acid), and derivatives of unsaturated carboxylic acids such as acid halides, amides, imides, acid anhydrides, and esters of the unsaturated carboxylic acids. Specific examples include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these, unsaturated dicarboxylic acids or their 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 (B) is shown below.
That is, poly-4-methyl-1-pentene is subjected to graph modification 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 proportion of the radical initiator used is 0.1 to 100 parts by weight, preferably 1 part by weight, per 100 parts by weight of poly4-methyl-1-pentene.
and 50 parts by weight. The proportion of the solvent used when carrying out the modification reaction in a solution state is as specified in 4- above.
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 methyl-1-pentene polymer. 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 250°C.
It ranges from 30 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,
Examples include aryl peroxide, acyl peroxide, aroyl peroxide, ketone peroxide, peroxycarbonate, peroxycarboxylate, and hydroperoxide. As the alkyl peroxide, diisopropyl peroxide,
Di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexine-3, etc.; aryl peroxides such as dicumyl peroxide; acyl peroxides such as dilauroyl peroxide; aroyl peroxides; is dibenzoyl peroxide, ketone peroxides are methyl ethyl ketone hydroperoxide, cyclohexanone peroxide, etc. hydroperoxides are 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 (B) is preferably obtained by a solution method. Another method is to graft a mixture of poly4-methyl-1-pentene, an unsaturated carboxylic acid or its derivative, and a radical initiator in an extruder; -1-Pentene is easily thermally decomposed, and it is difficult to obtain graft-modified 4-methyl-1-pentene having [η] and the amount of unsaturated carboxylic acid or its derivative grafted within the above range, which is used in the present invention. Grafting amount of carboxylic acid or its derivative is 0.5% by weight
Even in the case of polyester resins, [η] is often less than 0.3 dl/g, and even when used in the composition of the present invention, the effect of improving the heat denaturation temperature may be poor. Nylon 66 used in the present invention is a type of known polyamide obtained by polycondensation of hexamethylene diamine and adipic acid, and is not particularly limited as long as it has a molecular weight that can be used as a resin. The inorganic fiber (C) used in the present invention is a fibrous substance made of an inorganic material such as glass fiber, carbon fiber, boron fiber, potassium titanate fiber, wollastonite, and asbestos fiber. Additionally, the surface of the inorganic fibers can be coated with silane compounds such as vinyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane,
-aminopropyltrimethoxysilane, N-(β
-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or the like. The composition of the present invention comprises the poly-4-methyl-1-
Pentene (A): 10 to 90% by weight, preferably 10 to 70% by weight, graft modified poly-4-methyl-1
- Pentene (B): 0.1 to 40% by weight, preferably
0.5 to 20% by weight, nylon 66: 5 to 80% by weight, preferably 10 to 80% by weight, and inorganic fiber (C): 2 to 80% by weight, preferably 10 to 60%.
% by weight. Graft modified poly-4-methyl-1-pentene (B)
If the amount is less than 0.1% by weight, the effect of improving heat resistance and mechanical strength will be small, while if it exceeds 40% by weight,
The effect of improving mechanical strength is saturated. If the amount of nylon 66 is less than 5% by weight, the effect of improving heat resistance and mechanical strength will be small, and if it exceeds 80% by weight, water resistance, especially heat resistance, will decrease. If the amount of inorganic fiber (C) is less than 2% by weight, the effect of improving heat resistance and mechanical strength will be small, while if it exceeds 80% by weight, the inorganic fibers will stand out on the surface of the molded product, significantly impairing its appearance.
In addition, the content of the grafted unsaturated carboxylic acid or its derivative unit is poly-4-methyl-1-
Pentene (A) + graft modified poly 4-methyl-1-
It is preferably in the range of 0.01 to 5% by weight based on 100 parts by weight of pentene (B). Content is 0.01
If it is less than 5% by weight, the effect of improving heat resistance and mechanical strength may be poor, while if it exceeds 5% by weight, water absorption may increase. The composition of the present invention can be obtained by mixing the components (A), (B), nylon 66, and (C) within the ranges described above. There are various known mixing methods, such as mixing using a hexyl mixer, V-blender, ribbon blender, tumbler blender, etc. After mixing, melt kneading using a single screw extruder, twin screw extruder, kneader, etc., followed by granulation or An example is a method of 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 and improved mechanical strength than conventional glass fiber-reinforced poly-4-methyl-1-pentene.
It is applied to home appliances and automobile parts that require heat resistance, such as connectors, tuners, switches, heater ducts, and radiator fans. Next, the present invention will be explained in more detail with reference to Examples. Production example 1 4-methyl-1-pentene homopolymer ([η]
1.7dl/g, w/n7.5, melting point 241℃, crystallinity
The grafting reaction of maleic anhydride was carried out with dicumyl peroxide catalyst at 145 °C in toluene solvent using DSC parameter 3.0 (42%, DSC parameter 3.0). By adding a large excess of acetone to the obtained reaction product, the polymer was precipitated and collected, and the precipitate was repeatedly washed with acetone to obtain maleic anhydride graft-modified poly-4-methyl-1-pentene A.
(hereinafter referred to as graft-modified 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. Production example 2 4-methyl-1-pentene homopolymer ([η]
3.8dl/g, w/n7.3, melting point 240℃, crystallinity
41%, DSC parameter 3.2) for maleic anhydride and 2,5-dimethyl-2,5-ditert
Butylperoxy-hexyne-3 was added, and the mixture was supplied to a single-screw extruder set at 260°C under an _N2 atmosphere and melt-kneaded to obtain maleic anhydride-grafted poly-4-methyl-1-pentene B.
(hereinafter referred to as graft-modified TPX(B)) was obtained. The grafting ratio of maleic anhydride units in this modified polymer was 1.4% by weight, [η] 0.15dl/g,
Melting point 212℃, crystallinity 24%, w/n5.2, DSC
The parameter was 4.3. Examples 1 to 3 4-methyl-1-pentene homopolymer (hereinafter referred to as TPX) used in Production Example 1, nylon 66 (trade name Toray Alamine CM3006 manufactured by Toray Industries, Inc.), and the graft obtained in Production Example 1 Modified TPX-(A) and glass fiber (GF) were mixed in the proportions shown in Table 1, and then melt-kneaded in a single-screw extruder (molding temperature 280°C) to obtain a composition. The composition was molded using an injection molding machine (manufactured by Meiki Seisakusho).
A test piece was prepared using M100 (molding temperature: 280°C), and its physical properties were evaluated using the following method. Heat distortion temperature (HDT): ASTM D 648, load 264psi Izod impact strength (IZOD): ASTM D
256 Flexural Modulus (FM): ASTM D 790 Results are shown in Table 1. Comparative Examples 1 to 3 Nylon 6 (product name Toray Alamine CM1026 Toray Industries, Inc.) was used instead of nylon 66 used in Example 1.
The same procedure as in Examples 1 to 3 was carried out except that the following methods were used. The results are shown in Table 1. Comparative Example 4 Instead of the unsaturated carboxylic acid graft modified poly 4-methyl-1-pentene A used in Example 1,
The same procedure as in Example 1 was conducted except that the graft-modified TPX-(B) obtained in Production Example 2 was used. The results are shown in Table 1. 【table】

Claims (1)

[Claims] 1 Poly-4-methyl-1-pentene (A): 10 to
90% by weight, the amount of grafting of unsaturated carboxylic acid or its derivative component unit is 0.5 to 15% by weight (based on the graft modified product), and the intrinsic viscosity [η] is 0.3 to 10
Graft modified poly-4-methyl-1 in the range of dl/g
- Inorganic fiber-reinforced poly 4 comprising: 0.1 to 40% by weight of pentene (B), 5 to 85% by weight of nylon 66, and 2 to 80% by weight of inorganic fiber (C).
-Methyl-1-pentene composition.