JPS647620B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fiber-reinforced poly-4-methyl-1-pentene composition with excellent flame retardancy. More specifically, unsaturated carboxylic acid or its derivative modified poly-4-
A fiber-reinforced poly-4-methyl-1-pentene composition comprising methyl-1-pentene and a flame retardant. 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 at a temperature higher than the melting point of the polyolefin in the presence of an organic peroxide
41906), 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 polyolefins such as polyethylene and polypropylene. Furthermore, applying the method of Japanese Patent Publication No. 1983-31895, which uses aromatic carboxylic acid anhydride-modified polyolefin, to poly-4-methyl-1-pentene improves heat resistance and mechanical strength to some extent, but it is still not suitable for some applications. It wasn't enough. 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 has discovered that by further adding a flame retardant to such a composition, a composition that maintains heat resistance and mechanical strength and is excellent in flame retardant properties can be obtained. That is, the present invention provides poly4-methyl-1-pentene []: 80 to 99.99 parts by weight, poly4-methyl-1-pentene [ ]: 80 to 99.99 parts by weight,
The grafting amount of unsaturated carboxylic acid or its derivative component unit obtained by modifying 1-pentene with unsaturated carboxylic acid or its derivative in a solution state is
Range of 0.5 to 15% by weight and ultimate strength [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, fiber reinforcement []: 1 to 300 parts by weight, and the same [] +
[] = 100 parts by weight of flame retardant []: 10 or more
300 parts by weight of a flame-retardant fiber-reinforced poly-4-methyl-1-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,
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 [ ] refers to the poly-4-methyl-
It is a product obtained by graft copolymerizing unsaturated carboxylic acid or its derivatives to 1-pentene, 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
- Solubility in xylene, which can be confirmed by the absence of gel-like substances. Graft-modified poly-4-methyl- used in the present invention
1-pentene [ ] has a grafting amount of unsaturated carboxylic acid or its derivative component unit of 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. 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 distortion 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. Even when the composition of the present invention is used for graft-modified poly-4-methyl-1-pentene [ ] with [η] of less than 0.3 dl/g, 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. The present invention uses graft-modified poly(4-methyl-)
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, compare the melting area S of the measurement sample per unit amount with the melting area (So) on the recording paper corresponding to the melting energy (po) per unit amount of indium, which is a control sample. . 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: 27Joul/g (at156+0.5℃) P: 141.7Joul/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 obtained by dividing the melting area S of the sample measured by DSC described above by the peak height at the melting point (ie, the maximum peak). 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 unit constituting 1-pentene [] includes acrylic acid, maleic acid, fumaric acid, tetrahydralophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadzic acid ( Endocysubicyclo[2,2,1]hept-5-ene-
2,3-dicarboxylic acid] or derivatives thereof, such as acid halides, amides, imides, anhydrides, esters, etc.
Specific examples include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, 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 hexane, heptane oxane, decane, dodecane,
Aliphatic hydrocarbons such as tetradecane, kerosene, alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, cyclododecane, benzene, toluene,
Aromatic hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, trimethylbenzene, cymene, diisopropylbenzene, halogens such as chlorobenzene, bromobenzene, o-dichlorolobenzene, carbon tetrachloride, trichloroethane, trichloroethylene, tetrachloroethane, tetrachloroethylene Examples include hydrogenated hydrocarbons. 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, aryl peroxides, acyl peroxides, aroyl peroxides, ketone peroxides, peroxycarbonates, and peroxycarboxylates. , hydroperoxides, etc. As the alkyl peroxide, diisopropyl peroxide,
Di-tert-butyl peroxide, 2,5-dimethyl 2,5-di-tert-butylperoxy-hexyne-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 tart, etc.
-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 will be greater than 15% by weight, and the improvement effect will not be 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 the composition has a [η] of 0.3 dl/g or less, the effect of improving the heat distortion temperature is poor even when used in the composition of the present invention. 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. In addition, the surface of these fiber reinforcements is coated with a silane compound such as vinyltriethoxysilane, 2-
It may be treated with aminopropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane, or the like. Among these, inorganic fibers, particularly glass fibers, are preferred because they have excellent reinforcing effects and do not reduce flame retardancy. The flame retardants [] used in the present invention include phosphoric acid esters such as tricresyl phosphate, cresyl phenyl phosphate, triphenyl phosphate, diphenyloctyl phosphate, and tributyl phosphate, tris(β-chloroethyl) phosphate, Halogen-containing phosphoric acid esters such as tris(dichloropropyl) phosphate, tris(2,3-dibromopropyl) phosphate, tris(bromochloropropyl) phosphate, chlorinated paraffin, chlorinated polyethylene, brominated polyphenyl, chlorinated polyphenyl , dechlorane, dechlorane plus, tetrabromoethane, tetrabromobutane, 1,2-dibromo-3-chloropropane,
1,2,3-tribromopropane, hexabromocyclododecane, tetrabromobenzene, chlorinated diphenyl, decabromophenyl oxide,
Halogen compounds such as N,N'-ethylenebis-tetrabromophthalimide, antimony compounds such as antimony trioxide, potassium antimony tartrate, triphenylstibine, boron compounds such as borax, zinc borate, barium metaborate, hydroxide Metal hydroxides such as magnesium, aluminum hydroxide, calcium hydroxide, barium hydroxide, etc. Among these, halogen compounds, especially dechlorane, decabrom diphenyl oxide, N,N'-ethylenebis-tetrabromphthalimide It is preferable to use a combination of a halogen compound such as brominated epoxy and antimony trioxide, or magnesium hydroxide to impart a flame retardant without causing a decrease in heat resistance or mechanical strength. 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 poly-4-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, and flame retardant []: 10 to [] + [] = 100 parts by weight.
6 to 300 parts by weight, preferably 25 to 200 parts by weight, and when a halogen compound and antimony trioxide are used together as a flame retardant, 6 to 200 parts by weight of the halogen compound and 4 parts by weight of antimony trioxide.
or 100 parts by weight. If the amount of graft-modified poly-4-methyl-1-pentene [] is less than 0.01 part by weight, the effect of improving heat distortion temperature and mechanical strength will be small. On the other hand, if it exceeds 20 parts by weight, the effect of improving mechanical strength such as bending strength, tension strength, and impact strength will be 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 spoil the appearance. Flame retardants〔〕
If the amount is less than 10 parts by weight, flame retardancy will not be imparted, while if it exceeds 300 parts by weight, the mechanical strength (particularly impact strength) will be significantly reduced. In addition, the content of the grafted unsaturated carboxylic acid or its derivative component unit is 0.001 based on the entire composition (100 parts by weight).
It is preferably in the range of 2% to 2% by weight. The composition of the present invention can be obtained by mixing each of the above-mentioned components [ ], [ ], [ ] and [ ] within the above-mentioned ranges. As the mixing method, various known methods such as Henschel mixer, V-
Examples include a method of mixing as necessary with a 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 also flame retardant. , electronic components, housings, etc. 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))
The grafting reaction of maleic anhydride was carried out using 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 abbreviated as MAH−TPX(A))
I got it. 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 manufactured by Nitto Boseki Co., Ltd., TPX(I)+ _MAH −TPX( _A )=
After adding and mixing 42 parts by weight, 55 parts by weight and 13 parts by weight to 100 parts by weight, the mixture was granulated using an ordinary extruder 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 ASTMD790. The thickness of the specimen is 1/8 inch. (2) 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 . (3) Flame retardancy A vertical combustion experiment was conducted based on UL94. The thickness of the specimen is 1/8 inch. The results are shown in Table 1. Example 2 The same procedure as in Example 1 was carried out except that the amounts of DBDO and Sb ₂ O ₃ used in Example 1 were changed as shown in Table 1. The results are shown in Table 1. Examples 3 and 4 The same procedure as in Example 1 was carried out except that dechlorane or N,N'-ethylenebis-tetrabromophthalimide (hereinafter abbreviated as TBPI) was used instead of DBDO used in Example 1. The results are shown in Table 1. Example 5 Example 1 except that 140 parts by weight of magnesium hydroxide (hereinafter abbreviated as water mag) was used instead of DBDO and Sh ₂ O ₃ used in Example 1, and the amount of GF was 6 parts by weight.
I went in the same way. The results are shown in Table 1. Comparative Example 1 The same procedure as in Example 1 was conducted except that DBDO and Sh ₂ O ₃ used in Example 1 were not added and the amount of GF added was 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 Fiber reinforcement []: 1 to 300 parts by weight, [] + [] = 100 parts by weight, flame retardant []: 10] 300 parts by weight of a flame-retardant fiber-reinforced poly-4-methyl-1-pentene composition.