JPS60112846A - Fiber-reinforced polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain titled composition of improved rigidity by incorporating as fibrous filler rock wool fiber (and glass fiber) in a composition made up of polyphenylene ether resin and vinyl aromatic hydrocarbon resin. CONSTITUTION:The objective composition can be obtained by incorporating (A) a composition made up of polyphenylene ether resin and vinyl aromatic hydrocarbon resin in a weight ratio 95/5-5/95 with (B) 5-50 (pref. 10-40)wt%, based on the whole composition, of rock wool fiber (produced by melting a raw material such as blast furnace slag or ore consisting mainly of silicic acid in a cupola at (a 150 deg.C followed by centrifuging the resulting melt into fibrous form, a fiber length <=500mu, diameter 2-15mu, aspect ratio 20-40) or its combination with glass fiber (in a weight ratio of the rock wool to the glass fiber 3/1-1/10). Both fibrous fillers are preferably surface-treated with silane compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition with improved r1 rigidity strength. For more details, please refer to (AiF
This invention relates to a polyphenylene ether resin composition having improved rigidity and strength by blending rock wool fiber and glass fiber with rock wool layer 4 as "Filling 4".

Polyphenylene ether resin is disclosed in U.S. Patent No. 330<
5874 specification, US Pat.
It is well known that this resin is used in practical applications as a resin that also has various other excellent physical properties.

Although polyphenylene ether-based resins have excellent heat resistance, they require extrusion and molding at high temperatures. Extrusion and molding at high temperatures lead to thermal deterioration of the polyphenylene ether resin, and as a result, the polyphenylene ether resin loses its original performance. As a way to improve this shortcoming,
For example, US Pat. No. εi' 3,583,435 discloses a resin composition h"Lf!J containing polyphenylene ether and styrene resin, and teaches a technique for improving moldability.

However, with this resin m-acid, the excellent properties originally possessed by polyphenylene ether, such as rigidity strength and heat resistance represented by thermal temperature, are generally impaired, so in order to improve this drawback, Alternatively, fillers are used to more effectively exhibit the characteristics of polyphenylene ether. Commonly used fillers include glass fiber,
Examples include glass peas, carbon fibers, asbestos, titanates and their whiskers, silicates, calcium carbonate, silica, and the like. For example, JP-A-52-125-561 discloses a composition containing polyphenylene ether, styrene, and polygonal calcium silicate; JP-A-53-840/19 discloses Polyphenylene ether resin M or polyphenylene ether resin combined with 1l111 impact modifier, mineral filler 4'' and nf plasticizer 1. composition, special publication Sho 5
Publication No. 7-501966 discloses a composition containing a polyphenylene ether resin, a 11'd/1 continuous impact polymer-modified polystyrene, a non-iron oxide mineral (1/1 filler, and an effective plasticizer), Each is disclosed.

Conventionally, glass fiber has been commonly used as a filler that increases the rigid VL strength represented by the flexural modulus and the heat resistance represented by the heat distortion temperature of polyphenylene ether resin compositions. The use of glass fiber certainly achieves the intended purpose, but on the other hand, it has the following disadvantages:
1) Glass fiber is expensive, It) Significant wear of the mold during molding, 111) Poor machinability of the molded product, IV) Poor surface smoothness of the molded product,■ Weld strength is not very good. etc. are recognized.

Therefore, an alternative filler to glass beads that does not have these drawbacks is desired.

As a result of our earnest efforts to find a fiber filler that does not have these drawbacks found in glass fiber ff1li, the inventors of the present invention have found Rockwool 49 #lI: , using glass fiber in combination with glass fiber if desired. The inventors have discovered that the disadvantages observed in the case of the present invention can be improved, and have arrived at the resin composition of the present invention.

That is, the present invention provides a resin composition containing a polyphenylene ether resin and a vinyl aromatic hydrocarbon flux resin.
#! This is a mf4m reinforced polyphenylene ether resin composition formed by filling rock wool fibers or blending rock wool fibers with glass fibers.

The polyphenylene ether resin in the present invention refers to polyphenylene 01 obtained by polycondensing one or more monocyclic phenols represented by the general formula (I) (herein, R1 is lower alkyl having 1 to 2 carbon atoms). &, R
2 and R3 are a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms, and a lower alkyl substituent is always present at the ortho position of at least one of the hydroxyl groups.1. c. ) and a graft copolymer having polyphenylene ether as its base obtained by graft polymerizing a vinyl aromatic compound to this polyphenylene ether. This polyphenylene ether may be a single polymer or a copolymer.

Examples of the monocyclic phenol represented by the general formula (1) include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-di7"lobylphenol, and 2,6-dimethylphenol.
-Methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-propylphenol, m-') resol, 2,6-dimethylphenol,
2゜6-diethylphenol, 2.6-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl-3-propylphenol, 2-ethyl-3-methylphenol, 2-ethyl-3-propylphenol ,2
-propyl-3-methylphenol, 2-propyl-3
-Ethylphenol, 2,3.6-dolymethylphenol, 2,3.6-dolyethylphenol, 2゜3.6-
Examples include dolibrovirphenol, 2,6-dimethyl-6-ethylphenol, 2,6-dimethyl-6-probylphenol, and the like.

Examples of polyphenylene ether obtained by polycondensation of one or more of these phenols include poly(2,6-dimethyl-1°4-phenylene) ether and poly(2,6-ethyl-1,4-phenylene) ether. , poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-methyl-6-nityl-1゜4)
-phenylene) ether, poly(2-methyl-6-broby-1,4-phenylene) ether, poly(2-ethyl-6-broby-1,4-phenylene) ether, 2
．． 6-dimethylphenol/2,3.6-drimedylphenol copolymer, 2,6-dimethylphenol/21
5.6-Driethylphenol co-IR combination, 2°6-diegolphenol/2. filtration, 6-dolimethylphenol copolymer, 2,6-diprobylphenol/2,3.
6-Dolimethylphenol copolymer, Bo! I (2,6
- Graft copolymerized by graft polymerizing styrene onto (dimethyl-1,4-phenylene) ether, Graft copolymerized by graft polymerizing styrene onto 2,6-dimethylphenol/2,3,6-1-limethylphenol copolymer Examples include merging. In particular, poly(2゜6-cymethyl-1
, 4-phenylene) ether, 2,6-dimethylphenol/2,3.6-1-limethylphenol copolymer, and a graft copolymer obtained by graft-polymerizing each of the former two with styrene is the polyphenylene used in the present invention. It is preferable as an x-chill resin.

Next, the vinyl aromatic hydrocarbon resin in the present invention is
A structural unit is added to the monomer 11 represented by the following general formula (It),
The polymer contains at least 25 m1%4 (where R4 is a hydrogen atom or a lower alkyl group, O is a halogen atom or a lower alkyl group, and p is O or
It is a positive integer of ~6. ), such as polystyrene, rubber-modified polystyrene (MII impact-resistant polystyrene), styrene-butadiene copolymer,
styrene-butadiene-acrylonitrile copolymer,
Examples include styrene-acrylic acid rubber-7crylonitrile copolymer, styrene-α-methylstyrene copolymer, styrene-butadiene block copolymer, and two or more of these may be used as a mixture.

The ratio of polyphenylene ether resin to vinyl aromatic hydrocarbon resin in the resin composition of the present invention is generally 9515 to 5/95, preferably 85/15 to 15/95.
85, more preferably 70,150 to 30/70.

The rock wool fiber in the present invention is produced using raw materials such as blast furnace slag and ore containing silicic acid as a main component using a cupola.
It is an amorphous mineral fiber with an artificial surface color of white or grayish white, which is melted at 00''C and made fine by centrifugal force.The main components are 5102, CaαAa20s, MgO and Fe.
205, and the composition ratio of each is 68% by weight M%.
~42.56~42.12~18.4~8 and 1 or less.

Rock wool fibers are generally produced as long fibers, but they are inconvenient as they are when used as a filler for Ili1 fats and are usually cut. The longer the fiber length, the more it contributes to improving the rigidity and strength of the resin composition, but if the fiber length is longer than necessary, it is inconvenient in terms of workability during production.Therefore, it is suitable for the resin composition of the present invention. The fiber length of rock wool used for
It is 0μ, more preferably 100 to 250μ. The performance of the resin composition is affected not only by the delicate length but also by the fiber diameter11, but the rock wool fibers suitably used in the resin composition of the present invention have a fiber diameter of 2 to 15μ,
Preferably it is 3 to 10μ, and the anubect ratio is 2
0-40 is preferred. The amount of rock wool fiber added in the resin composition of the present invention varies depending on the purpose, but is generally 5 to 50% by weight, preferably 10% by weight based on the total resin composition.
It is used in amounts ranging from -40% by weight. If the amount is below the lower limit, the effect of adding rock wool fibers will be difficult to recognize, and if the amount exceeds the upper limit, moldability will decrease.

The price of rock wool fiber is 190-250 yen/kg, and the price of glass fiber (500-400 yen/kg)
It is cheap in comparison. Since it is soft to the touch and has flexibility, the resin composition of the present invention containing rock wool fibers improves the above-mentioned drawbacks of glass fibers and improves rigidity and strength. Rock wool fibers may be used as they are, but in order to improve rigidity and strength, it is more desirable to treat the surface of the rock wool fibers with a surface treatment agent. A silane compound is preferable as the surface treatment agent.

Although the above-mentioned effects can be achieved by using only rock wool fibers, when rock wool fibers and glass fibers are used in combination, a synergistic effect is observed in improving rigidity and strength. In other words, when the rigidity strength when rock wool fiber is used alone and the rigidity strength when glass fiber is used alone are the same at the same additive level, when both are used together, the μmU strength is higher than when each is used alone. is also clearly improved. In addition, when the rigidity strength when Rockwool fibers are used alone is inferior to that when glass fibers are used alone, even if some of the glass fibers are replaced with Rockwool fibers, the rigidity strength does not decrease, but rather improves slightly. Rock wool fibers are commercially available in Japan under the trade name "Microfiber" from Nitto Boseki ■ and "Varnish Fiber FF" from Nippon Steel Chemical 1m.

The glass fibers used in the resin composition of the present invention are conventionally used in resins. You can use any one that is normally used for heavy duty. Glasses are generally classified into E-glass, C-glass, 8-glass, S-glass, etc. according to their composition, and have performance according to their composition.

Any of these can be used in the resin composition of the present invention, but E-glass is preferred in terms of performance and price.

Depending on the purpose of use, the average diameter of glass fibers is 6.
．． A variety of fibers are manufactured, ranging from B-fibers with an average diameter of 2μ to P-fibers with an average diameter of 18μ, but the resin composition of the present invention includes G-fibers with an average diameter of 9.4μ,
Alternatively, one fiber of 15μ is preferred. Glass fibers can be manually processed in the form of chopped strands or rovings, but any of them can be used in the resin composition of j of the present invention.

Although the glass fibers used here can be used as they are, it is more desirable that they be treated with a surface treatment agent, such as a silane compound.

Regarding the addition h when rock wool fiber and glass fiber tit are used together, the combined strength of both is 5 to 5% in the total resin composition.
50η (J11%, preferably Jf in the range of 10 to 40% by weight is sufficient. If the amount is below the lower limit, it is difficult to see the effect of both inno-one rivers, and if the upper limit is exceeded, the molding of the resin composition Processability is lowered.The ratio of rock wool fibers and glass fibers in combination is selected in the range of rock wool fibers/glass fibers - 6/1 to 1/10 (weight ratio).

Various elastomers or various additives that can be generally used in polyphenylene ether resin compositions may be added to the fiber-reinforced polyphenylene ether resin composition of the present invention, if desired.

The elastomer component is a common elastomer, such as A, V, Tobol-5k.
Written by y+Properties and 5tructu
res of Polymers” (John Wi
ley & 5ons, Inc.

1960) on pages 71 to 78, an elastomer is defined as having a Young's modulus of 105 at room temperature.
~109dyneS/crnl (0°1~1020'%
) means a polymer that is Specific examples of elastomers include A-B-A' sub-type elastomer block copolymer, A-B-
*Type elastomeric block copolymers, polybutadiene, polyisoprene, copolymers of diene compounds and vinyl aromatic compounds, nitrile rubber, ethylene-propylene copolymers, ethylene-propylene-diene copolymers (EP
DM), thiocol rubber, polysulfide rubber, acrylic acid rubber, polyurethane rubber, a graft product of butyl rubber and polyethylene, polyester elastomer, polyamide elastomer, and the like. In particular, A-B-
*Type elastomeric block copolymers are preferred. The terminal blocks A and 8 of this block copolymer are polymerized vinyl aromatic hydrocarbon block τ blocks, and B is a polymerized conjugated diene block or a conjugated diene block in which most of the double bonds are hydrogenated. The molecular weight of the B block is preferably larger than the combined molecular weight of the A and A' blocks. Terminal blocks A and A'
may be the same or different, and the block is a thermoplastic homopolymer or copolymer derived from a vinyl aromatic compound in which the aromatic moiety may be monocyclic or polycyclic.

Examples of cacarhinyl aromatic compounds include styrene, (χ-methylspoon, vinyltoluene, vinylxylene, ethylvinylgysylene, vinylnaphthalene and mixtures thereof. The central block B is a conjugated diene-based hydrogen ash, For example, elastomeric polymers derived from 1,6-butadiene, 2,6-dimethylbutadiene, isoprene and 1,6-pentadiene and mixtures thereof.The molecular weight of each end block A and N is preferably about 2 .ODD to about 10n,000, while the molecular weight of central block B is preferably about 25,000
00 to about 1.000,000. When using an elastomer in the resin composition of the present invention, the proportion of the elastomer in 100 parts by weight of the resin component is 0.
．． It is 5 parts by weight or more.

Examples of additives that can be used in the composition of the present invention include known flame retardants such as organic phosphate compounds, organic phosphonate compounds, and halogen-containing organic compounds; Known stabilizers exemplified by night compounds, hydrazine derivatives, amine derivatives, metal sulfides, etc.; exemplified by benzotriazole compounds, benzophenone compounds, sterically hindered amines, oxalic acid diamide derivatives, organic nickel complexes, etc. UV absorbers; olefin waxes such as polyethylene wax and polypropylene socks; additives such as oxidized chiku 7, zinc oxide, and carbon pro-7; glass fibers, glass peas,
Examples include inorganic fillers such as asbestos, wollastonite, mica, clay, talc, calcium oxide, and silica; carbon fibers, amide fibers, and heat-resistant phenolic resin fibers.

Hereinafter, the resin composition of the present invention will be specifically explained with reference to Examples and Comparative Examples. Unless otherwise specified, the parts and percentages of each constituent component of the 4ii1 fat composition are 1ff, 1ff,
fM group 3 (expressed as 1°).

Example 1 and Comparative Example 1 Intrinsic 1'b degree υ, 52607 g (25°C, in Rioloform) of 2.6-dimethylphenol/2I6.6
−)! 52 parts of J methylphenol copolymer (the latter proportion is 5 mol %), MIJ MB-resistant polystyrene (25°
Intrinsic viscosity of polystyrene matrix measured at C in chloroform as solvent: 0.95 dA/g, gel content measured in methyl ethyl ketone-acetone as solvent: 17° 1%) 48 parts, rock wool fiber [trade name:
Varnish fiber FFj, new 1 piece made by Tetsusei Kagaku ■, surface untreated, fiber length: average 120μ, fiber diameter, average 4μ,
Aspect ratio = 20-4o] 25.1 parts (equivalent to 20%), hydrogenated bisphenol A phosphite resin 0
．． 2 parts and 2°2'-methylene-bis(4-methyl-
(6-tert-butylphenol) o and s parts were warmed using a Henschel mixer. The resulting mixture was pelletized by extrusion using an AS-30 type twin-screw extrusion mill (manufactured by Nakayo Kikai Seisakusho) whose maximum cylinder temperature was set at 290"C, and then pelletized at a cylinder maximum temperature of 295"C.
A test piece was molded at an injection pressure of 1510 using a 5J-5513 injection molding machine (manufactured by Kagaki Seisakusho) set to 1510 (Example 1).

For comparison, a test piece was obtained using the same composition as in Example 1 and the same operation except that no rock wool fiber was used. However, the maximum temperature setting of the cylinder of the injection molding machine is 290℃,
The injection pressure was 1050kjXI (Comparative Example 1).

The main performance measurement results are shown below.

Example 1 Comparative Example 1 Heat deformation 1 plating CC) (264psi) 141.8 L5
2.4 Flexural strength (YI) 1072 1042 Flexural modulus of 0 35900 24400 By adding rock wool fibers, improvements in heat deformation temperature and flexural modulus were observed.

Example 2 and Comparative Example 2 In Example 1, rock wool fiber [varnish fiber F
Rock wool fiber "Microfiber-5I" instead of FJ
XjC product name, Nitto Boseki ■, surface treated with aminosilane compound, fiber length 150μ, #Jll! A test piece was obtained by performing the same operation and having the same composition as in Example 1, except that JL diameter: average 5μ] was used (Example 2).

For comparison, in Example 2, glass fiber [trade name rcsO6MA497], made by Asahi Fiberglass ■, chopped strand, E-glass was used, surface treated with a silane compound, fiber length: 6
A test piece was obtained in the same manner as in Example 1 with the same composition as in Example 1, except that a . Example 2).

The main performance measurement results and visual inspection results of the surface condition are shown below.

Example 2 Comparative Example 2 Heat distortion temperature ("C;) (2S4psi) 141.5
141.0 Flexural strength (YI) 109 1099 Flexural modulus (Y Rigid strength was achieved and the surface condition was better than in the case of glass fibers.

Examples 6 to 5 and Comparative Example 6 In Example 1, the composition was the same as in Example 1, except that 25.1 parts of varnish fiber FFJ was changed by 45.1 parts (equivalent to 50% trap) K, and the same procedure was followed. A test piece was obtained (Example 5).

28.7 parts (20%) of "varnish fiber FF" used in Example 1 and 14.3 parts of glass fiber used in Comparative Example 2
5 parts (10%)',,) Ka (y Mi Example 4), or "varnish fiber FF" at 14.55
(10%) and glass fiber used in Comparative Example 2 28.
7 parts (20%) (Example 5), and a test piece was obtained with the same composition and same operation as in Example 1, except that a blender was used to mix the glass fiber and other raw materials. Ta.

In addition, in Comparative Example 2, 1 part of glass fiber at 45° (50°
A test piece was obtained using the same composition as in Comparative Example 2 and the same operation except for using the same composition as in Comparative Example 6 (Comparative Example 6).

The main initial performance measurement results and visual inspection results of the surface condition are shown below.

Comparing Example 5 and Comparative Example 6, the bending strength is the same, and the bending strength of Example 4 is greater than the value estimated from additivity based on the values of Example 6 and Comparative Example 6. It is.

Example 6 and Comparative Example 4 2,6-dimethylphenol/2, used in Example 1
5.6-drimethylphenol copolymer 67 parts, impact-resistant polystyrene used in Example 1 66 parts, trifluorphosphate 6 parts, rock wool fiber used in Example 2 45.6 parts (60%) ), hydrogenated bisphenol A phosphor), 4HIff
A test piece was obtained in the same manner as in Example 1 except that 0.3 part of t-butylphenol was used (Example 6).

In addition, in Example B, the procedure was the same as in Example 6, except that the glass fiber used in Comparative Example 2 was used instead of the rock wool fiber, and a KV-blender for mixing glass fiber and other raw materials was used. A test piece was obtained (Comparative Example 4).

The main initial performance measurement results and visual inspection results of the surface condition are shown below.

Example 6 Comparative Example 4 Heat distortion temperature (264psi) 157.2 15
8.0 Bending strength (¥1), 1565 1ro90 Bending modulus (?) 61ooo 62200UL947L/-
(1/1+M7-)) V-I V-1 Surface condition Good Good Bad Examples 7 to 9 In Example B, except for using the Rosfural fiber used in Example 1 as the rock wool fiber. , Example 6
was repeated (Example 7).

In Example B, 60° 4 parts (2
0%) and the glass fiber used in Comparative Example 2 15.
2 parts (1096) (actual ['118)] or 15.2 parts (10%) of rock wool fiber and 60.4 parts (20%) of the glass fiber used in Comparative Example 2. Example 6) except that Example 9) was used, and a blender was used for mixing the glass fibers and the mixture of other raw materials.
The same operation was repeated with the same composition.

Major initial performance? ) 1.11 The results of determination and visual inspection of the surface condition are shown below.

For comparison, the results of Comparative Example 4 are also listed.

Comparing Example 9 and Comparative Example 4, the heat distortion temperature and bending strength are substantially the same, and in Example 8, the heat distortion temperature is equivalent to Comparative Example 4, and the bending strength is the same as that of Example 7 and Comparative Example 4. il under the assumption of additivity based on the values of Comparative Example 4.
is greater than the calculated value.

Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Representative Kazuyoshi Nagano

Claims (1)

[Claims] A +a+fat composition containing a polyphenylene ether-based 4M fat and a vinyl aromatic hydrocarbon water flux resin is added with fiber 2 ([rock wool fiber or rock wool as a filler ←'r #
tf jlc made by blending Ii and glass fiber! 1
IJi-based polyphenylene ether resin composition