JPS60258254A - Polyphenylene ether composition with improved moldability - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (+) BACKGROUND OF THE INVENTION The present invention relates to polyphenylene ether compositions, particularly polyphenylene ether compositions with improved moldability.

Polyphenylene ether has excellent electrical and mechanical properties, high heat distortion temperature, and self-extinguishing properties.
It is attracting attention as an extremely useful engineering plastic material. However, it has low impact strength and is somewhat brittle. Furthermore, since this resin has a high melting temperature and high melt viscosity, high molding temperatures and pressures are required during molding, making molding by melting difficult.

As one method for improving the moldability of polyphenylene ether, attempts have been made to blend it with other resins. For example, Japanese Patent Publication No. 43-17812 describes blending a high impact polystyrene resin with polyphenylene ether.

Although this composition has improved moldability and impact resistance, it is said that the moldability is still insufficient.

Another method to improve the moldability of polyphenylene ether is to add a plasticizer to polyphenylene ether.
No. 5220 discloses aromatic organic acid esters having good compatibility with polyphenylene ether resins, polyesters having aromatic groups, organic phosphate esters having aromatic groups, and chlorinated aromatic hydrocarbons. It has been shown that blending selected compounds into polyphenylene ethers or compositions of polyphenylene ethers and styrenic resins improves moldability.

However, a plasticizer (
For example, blending organic phosphate esters with aromatic groups improves molding processability, but significantly lowers thermal performance. This is because the blended plasticizer is extremely uniformly dispersed (molecularly dispersed) in a matrix made of polyphenylene ether or a composition of polyphenylene ether and styrene resin. It is thought that the point (Tg) decreases, and as a result, the heat resistance decreases.

The present inventors considered that it is desirable for the additive to have the following properties in order to suppress this decrease in thermal performance (heat resistance) and improve moldability (fluidity).

(1) At the time of molding, that is, under the flow state of the system, it must have good compatibility with M) I) Tux components and exhibit the same fluidity-improving effect as a plasticizer.

(2) During use, that is, under flow-stopped conditions (temperature range below 1 of the matrix), phase separation occurs from the matrix components,
It must not lower the Tg of the matrix.
1::.

However, in order to prevent a decrease in mechanical strength, it is necessary that the interfacial adhesive force between the phase-separated matrix and the matrix is strong to a certain extent, and it must have affinity with the matrix.

As a result of intensive studies from this perspective, the present inventors found that
This has led to the present invention.

[11] Summary of the invention The present invention provides polyphenylene ether, or 1, t'l
J phenylene ether and styrenic m fat! The object of the present invention is to provide a means for improving the moldability of the composition.

That is, the present invention provides polyphenylene ether, polyphenylene ether, a composition of polyphenylene ether and styrene resin,
The object of the present invention is to provide a polyphenylene ether composition with improved moldability, which is characterized by being mixed with a triazine compound represented by the following formula.

(Left below) R1, R2, R8: Saturated or unsaturated chain hydrocarbon residue having a linear or side chain having 1 to 10 carbon atoms, alicyclic hydrocarbon group, or aromatic hydrocarbon residue , or derivative residues thereof.

(R"l R21R' may be the same or different) Detailed description of the invention (1) Polyphenylene ether The polyphenylene ether used in the present invention has a cyclic structural unit represented by the general formula, The ether oxygen atom of one unit is connected to the benzene nucleus of the next adjacent unit, n is at least 50, and Q is independently a hydrocarbon containing no hydrogen, halogen, or tertiary α-carbon atom. groups, halohydrocarbon groups having at least 2 carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy groups and halocarbon groups having at least 2 carbon atoms between the halogen atom and the phenyl nucleus Indicates a monovalent substituent selected from the group consisting of hydrogenoxy groups.

A typical example of polyphenylene ether is poly(
2,6-Simethyl-1,4-phenylene) ether, poly(2,6-siethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2- Methyl-6-broby-1.4
-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-ethyl-6)
-broby-1,4-phenylene)ether, holJ
(2,6-')7"thyl-1°4-phenylene) ether, poly(2,6-') flobenyl-1,4-phenylene) ether, poly(2°6-dilauryl-1,4-phenylene) ) Ether, HoIJ (2,6-Sifenyl-1
, 4-phenylene) ether, poly(2,6-simethoxy 1,4-phenylene) ether, poly(2,6-simethoxy 1,4-phenylene) ether, poly(2-
Methoxy-6-ethoxy-1,4-phenylene) ether, poly(2-ethyl-6-cutialyloxy-1,4)
-phenylene) ether, poly(2,6-digerol-1,4-phenylene) ether, poly(2-methyl-6)
-Phenyl-1,4-phenylene)ether, H')
(2+6ybenzyl-1,4-phenylene)ether1. I-'IJ (2-ethoxy-1,4-phenylene)
ether, poly(2-chloro-1,4-phenylene) ether, poly(2,5-dibromo-1,4-phenylene) ether and the like.

Also, 2,6-dimethylphenol and 2.3.6-)su1fk7Z/-Ago□□, 2r6-'/)fl'7
! -” Copolymer of enol and 2,3,5,6-thitramethylphenol, 2,6-ethylphenol and 2,3
．． Mention may also be made of copolymers such as copolymers of 6-trimethylphenol.

Furthermore, the polyphenylene ether used in the present invention is
It also includes modified polyphenylene ethers such as polyphenylene ethers defined by the above general formula grafted with styrenic monomers (eg, EVA, styrene, p-methylstyrene, α-methylstyrene, etc.).

Methods for producing polyphenylene ethers corresponding to the above are known, for example, U.S. Pat.
No. 06875, No. 3257357 and No. 32573
58 Composite Specification and Japanese Patent Publication No. 52-1788
No. 0 and JP-A-50-51197.

A group of polyphenylene ethers which are preferred for the purposes of the present invention are those having alkyl substituents in the two positions ortho to the ether oxygen atom and also copolymers of 2,6-dialkylphenol and 2,3,6-trialkylphenol. is a graft polymer obtained by grafting these polyphthalate-1 non-+Pn+pn+p-p-p-1, enolyte, and irradiate.

(2) Styrenic resin The styrenic resin used in the present invention includes homopolymers such as polystyrene, poly-α-methylstyrene, poly-p-methylstyrene, butadiene rubber, styrene-butadiene copolymer, ethylene- High impact polystyrene modified with various rubbers such as propylene copolymer, ethylene-propylene-diene terpolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, Examples include acrylonitrile-butadiene copolymer, styrene-methyl methacrylate copolymer, etc., and these styrene resins are mixed in a proportion of 0 to 2000 parts by weight per 100 parts by weight of polyphenylene ether resin.

(3) Addition of other polymers Other polymers can be added to polyphenylene ether or a composition of polyphenylene ether and styrene resin for the purpose of improving impact resistance, etc. The added polymers include natural or There are synthetic rubber-like elastomeric polymers, such as natural rubber, polyisoprene,
Polybutadiene, a copolymer of styrene and a butadiene conjugated diene (including a block copolymer), an ethylene-propylene copolymer, an ethylene-propylene-non-conjugated diene terpolymer, etc. can be used.

In addition, polymers that have been imparted with sensitivity by introducing polar groups can also be used, such as rubber-like elastic polymers that have been imparted with sensitivity, as well as polyethylene, ethylene-vinyl acetate copolymers, polypropylene, etc. It is also possible to use a polymer in which sensitivity has been imparted to the polyolefin polymer of , itaconic acid, their anhydrides, etc.) or an unsaturated silane compound.

Moreover, the polymer imparted with sensitivity can be produced by block or random polymerization of ethylene and a vinyl monomer or vinyl silane having a polar group such as an unsaturated organic acid such as acrylic acid or an ester thereof.

When using rubber-modified polystyrene, the amount of the rubber-like elastic polymer or polymer imparted with sensitivity added is such that the total amount including the rubber content derived from it is 0.5 to 0.5 to the total amount of all polymer components. 50% by weight, preferably 2 to 40% by weight.

Moreover, when using a polymer imparted with sensitivity, it is preferable to add an inorganic filler. When a sensitized polymer and an inorganic filler are used together, the sensitized polymer is dispersed in the matrix of polyphenylene ether or a composition of polyphenylene ether and styrene resin, and the sensitized polymer is dispersed in the sensitized polymer. It forms a special structure that is selectively filled with inorganic fillers, and can obtain excellent physical properties such as mechanical strength. 1. □Inorganic fillers include titanium oxide, zinc oxide, talc,
Inorganic powders known as fillers for synthetic resins, such as clay, calcium carbonate, and silica, can be used.

The average particle diameter of the inorganic filler is preferably 0.05 to 1.0 μm, and the amount of the inorganic filler is 0.5 to 60% by weight, preferably 1 to 45% by weight, based on the entire composition obtained by mixing. used.

Furthermore, other polymers include polyphenylene ether,
Alternatively, a polyolefin graft polymerized with a styrene resin can also be used.

Polyphenylene ether graft polyolefin is a polyolefin that has a carboxyl group or silicic anhydride group in the main chain or side chain, such as ethylene/acrylic acid copolymer, ethylene/acrylic acid copolymer, etc. It can be obtained by grafting onto a methacrylic acid copolymer, maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic anhydride-modified ethylene/vinyl acetate copolymer, or the like.

Polyphenylene ether grafted polyolefins can also be obtained by grafting polyphenylene ether onto polyolefins having glycidyl groups in their side chains, such as ethylene/glycidyl methacrylate copolymers, ethylene/vinyl acetate/glycidyl methacrylate copolymers, etc. be able to.

In addition, as polystyrene craft polyolefin,
Styrene copolymers having a carboxylic acid group or cyclic acid anhydride group in the main chain or side chain of polystyrene, such as styrene/maleic anhydride copolymer, styrene/citraconic anhydride copolymer, styrene/itaconic anhydride copolymer Polyolefins having glycidyl groups in their side chains, such as polymers, styrene/asconitic anhydride copolymers, styrene/acrylic acid copolymers, styrene/methacrylic acid copolymers, etc.
For example, it can be obtained by grafting ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, or the like.

The amount added is based on polyphenylene ether or a composition of polyphenylene ether and styrene resin, and
Polyphenylene ether graft polyolefin and/or
Or, based on the total amount of polystyrene graft polyolefin, 0.1 to 50% by weight of polyphenylene ether graft polyolefin, preferably 1 to 30% by weight, 1 to 80% by weight of polystyrene graft polyolefin,
Preferably, a range of 1 to 30% by weight is used.

The grafted polyolefin can be added after graft polymerization in advance, but when using a polyolefin having a glycidyl group, it is necessary to combine it with a styrene resin having a polyphenylene ether or carboxylic acid or anhydride group at 150°C or higher. The graft reaction can be carried out by kneading at a high temperature.

Therefore, by kneading glycidyl group-containing polyolefin and polyphenylene ether or a composition of polyphenylene ether and styrene resin at high temperature, each component is mixed uniformly, and at the same time, the polyphenylene ether produced by the progress of the graft reaction A composition containing the graft polyolefin and/or the polystyrene graft polyolefin can be obtained all at once, and is the most preferred method from an economical point of view.

(4) Triazine compound The triazine compound used in the present invention is represented by the following formula.

R"+ R21R": A saturated or unsaturated chain hydrocarbon residue having a linear or bent side chain having 1 to 10 carbon atoms, an alicyclic hydrocarbon residue, or an aromatic hydrocarbon residue, or , tore, etc. derivative residues, (hi, g", nFu, .-a, eg'r l'□ are also good) R1, R2, R8 are, for example, methyl group, ethyl group, propyl group, Examples include inpropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, phenyl group, naphthyl group, etc. It will be done.

R'', R'' and V can have one or more substituents, for example the following can be used as substituents.

-R'(R': 01-CIG hydrocarbon group) -X
(X: halogen such as C1, Br, F, etc.) -OR5(
R': H or C1 to C1o hydrocarbon group) -NR'R7
(R6, R”: H or C1 to CIO hydrocarbon group) O
COR' (R8: C1-Cl0 hydrocarbon group) -C
0OR'(R": H or a hydrocarbon group from 01 to CXI) -COR"(R": a hydrocarbon residue from C1 to CIO) SOaR"(R": OH or CI -CI
Hydrocarbon group of O]oz -N.

CN The triazine compound of the present invention is intended to be compatible with the matrix component in a fluid state during molding, and crystallize and phase separate from the matrix component during use. Therefore, it is desirable that the melting point of the triazine compound of the present invention is slightly lower than the molding temperature.

Generally, the molding temperature of polyphenylene ether compositions is 11
05 to 350°C, preferably tL<H20'O to 300°C. Therefore, the triazine compound used in the present invention has a melting point of 105 to 350°C, preferably 150 to 300°C.
It is desirable that the temperature be within the range of ℃.

However, if the molding temperature is outside the above range due to the addition of a stabilizer or plasticizer, a triazine compound having a different melting point can be used accordingly. The amount added is 0.1 to 2.5 parts by weight, preferably 0.5 to 2.0 parts by weight, particularly preferably 2 to 2.0 parts by weight, per 100 parts by weight of all polymers.
10 parts by weight is desirable.

(5) Additives In the present invention, other additives may be used depending on the purpose.

Examples of additives include stabilizers, plasticizers, flame retardants, various inorganic fillers, mold release agents, and colorants.

The polyphenylene ether composition of the present invention is characterized by improved fluidity and is easily molded even when other additives are added.

[IV] Example Hereinafter, the present invention will be specifically explained with reference to Examples.

[Example-1] Parts by weight of poly-z,6-)methyl-1,4-phenylene ether (manufactured by Mitsubishi Yuka Co., Ltd., intrinsic viscosity in chloroform at 25°C) and high impact polystyrene (
(manufactured by Mitsubishi Yuka Co., Ltd., number average molecular weight 55,000, weight average molecular weight 200,000, microgel content 14.5% by weight)
50 parts by weight and 5 parts by weight of triphenyl cyanurate represented by the following structural formula (melting point measured with Yamato Kagaku's H1 melting point analyzer MP-1 model; 232°C) were heated to 260°C using a plastic bender. The mixture was melt-kneaded for 7.5 minutes.

After the cross-crossing was completed, the melt index (250°C, 4 loads on 10), which indicates moldability (fluidity), was measured, and a prescribed test piece was produced using a press, and the heat distortion temperature was measured (18.6 Kg/J load). Display the results -
Shown in 1.

[Comparative Example-1] Table 1 shows the results obtained in the same manner as in Example 11 except that triphenyl cyanurate was not used.

[Comparative Example-2] Table 1 shows the results obtained in the same manner as in Example-1, except that 5 parts by weight of altriphenyl phosphate (melting point: SO ℃) was used as a plasticizer in place of triphenyl cyanurate.
Shown in 1.

As is clear from Table 1, the use of triphenyl cyanurate significantly improves fluidity (moldability) and suppresses deterioration in heat resistance.

Although the plasticizer improves the fluidity, the heat resistance is greatly reduced, and the effect of the present invention can be understood.

Table-1 [Example-2] Obtained in the same manner as in Example-1 except that 5 parts by weight of )-0-tolylisocyanurate (melting point: 168°C) was used as a substitute for triphenyl cyanurate. Table 2 shows the results.
Shown below.

(Blank below) Procedural amendment (voluntary) 21 Name of the invention Polyphenylene ether composition with improved formability 3 Relationship with the case of the person making the amendment Patent applicant 2-5-2-5 Marunouchi, Chiyoda-ku, Tokyo, Amendment Column 6 of Detailed Description of the Invention in the Subject Specification, Contents of Amendment (1) From line 17 on page 18 to line 19 of the same page of the specification, ``It is desirable that the amount added should be...'' ``The amount added is 0.1 to 25% per 100 weights of all polymers in total.
Parts by weight are preferably Fio, 5 to 20 parts by weight, particularly preferably 2 to 10 parts by weight. ”.

Claims (1)

[Scope of Claims] A polyphenylene ether composition with improved moldability characterized by mixing polyphenylene ether or a composition of polyphenylene ether and styrene resin with a triazine compound represented by the following formula. , R" + R2+ R: a saturated or unsaturated chain hydrocarbon residue having a linear or side chain having 1 to 10 carbon atoms, an alicyclic hydrocarbon residue, or an aromatic hydrocarbon residue, or These derivative residues. (R" and 121 R" may be the same or different)