JPS6038456A - Polyarylene ester resin composition - Google Patents

Abstract

PURPOSE:To provide the titled resin compsn. having excellent heat resistance, rigidity, strength, etc., low mold shrinkage factor and excellent mold release characteristics and suitable for use in the production of electrical parts, etc., by blending a reinforcing fiber or an inorg. filler and a fluororesin with a polyarylene ester. CONSTITUTION:20-80wt% polyarylene ester synthesized from a dihydric phenol (derivative) and an arom. dibasic acid (derivative), 10-70wt% reinforcing fiber (e.g. glass fiber or carbon fiber) or inorg. filler (e.g. talc or calcium carbonate) and 0.5-20wt% fluororesin are mixed together to obtain the desired polyarylene ester resin compsn. Examples of the fluororesin are teterafluoroethylene resin, tetrafluoroethylene/hexafluoropropylene copolymer resin, vinylidene fluoride resin, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyarylene ester resin composition having high heat resistance, excellent mechanical properties, low mold shrinkage and good heat moldability.

Polyarylene esters are highly sought after as engineering plastics with excellent heat resistance, strength, rigidity, flame retardance, and chemical resistance, especially in applications such as electrical parts and automobile parts.

However, in this application, the flame retardancy, which is a feature of the resin,
Along with the technological progress in this field, there is a demand for materials that have even higher heat resistance, rigidity, and dimensional accuracy (low mold shrinkage) while maintaining chemical resistance, electrical properties, and the like.

Generally, resins are supplemented with fibrous reinforcing materials such as glass fibers and carbon IA fibers, as well as talc, calcium carbonate, magnesium carbonate, calcium sulfite, aluminum hydroxide, mica, molyphine disulfide, wollastonite, graphite, titanium white, and glass beads. It is known that heat resistance, rigidity, and molding shrinkage rate can be improved by blending inorganic fillers in the form of powder, needles, or flakes.

When the above-mentioned reinforcing materials and fillers are blended in polyarylene ester hatsumode as well, heat resistance and rigidity are improved and the cylindrical shrinkage rate is reduced depending on the amount blended. The molding shrinkage rate decreases as the amount of the reinforcing material or filler increases, and the mold fidelity in injection molding etc. becomes better, but as the molding shrinkage rate decreases, the mold releasability during injection molding decreases. This can cause problems such as a rack that makes it extremely difficult to remove the molded product from the mold, deformation during ejection, and even breakage.

Therefore, although there is a strong need for a hatsumode composition that has a high mold shrinkage rate, good mold fidelity, and good dimensional accuracy, In reality, the amount of reinforcing phase and filler added is limited in order to achieve a molding yield rate that does not cause any problems.

To obtain a composition having high heat resistance, high FLLJ property, good strength, low mold shrinkage rate, and good heat moldability by blending an organic filler or an inorganic filler and further using a specific amount of fluororesin. He discovered that it was possible to do this and came up with a storage invention.

IX seal 1 is polyarylene ester 20~8゜wt%
, fibrous reinforcement, or inorganic filler 10-7Qwt%
This is a polyarylene ester resin composition characterized by comprising 05 to 2Q wt% of a fluororesin.

The polyarylene ester used in the present invention is a polyester synthesized from a dihydric phenol or its derivative and an aromatic dibasic acid or its derivative.

Specifically, the dihydric phenol is represented by the following general formula.

fftJ''+Ar represents an aromatic nucleus such as a phenylene nucleus, a hifhenyleph nucleus, or a naphthylene nucleus, and J(, represents a hydrogen atom, an alkyl group (e.g., methyl group and ethyl group), a halogenated alkyl group, an aryl group (e.g., a phenyl group). and naphthyl groups), halogenated aryl groups, aralkyl groups (
Examples are benzyl group and phenylethyl group], halokenated aralkyl group (alkyl IK1'-substituted aryl group, halogenated alkyl-substituted aryl group, alicyclic group or halokenated bile substituent 'r7i': Ly, X is methyl non-group,
alkyresinoj such as ethyrefumi;
or alkyritene group: aromatic group, tertiary amitzvah (-
N(alk)-), an ether group (-0-), a carbonyl group (-CO-), or a sulfur-containing group, such as sulfide (-S-), sulfide (-SO-) or sulfonyl (-802 -) indicates two or more alkylene or alkyritene groups interconnected by a group.

X may also be an alicyclic group or a sulfur 9''↓ containing group, such as a sulfide, sulfoxide or sulfonyl group, an ether group, a carbonyl group or a tertiary amino group.

l is a halogen atom, a 21.0 group or a group represented by it R' or possibly OR' (however, '' also has the same meaning as R mentioned above), nl is a group from O to X; The integer n up to the number of replaceable hydrogen atoms is O to 2'' on the aromatic nucleus Ar.
an integer up to the number of replaceable hydrogen atoms, P is an integer of at least 61, q is an integer from 0 to io);
, even if r is 0, it indicates J:i).

In the diphenol shown by the above formula, when there are - or more substituents Y, the q substituents iJ may be the same or different. The same can be said about Rin and ■1. The 16-substituent)' of the aromatic nucleus and the hydroxyl group may be in the ortho-, meta-o or para-position.

Alternatively, a mixture of these may be used.

Examples of synenol represented by the general formula shown below and suitable for carrying out the method of the invention are as follows.

his(4-hydroxyphenyl)-methane, bis(4-
hydroxy-3-methylenyl)-methane, his(4
-hydroxy-3,5-dichlorophenyl)-methane,
His(4-hydroxy-3,5-dibromophenyl)-
Methane, bis(4-hydroxy-8,5-difluorophenyl)-methane, bis(4-hydroxyphenyl)-
Ketone, bis(4-hydroxyphenyl)-sulfide, bis(4-hydroxyphenyl)-sulfuric acid, 4
．． 4-dihydroxydiphenyl ether, 1,1-bis(4-hydroxyphenyl)-ethane, 2,2-bis(
4-hydroxyphenyl)-propane, 2,2-his(
Hydroxy-3-methylphenyl)-propane, 2,2
-His(4-hydroxy-8-chlorophenyl)-propane, 2,2-bis(4-hydroxy-3,5-dichloroenyl)-propane, 2,2-bis(4-hydroxynaphthyl)-propane, bis (4-hydroxyphenyl)-phenylmethane, his(4-1 nitroxyphenyl)-diphenylmethane, bis(4-hydroxyphenyl)-4-methylphenylmethane, ■, ■-bis(4-
Hydroxyphenyl)-? , 2.2-trichloroethane, bis(4-hydroxyphenyl)-(4-chlorophenyl)-methane, , l, 1-bis(4-hydroxyphenyl)-cyclohexacy, his(4-hydroxyphenyl)-cyclo l-xacylmethane , 4.4-dihydroxydiphenyl, 2,2-dihydroxydiphenyl, 2.
6-hydroxynafclef's 'JA', 17 xynancrene, hydrochlorinone, resorcinol, 2.6
-dihydroxytoluene, 2,6-dihydroxytoluene, 3,6-dihydroxy-1-luene.

Specifically, the derivative of dihydric phenol is a diester such as alkyl or phenyl of the dihydric phenol.

A mixture of these 'F'A', r/TJ may also be used.

Aromatic dihydrochloric acid is represented by the following general formula.

B 00 C-Ar' -COOJJ In E above, Ar' represents an arylene group such as 0-phenylene group, l11-phenylene group, ■)-phenylene group, and naphthylene group, and these arylene groups are alkyl groups or halocarbon groups. 〉Atom may be replaced with %'.

A mixture of these may also be used.

The derivative of an aromatic dibasic acid is a dichloride or alkyl of the aromatic dibasic acid. Diesters such as phenyl. A mixture of these may also be used.

The derivative of the aromatic dibasic acid is a dichloride or a diester of alkyl, phenyl, etc. of the aromatic dibasic acid.A mixture thereof may also be used.

The polyarylene ester used as a component of the composition of the present invention is obtained by combining the above-mentioned dihydric phenol or its derivative and the above-mentioned aromatic dibasic acid or its derivative by interfacial polycondensation method, solution polycondensation method, melt polycondensation method, etc. Synthesized by any method.

A preferred polyarylene ester is bisphenol A (
2,2-bis(4-hydroxyphenyl)-propane]
It has a structure consisting of a terephthalic acid residue and an isophthalic acid residue.

This is marketed as ``U Polymer'' by Unitika ■.

The a-string reinforcing material used as a component of the composition of the present invention is glass fiber, carbon fiber, aromatic polyamide fiber, silicon carbide fiber, silicon nitride fiber, alumina fiber, potassium titanate fiber 11, mineral Fibers, etc., and generally the heat resistance of resins,
The m-fiber reinforcement used to improve strength, rigidity, etc. is applied.

Inorganic fillers used as components of the composition of the present invention include curcum, calcium carbonate, magnesium carbonate, calcium sulfite, aluminum hydroxide, mica, molybdenum disulfide, wollastonite, crafite, white titanium, oat heath, zirconia. , silica, etc. should be applied.

The m-thin reinforcing material or inorganic filler can be used without any treatment, or it can be used with a silane coupling agent such as aminosilane or epoxysilane, chromic chloride, or other materials depending on the purpose in order to have layer compatibility with the polyarylene ester. A light surface treatment agent may be used.

The non-base resin used as a component of the composition of the present invention is:
A synthetic polymer containing a fluorine atom (F) in its molecule, examples of which include tetrafluoroethylene resin, Nishifurinated ethylene hooper chloroalkyl hinyl ether, synthetic resin, and tetrafluoroethylene hooper chloroalkyl hinyl ether. Examples include propylene chloride copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluorochloride ethylene resin, and vinyl fluoride resin.

The fluororesin, tetrafluoroethylene resin (polytetrafluoroethylene), has a melting point of about 330° C., or has a high melting temperature and does not flow even above the melting point. Therefore, it is preferable because the dispersion state in the composition does not change easily depending on the molding processing conditions, and the properties, mechanical strength, and formability during injection molding of the composition do not change easily.

The blending amount is polyarylene ester 20~8Q
wt%, fibrous reinforcement or inorganic filler lO~7Qw
t%, fluororesin 0.5 to 2 Qwt (the total amount of N & fibrous reinforcing material or inorganic filler and fluororesin is 20 to s wjl of the total resin composition) is effective.

That is, when the total amount of the reinforcing material or the filler and the fluororesin exceeds 3Qwt% in the resin composition, and the amount of polyarylene ester is less than 20wt%, the mixing is insufficient and a uniform composition cannot be obtained. is not obtained, the fluidity of the resin composition is lost, and molding becomes difficult. Further, when the total amount of the reinforcement or the filler and the fluororesin is less than 20 wt, a sufficient effect of lowering the molding shrinkage rate cannot be obtained.

The total amount of the reinforcing material or the filling material and the fluorine resin is 20 to 8. Even in the case of Owt and -C, if the amount of the reinforcing material or the filler is less than 1Qwt%, the effect of reducing the molding shrinkage rate is insufficient;
If it is less than %, M-type properties during injection molding etc. will not be sufficient.

Moreover, if the reinforcing material or the filler exceeds 7 QwL, mixing becomes insufficient, the compounding process becomes difficult, and a uniform composition cannot be obtained. If the amount of fluororesin exceeds 2Q wt%, the strength of the obtained molded product will decrease significantly, which is not preferable.

The means of blending the composition of the present invention is not particularly limited. It is possible to feed the polyarylene ester, the powdered reinforcing material or the inorganic filler, and the fluororesin separately to a melt mixer, and these raw materials can be mixed in advance in a mortar, Henschel mixer, whole mill, or ribbon. It is also possible to pre-mix using a blender or the like and then supply it to a melt mixer.

The composition of the present invention may contain antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, dyes, and other additives that do not impair the purpose of the present invention. One or more conventional additives such as colorants, flame retardants, flame retardant aids, and antistatic agents may be added.

i fL, other thermoplastic resins (e.g. polyethylene, polypropylene, polyamide, polycarbonate,
Polyester carbonate, polyethylene terephthalate, polyethylene terephthalate, polysulfone, polyether sulfone, modified polyphenylene oxide, acrylonitrile-styrene-butadiene hatsumode (AI3S)
resin), polyphenylene sulfide resin, etc.), thermosetting resin (e.g., phenolic resin, epoxy resin, etc.)
can be mixed according to the purpose.

In particular, polycarbonate, polyester carbonate,
Polyethylene terephthalate and polyethylene terephthalate have good compatibility with the polyethylene ester, and have an excellent improvement effect when it comes to improving processability.
- preferable.

Also, Boria 2iζ, for example, nylon 6, nylon 66
is preferred because it improves the processability of the polyarylene ester and also improves its chemical resistance.

Hereinafter, the present invention will be specifically explained with reference to Examples, which are illustrative of preferred embodiments and are not limited to the compositions of Examples.

Examples 1 to 5 A polyarylene resin ester (manufactured by Unitika, U-Polymer U-100) having the following structure as its main structure (m/n-approximately 515) and wollastonite (
Nagashio Sangyo N Y A D-G, Cabin 3 project!
) and tetrafluoroethylene resin (ICI Fluon Li
2Q) were mixed with the composition shown in Table 1, melted and kneaded at a temperature of 340°C using a twin-screw extruder (POM-30 manufactured by Hoseitetsu Kogyo Co., Ltd.), and then the strands were cooled with water and cut to obtain pellets. Ta.

Injection molding of recycled pellets (Residence - Nenutar 47/
28 A 11i Rona test piece was molded using an injection molding machine (cylinder temperature BLE +60°C, mold temperature 1aO°C). After opening the mold, the resistance when the molded product was ejected by the ejector turbine was measured using a Nutrain gauge type pressure sensor.

Using the obtained bending test pieces, bending strength, curved elastic modulus, heat deformation temperature, and molding shrinkage were measured.

song? -1 Intensity A S 'I'MD -790,,%
'l type temperature is A81'M D-648 (18,6Xr/
σ ). The results are shown in Table 1.

Comparative Examples 1 to 5 The polyarylene ester and wollastonite used in Examples 1 to 5 were mixed in the proportions shown in Table 1, and processed in the same manner as in Examples 1 to 5. ,
611 physical properties were determined.

The results are shown in Table 1.

It can be seen that the composition of the present invention has improved heat resistance and rigidity (modulus of elasticity) of polyarylene ester, has high strength, and has low molding yield and excellent properties (actual b.
'Jb) l~5).

In addition, in compositions other than the composition of the present invention, the improvement in molding shrinkage rate was not sufficient (Comparative Example 2), the strength was significantly reduced, I stiffness (Example 4), and the mold releasability was poor. The intended good characteristics were not achieved, such as insufficient (Comparative Example 5).

Claims (1)

[Claims] A polyarylene ester resin composition comprising 20 to 80 wt% of polyarylene ester, 1O to 7 Q wt% of II fibrous reinforcing material or inorganic filler, and 0.5 to 2 Q wt% of fluororesin.