JPH11140315A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition with an improved flowability and an increased crystallization rate by including a polyarylene sulfide with an aromatic carboxylic acid, an ester or an anhydride thereof, or a difunctional arylene compound having a melting point of a specific temperature or above. SOLUTION: A resin composition is obtained by adding and kneading 0.1-5 pts.wt. of an aromatic carboxylic acid of the formula: ArXn such as phthalic acid, methyl phthalate, phthalic anhydride or the like, an ester or an anhydride thereof or a difunctional arylene compound of the formula: Y-Ar'-Y' having a melting point of 150 deg.C or above such as terephthalonitrile or the like to 100 pts.wt. of a polyarylene sulfide and kneading the same. The polyarylene sulfide is a resin comprising repeating units of the formulae I-IV or the like and preferably has a melt viscosity (300 deg.C, 20 kgf/cm<2> ) of 50-30,000 poise. In the formulae, Ar is an arylene; X is -COOH or the like; m is 1-4; Ar' is 1,4-phenylene, 1,5- nephtylene or the like; and Y and Y' are each functional groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyarylene sulfide resin composition having improved flowability.

[0002]

2. Description of the Related Art Polyarylene sulfide (hereinafter referred to as PA)
S may be abbreviated as S), because of its excellent electrical properties, heat resistance, chemical resistance, moldability, flame retardancy, and dimensional stability, it is used for electronic / electrical parts and mechanical parts.
In particular, as a sealing material for electronic and electric parts, it is more excellent in heat resistance and electrical characteristics than conventional epoxy resins, silicon resins, and the like, and the possibility of use in such applications is increasing.
In molding these parts, good fluidity during processing is required. However, improving the fluidity of the PAS lowers the viscosity of the PAS, so that only a PAS having a low molecular weight and poor mechanical properties could be prepared. Therefore, in order to maintain the mechanical properties, a high-viscosity PAS having a certain high molecular weight had to be used.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyarylene sulfide having a P
It is an object of the present invention to provide a polyarylene sulfide resin composition in which the viscosity of AS is reduced to improve the fluidity and the crystallization speed is improved.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that aromatic carboxylic acids, aromatic carboxylic acid esters, aromatic carboxylic acid anhydrides, Alternatively, the addition of a specific bifunctional arylene compound having a melting point of 150 ° C. or higher improves fluidity, and finds that the crystallization rate is improved,
The present invention has been completed. That is, the first invention of the present invention is:
(A) 100 parts by weight of a polyarylene sulfide and (B) a general formula ArX _m [wherein, Ar represents an arylene group, X represents -COOH or -COOR (R represents an alkyl group)
And m is 1 to 4. The polyarylene sulfide resin composition having improved fluidity comprising 0.1 to 5 parts by weight of an aromatic carboxylic acid, an aromatic carboxylic acid ester or an aromatic carboxylic acid anhydride represented by the formula The invention of (2) is characterized by the fact that (A) 100 parts by weight of polyarylene sulfide and (B ′) a general formula YA having a melting point of
r'-Y '(provided that the Ar' group is 1,4-phenylene,
1,5-naphthylene, 2,6-naphthylene, 4,4'-
Biphenylene, 4,4'-diphenyl ether, 4,
It is 4'-diphenylmethane or 4,4'-diphenylsulfone, and Y and Y 'are functional groups. The present invention is a polyarylene sulfide resin composition having improved fluidity, comprising 0.1 to 5 parts by weight of a bifunctional arylene compound represented by the formula (1).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) polyarylene sulfide resin (PAS) used in the present invention is a polymer substantially consisting of repeating units -RS- (R: aryl group). Preferably, a paraphenylene group is a repeating unit, and the formula

[0006]

Embedded image A paraphenylene group as a main component, and other arylene groups such as an m-phenylene group as a minor component.

[0007]

Embedded image , O-phenylene group

[0008]

Embedded image , Alkyl-substituted phenylene group

[0009]

Embedded image , P, p'-diphenylene sulfone group

[0010]

Embedded image , P, p'-biphenylene group

[0011]

Embedded image , P, p'-diphenylene ether group

[0012]

Embedded image , P, p'-diphenylenecarbonyl group

[0013]

Embedded image , Naphthalene group

[0014]

Embedded image And a random copolymer and a block copolymer having the same. Further, these polyarylene sulfide resins may be a mixture. Particularly preferred resin is polyparaphenylene sulfide resin (hereinafter referred to as PP).
S).

As PPS, for example, Japanese Patent Publication No. 45-3
No. 368, PPS obtained by a method of reacting an alkali metal sulfide with a polyhalo aromatic compound in an organic amide solvent, various polymerization aids such as alkali metal carboxylate and aromatic carboxylic acid. First, a high-molecular weight PPS obtained by using an alkali metal salt, an alkali metal halide, or the like is reacted with an alkali metal sulfide and a polyhalo aromatic compound at 180 to 235 ° C. to 50 to 98%, and then water is added. The PPS obtained by further increasing the temperature and polymerizing in two steps, the alkali metal sulfide and the polyhaloaromatic compound are reacted in an organic amide solvent, and then washed with an organic amide solvent while being heated, to thereby inhibit the polymerization inhibitor and PPS obtained by removing unreacted substances and further reacting at 200 to 260 ° C., and further, a branching agent such as 1,3,5-trichlorobenzene at the time of reaction. P branched obtained by pressurizing the polymerization
PS or a linear PPS obtained by cooling a gas phase portion of a reaction vessel to reflux a part of the gas phase into a liquid phase (Japanese Patent Application Laid-Open No. 5-222196).

PA as the component (A) used in the present invention
As S, a polymer obtained by curing by oxidative crosslinking or thermal crosslinking can also be used, but preferred is a polymer having a substantially linear molecular structure. Above all 300
° C., preferably linear polymer is in the range melt viscosity V ₃₀ is 50 to 30,000 poise measured at a load 20 kgf / cm ^2, particularly preferably 100 to 10000 poise.

The aromatic carboxylic acid, aromatic carboxylic acid ester or aromatic carboxylic anhydride (B) used in the first invention of the present invention has the general formula ArX _m [wherein ArX _m
Represents an arylene group, and X represents -COOH or -COOR.
(R is an alkyl group), and m is 1-4. ].

In the above general formula, the arylene group of Ar is an arylene group such as a benzene ring, a naphthalene ring, a biphenyl ring and diphenyl ether, diphenylmethane and diphenylsulfone, and preferably a benzene ring and a naphthalene ring. Specifically, when it has one functional group with m = 1, a phenyl group, a naphthyl group, a biphenyl group, a diphenyl ether group, a diphenylmethane group,
In the case of having a bifunctional group with m = 2, the position of the substituent is 1,2.
-Phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthylene, 1,3-naphthylene, 1,4
-Naphthylene, 1,5-naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,3
-Naphthylene, 2,6-naphthylene, 2,7-naphthylene, 2,2'-biphenylene, 2,3'-biphenylene, 4,4'-biphenylene, 2,2'-diphenylether group, 2,3'-diphenylether Group, 4,4 '
-Diphenyl ether group, 2,2'-diphenylmethane group, 2,3'-diphenylmethane group, 4,4'-diphenylmethane group, 2,2'-diphenylsulfone group, 2,
Examples thereof include a 3′-diphenylsulfone group and a 4,4′-diphenylsulfone group. When the compound has a trifunctional group with m = 3, 1,2,3-phenyl, 1,2,4-phenyl, 1,3,5-phenyl, 1,2,5-naphthyl,
1,2,6-naphthyl, 1,3,5-naphthyl, 1,
3,7-naphthyl, 1,4,5-naphthyl, 2,3,6
-Naphthyl, and in the case of having a 4-functional group with m = 4, 1,2,3,5-phenyl, 1,2,4,
5-phenyl, 1,2,4,6-naphthyl, 1,2,2
5,6-naphthyl, 1,2,5,7-naphthyl, 1,
2,6,7-naphthyl, 1,3,5,7-naphthyl,
Examples thereof include 1,3,6,7-naphthyl, 1,4,5,8-naphthyl, and 2,3,6,7-naphthyl.
Among these, 1,3,5-phenyl, 1,3,7-
Naphthyl, 1,2,5,6-naphthyl, 1,3,5,7
-Naphthyl, 1,4,5,8-naphthyl and 2,3
6,7-Naphthyl is particularly preferred. This Ar is
If necessary, one or more types may be substituted with a lower alkyl group, another aromatic group, a hydroxyl group, F, Br, Cl, I or the like.

In the above formula, the alkyl group represented by R is an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group. X may be the same or different, and may include anhydrides in dehydrated form as needed.

Specific compounds of component (B) include benzoic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, 1,2,4,5-benzenetetracarboxylic acid, trimellitic acid, and trimellitate Acid anhydride, methyl phthalate, dimethyl phthalate, methyl isophthalate, dimethyl isophthalate, dimethyl terephthalate, ethyl phthalate, diethyl phthalate, diethyl isophthalate, diethyl terephthalate, propyl phthalate, dipropyl phthalate, isophthalic acid Examples thereof include dipropyl, dipropyl terephthalate, 2-naphthalenecarboxylic acid, 2,6-naphthalenedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic anhydride, trimesic acid, and melophanic acid.

The bifunctional arylene compound (B ') used in the second invention of the present invention has the general formula Y-Ar'-
An arylene compound represented by Y '. In the above general formula, the arylene group for Ar ′ includes a benzene ring,
Naphthalene ring, biphenyl ring and diphenyl ether,
Arylene groups of diphenylmethane and diphenylsulfone, and the positions of the functional groups are 1,4-phenylene, 1,5-naphthylene, 2,6-naphthylene,
4′-biphenylene, 4,4′-diphenyl ether,
4,4'-diphenylmethane and 4,4'-diphenylsulfone. As for the position of the functional group, the structure close to a linear shape as described above increases the crystallinity, and while maintaining the molecular weight of the PAS, reduces the viscosity of the PAS to improve the flowability and improve the crystallization rate. The effects of the present invention are exhibited. Also,
This Ar 'may be optionally substituted with one or more kinds of lower alkyl groups, other aromatic groups and the like.

In the above general formula, the functional groups Y and Y 'are OH, NH ₂ , Z, NO ₂ , SO ₃ H, S
O ₂ NH ₂ , OR ′, NHR ′, NR ′ ₂ , SO ₂ Z, C
N, CONH ₂ , CONHR ′ (R ′ is an alkyl group, Z
Represents a halogen atom. ), Which may be the same or different and, if necessary, include the anhydrous form in dehydrated form. The alkyl group for R ′ has 1 to 1 carbon atoms.
Examples of the 10 alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl. Of these, halogen atoms, nitro groups,
Compounds containing hydroxyl groups are preferred.

The component (B ') must have a melting point of 150 ° C. or higher. If the melting point is less than 150 ° C,
The viscosity of PAS significantly decreases, which is not preferable. Specific compounds of the component (B ′) include p-dinitrobenzene, terephthalonitrile, terephthalic diamide,
-Aminophenol, sulfanilic acid, sulfanilamide, p-aminobenzamide, p-nitrobenzsulfonamide, p-nitrobenzonitrile, p-nitrobenzamide, p-nitrobenzanilide, p-sulfonebenzoic diamide, 1,5 -Naphthalene diol,
2,6-naphthalenediol, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,6-dibromonaphthalene, 2,6-diiodonaphthalene, 1,5-naphthalenedisulfonic acid diamide, 2,6-naphthalene Disulfonic acid dichloride, 2,6-naphthalenedisulfonic acid diamide, 1,5-naphthalenedinitrile, 1,5-
Dinitronaphthalene, 2,6-dinitronaphthalene,
Examples thereof include 1,5-naphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid dimethyl ester, 2,6-naphthalenedinitrile, and 2,6-naphthalenedianilide.

The amount of the aromatic carboxylic acid, aromatic carboxylic acid ester or aromatic carboxylic acid anhydride component (B) or the specific bifunctional arylene compound (B ') having a melting point of 150 ° C. or more is 100 parts by weight of PAS. 0.1 per
To 5 parts by weight, preferably 0.5 to 3 parts by weight. 0.
If the amount is less than 1 part by weight, the effect of improving the fluidity of PAS is not exhibited. On the other hand, if it exceeds 5 parts by weight, the melt viscosity is extremely lowered, which is not preferable.

For blending the component (B) or the component (B ') into the PAS, each component is dry-blended in advance using a Henschel mixer or the like, kneaded using a single-screw or twin-screw extruder, and extruded. Method for forming pellets, or
In addition to the method of adding and kneading phthalic acid ester from the side feeder port of the extruder and extruding to form pellets for molding, there is also a method of dissolving a predetermined amount in a solution at the time of PAS synthesis so as to be contained. It can also be used.

In the present invention, if necessary, in addition to the component (B) or the component (B '), a molded article having excellent properties such as mechanical strength, heat resistance, dimensional stability, and electrical properties can be obtained. May be blended with an inorganic filler.

As the inorganic filler, known fillers such as fibrous, powdery and plate-like fillers are used. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, and stainless steel. Inorganic fibrous materials such as fibrous materials of metals such as aluminum, titanium, copper, and brass can be used. Particularly typical fibrous fillers are glass fibers and carbon fibers. In addition, high melting point organic fibrous substances such as polyamide, fluororesin, polyester resin, and acrylic resin can also be used. Examples of the particulate filler include carbon black, silica, quartz powder, glass beads, glass powder, silicates such as calcium silicate, kaolin, talc, clay, diatomaceous earth, and wollastonite, and iron chloride. Metal oxides such as titanium oxide, zinc oxide and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; and other silicon carbide, silicon nitride and boron nitride And various metal powders.
Examples of the plate-like filler include mica, glass flake, various metal foils, and the like. These inorganic fillers can be used alone or in combination of two or more. The combination of fibrous fillers, especially glass or carbon fibers, with particulate and / or plate-like fillers is a particularly preferred combination.

The amount of the inorganic filler used is determined by the amount of the component (A) PAS
400 parts by weight or less with respect to 100 parts by weight of
More preferably, it is 10 to 250 parts by weight. If the amount exceeds 400 parts by weight, the molding operation becomes difficult, which is not preferable.

In using the above-mentioned inorganic filler, it is preferable to use a sizing agent or a surface treatment agent if necessary. For example, functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, and the like. These compounds may be used by subjecting an inorganic filler to a surface treatment or a convergence treatment in advance, or may be added at the same time when the composition is prepared.

Further, the resin composition of the present invention contains a known substance generally added to a thermoplastic resin and a thermosetting resin,
For example, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, coloring agents such as dyes and pigments, lubricants, crystallization accelerators, and the like can be appropriately added as necessary.

The preparation of the polyarylene sulfide resin composition of the present invention can be carried out by equipment and a method generally used for preparing a synthetic resin composition. That is, necessary components are mixed, kneaded using a single-screw or twin-screw extruder, and extruded into molding pellets. A method of mixing and molding a part of the necessary components as a master batch, In order to improve the dispersion and mixing of the components, any or all of the polyarylene sulfide resin may be pulverized, mixed, and melt-extruded.

[0032]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The measuring methods used in the examples and comparative examples are as follows. (1) Melt viscosity V ₃₀ : Shimadzu Flow Tester CFT
Using -500C, the viscosity (poise) after holding at a cylinder set temperature of 300 ° C., a load of 20 kgf / cm ² and a die L / D = 10 for 30 minutes was measured.

(2) Molecular weight (Mp): For the molecular weight, the retention time measured at 210 ° C. by gel permeation chromatography using 1-chloronaphthalene as a moving layer was converted into a standard polystyrene molecular weight, and further corrected by the universal calibration method. It is the peak top molecular weight obtained. The device used was SSC-7000 manufactured by Senshu Kagaku.

(3) Crystallization temperature (T _C2 ): Measured as follows using a differential scanning calorimeter SSC / 5200 manufactured by Seiko Denshi. 10 mg of a sample was placed in a nitrogen atmosphere.
After the temperature was raised from room temperature to 340 ° C. at a rate of 0 ° C./min, the temperature was maintained for 5 minutes, and the peak top temperature of the exothermic peak when the temperature was lowered to room temperature at a rate of 10 ° C./min again was read to determine the crystallization temperature. And

Examples 1 to 15 and Comparative Examples 1 and 2 PPS (T-1, manufactured by Toprene Co., Ltd.) and an aromatic carboxylic acid or a derivative thereof in the amounts shown in Table 1 were premixed with a Henschel mixer for 1 minute. And then homogenized, twin-screw kneader (screw diameter: 20 mm, barrel temperature: 310 ° C)
And a PPS composition was obtained. PPS obtained
Table 1 shows the physical property values of the composition.

[0036]

[Table 1]

As apparent from Table 1, the aromatic carboxylic acid, aromatic carboxylic acid ester and aromatic carboxylic anhydride of the present invention were compared with those of PPS alone (Comparative Example 1). The composition blended with PPS in a range of amounts has no decrease in molecular weight, has a low melt viscosity, has remarkably improved fluidity, and has an improved crystallization temperature (Examples 1 to 1).
5). On the other hand, in the case of a PPS composition in which the amount of the aromatic carboxylic acid is out of the range of the present invention, the viscosity is drastically reduced, the gas generation amount is sharply increased, and the sample cannot be evaluated (Comparative Example 2).

Examples 16 to 22, Comparative Examples 3 to 6 PPS (T-1, manufactured by Toprene Co., Ltd.) and a polyfunctional arylene compound having the compounding amounts shown in Table 2 were premixed with a Henschel mixer for 1 minute to obtain a uniform mixture. After that, the mixture was pelletized with a twin-screw kneader (screw diameter: 20 mm, barrel temperature: 310 ° C.) to obtain a PPS composition. Table 2 shows the physical property values of the obtained PPS composition.

[0039]

[Table 2]

As is clear from Table 2, the bifunctional arylene compound having a melting point of 150 ° C. or more and a specific position of the substituent of the present invention was compared with that of PPS alone (Comparative Example 1). In the range of the invention, the composition blended with PPS had no decrease in molecular weight, reduced melt viscosity, markedly improved fluidity, and improved crystallization temperature (Examples 16 to 2).
2). On the other hand, bifunctional arylene compounds (2,6-dichloronaphthalene and 1,4-
When dibromonaphthalene) is used, the viscosity decreases significantly,
The amount of gas generation increased rapidly and sample evaluation was not possible (Comparative Examples 3 and 6). When 1,3,5-triiodobenzene having three functional groups is used, the viscosity is remarkably increased, and the viscosity cannot be measured. Due to gel formation, there is a portion insoluble in a solvent for molecular weight measurement, and accurate molecular weight measurement is performed. (Comparative Example 5). In the 2,3-naphthyl type in which the position of the substituent is not linear, the melt viscosity is not sufficiently lowered and the crystallization temperature is not improved (Comparative Example 4).

[0041]

Industrial Applicability The polyarylene composition of the present invention has no decrease in molecular weight, and has improved fluidity and crystallization rate, so that it can be industrially used as a material for polyarylene products having high fluidity and high toughness. It is a versatile composition.

Claims (3)

[Claims] (A) Polyarylene sulfide 100
Parts and (B) in the general formula ArX _m [wherein, Ar represents an arylene group, X is -COOH or -COOR (R is an alkyl group) a, m is 1-4. ] A polyarylene sulfide resin composition having improved fluidity, comprising 0.1 to 5 parts by weight of an aromatic carboxylic acid, an aromatic carboxylic acid ester or an aromatic carboxylic acid anhydride represented by the formula: 2. (A) Polyarylene sulfide 100
Parts by weight and (B ′) a general formula YA having a melting point of 150 ° C. or more
r′-Y ′ (wherein, the Ar ′ group is 1,4-phenylene,
1,5-naphthylene, 2,6-naphthylene, 4,4'-
Biphenylene, 4,4'-diphenyl ether, 4,
It is 4'-diphenylmethane or 4,4'-diphenylsulfone, and Y and Y 'are functional groups. A polyarylene sulfide resin composition having improved fluidity, comprising 0.1 to 5 parts by weight of a bifunctional arylene compound represented by the formula (1). 3. The polyarylene sulfide resin composition according to claim 2, wherein the functional group in the bifunctional arylene compound (B ′) having a melting point of 150 ° C. or higher is a nitro group, a halogen atom or a hydroxyl group.