JPH0391563A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To prepare a highly heat-resistant polyphenylene sulfide resin compsn. having a high crystallizability and showing a high degree of crystallization even when molded at low temp. by compounding a polyphenylene sulfide resin with a phosphate compd. CONSTITUTION:A polyphenylene sulfide resin compsn. with a high crystallizability is prepd. by compounding 100 pts.wt. polyphenylene sulfide resin in which 70mol% or higher of the repeating units are phenylene sulfide units and which pref. has a low crosslinking degree with 0.01-40 pts.wt., pref. 0.5-20 pts.wt., phosphate compd. (e.g. triphenyl phosphate).

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to polyphenylene sulfide (hereinafter referred to as PPS) resin compositions, and more specifically, polyphenylene sulfide resin compositions with excellent crystallinity. relating to things.

(Prior Art) PPS resin is a crystalline polymer, and the properties of PPS resin largely depend on the degree of crystallinity.

Among them, those with a high degree of crystallinity are useful because they have a high heat distortion temperature and are heat resistant. Therefore, in order to obtain a PPS resin with sufficient heat resistance, the following methods are usually used:
100℃ or less) molded at a mold temperature (partially crystallized) is post-heat treated to promote crystallization.
The degree of crystallinity is increased by such methods.

(Problems to be Solved by the Invention) However, the molding method described in (1) above is dangerous and expensive because it is carried out at high temperatures. Further, the post-processing (heating) treatment of (3) also makes the work complicated and is also difficult in terms of economy.

Therefore, an object of the present invention is to obtain a PPS resin composition that has good crystallinity and has a high degree of crystallinity even when molded at low temperatures.

(Means for Solving the Problems) As a result of intensive studies to achieve the above object, the present inventors found that when a sulfonic acid ester compound is blended into a PPS resin composition, low temperature For example, it was discovered that even when molded at a mold temperature of 80° C. or lower, a molded amount with a high degree of crystallinity and a high heat distortion temperature can be obtained, and the present invention was completed based on this finding.

That is, the PPS resin composition of the present invention is a resin composition containing a polyphenylene sulfide resin, in which a phosphoric acid ester compound is added to 100 parts of the polyphenylene sulfide resin by o, oi to 40. It is characterized by containing parts by weight.

First, the resin composition of the present invention contains PPS and has a favorable structural unit, and a resin composition containing 70 mol% or more of this structural unit is preferable because it provides a composition with excellent properties.

PPS polymerization methods include polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or polymerizing p-dichlorobenzene in the presence of sodium sulfide, sodium hydrosulfide and sodium hydroxide, or hydrogen sulfide and sodium hydroxide in a polar solvent. Polymerization methods include self-condensation of p-chlorothiophenol, but sodium sulfide and p,-dichlorobenzene are used in an amide solvent such as N-methylpyrrolidone or dimethylacetamide, or a sulfonic solvent such as sulfur or holane. A method of reacting is suitable. At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide.

If it is less than 30 mol% as a copolymerization component, it indicates meta-linked benido, phenyl, alkoxy, carboxylic acid, or a metal base of carboxylic acid. Trifunctional phenyl may be present as long as it does not significantly affect the crystallinity of the polymer. but,
Preferably, the copolymerization component is 10 mol% or less. Especially 3
When phenyl, biphenyl, naphthyl sulfide bonds, etc. having higher functionality are selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less.

Such PPS can be produced by common manufacturing methods, such as (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (see U.S. Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671 and Japanese Patent Publication No. 45-3368); 2) Condensation reaction of thiophenols in the coexistence of an alkali catalyst or copper salt (see US Pat. No. 3,274,165@, British Patent No. 1,160,560), (3) Condensation reaction of thiophenols in the coexistence of an alkali catalyst or a copper salt, etc. (3) Condensation reaction of an aromatic compound with sulfur chloride in the coexistence of a Lewis acid catalyst. Condensation reaction in
6-27255, Belgian Patent No. 29437)
etc., and can be arbitrarily selected depending on the purpose.

PPS is currently owned by Philips Petroleum ■, O, Tosoh Sasteel ■, Toprene and Kureha Chemical.
It is offered to the market from etc. There are various grades depending on crosslinking density and viscosity, and PPS with less crosslinking structure is preferred for the present invention.

A feature of the present invention is that a phosphoric acid ester compound is blended in order to improve the crystallinity of the above-mentioned PPS resin.

Phosphate ester compounds that can be used in the present invention include, for example, the following formula: % Formula % Each independently represents a hydrogen atom or an organic group, but R1=
R2=R3=R' = excluding the s combination of H<. x represents a divalent or higher organic group, p is O or 1, q represents an integer of 1 or more, for example 30 or less, and r represents an integer of 0 or more. ) Examples include phosphoric acid ester compounds represented by the following.

However, it is not limited to these.

In the above formula, examples of the organic group include an alkyl group that may or may not be substituted, a cycloalkyl group, and an aryl group. In addition, when substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group,
Examples include arylthio group, halogenated aryl group, etc.
Also, a group in which these substituents are combined (for example, an arylalkoxyalkyl group, etc.) or a group in which these substituents are combined through an oxygen atom, a sulfur atom, a nitrogen atom, etc.
For example, an arylsulfonylaryl group, etc.) may be used as a substituent. Furthermore, the term "divalent or higher valence organic group" means a divalent or higher valence group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above-mentioned organic group. For example alkylene groups, and preferably (substituted) phenylene groups,
Examples include polynuclear phenols, such as those derived from bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred are hydroquinone,
Resorcinol; diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'
-dihydroxydiphenylsulfone, dihydroxynaphthalene, etc.

Examples of specific phosphate ester compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tryptoxyethyl phosphate, triphenyl phosphate,
Tricresyl phosphate, cresyl phenyl phosphate, octyldiphenyl phosphate, diisopropylphenyl phosphate, tris(chloroethyl) phosphate, tris(dichloropropyl) phosphate,
Tris(chloropropyl)phosphate, bis(2,3
-dibromopropyl)-2,3-dichloropropyl phosphate, tris(2,3-dibromopropyl) phosphate and bis(chloropropyl) monooctyl phosphate, in which R1-R4 are alkoxy such as methoxy, ethoxy and propoxy, or preferably (substituted ) Phenoxy, such as phenoxy, methyl (substituted) phenoxy, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, trioxybenzene triphosphate, etc., preferably triphenyl phosphate and various triphosphates.

In the present invention, in order to improve the crystallinity of the above-mentioned PPS resin, the above-mentioned phosphoric ester compound is added to PP3.
The amount is 0.01 to 40 parts by weight, preferably 0.5 to 20 parts by weight, per 100 parts by weight.

The resin composition of the present invention has the purpose of supplementing the properties of PPS, that is, improving dimensional accuracy, brittleness, heat resistance, etc., within a range where PPS is contained preferably at least 20% by weight of the entire resin composition. In addition to the above-mentioned PPS, other resins may optionally be included in order to achieve this. Examples of such resins include polyphenylene ether (PPE).
, polycarbonate (PC), polyester, polyester elastomer, polyester oxide (PEI),
ABS resin, AES (acrylonitrile ethylene propylene styrene) resin, AS (acrylonitrile styrene) resin, polyamide (PA), polystyrene (P)
S), etc., and these can be used alone or in combination of two or more, and optionally mixed with a compatibilizing agent or modified to enable compatibilization.

Specific examples of polymer blends of PPS and other resins include Japanese Patent Application Nos. 1-43200 and 1-128.
Mention may be made of the PPS/PPE polymer blends described in No. 943, which contain as compatibilizers copolymers containing oxazolinyl or epoxy groups, citric acid and aminosilanes.

In another example, P as described in Japanese Patent Application No. 1-41649
PS/PPE/PA polymer blend, patent application No. 1-11
There are PPS/modified PPE polymer blends described in No. 5173.

The composition of the present invention contains a rubber-like material as an optional component to significantly improve the impact strength, and the total of PPS and PA is 1
For example, it can be included in an amount of 80 parts by weight or less per 00 parts by weight.

Rubbery materials include natural and synthetic polymeric materials that are elastic at room temperature. Specific examples include natural rubber, butadiene polymer, styrene-isoprene copolymer, butadiene-styrene copolymer (random copolymer,
block copolymers, graft copolymers, etc.), isoprene polymers, chlorobutadiene polymers, butadiene-acrylonitrile copolymers, isobutylene polymers, isobutylene-butadiene copolymers, isobutylene-imprene copolymers, acrylic ester polymer,
Examples include ethylene-propylene copolymer, ethylene-propylene-diene copolymer, thiokol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (eg, polypropylene oxide, etc.), shrimp chlorohydrin rubber, and the like.

These rubbery substances can be produced using any polymerization method (e.g. emulsion polymerization, solution polymerization), any catalyst (e.g. peroxide,
Trialkylaluminum, halo, lithium genide, nickel-based catalysts) may also be used. Furthermore, rubber particles having various degrees of crosslinking, microstructures of various proportions (for example, cis structure, trans structure, vinyl group, etc.), or rubber particles having various average particle diameters are also used.

Further, as the copolymer, any of various copolymers such as a random copolymer, a block copolymer, a graft copolymer, etc. can be used. Furthermore, in producing these rubbery substances, it is also possible to copolymerize with monomers such as other olefins, dienes, aromatic vinyl compounds, acrylic acid, acrylic esters, and methacrylic esters. Any method such as random copolymerization, block copolymerization, graft copolymerization, etc. can be used for their copolymerization. Specific examples of these monomers include ethylene, propylene, styrene, chlorostyrene, α-methylstyrene, butadiene, isobutylene, chlorobutadiene, butene, isobutylene, methyl acrylate, acrylic acid, ethyl acrylate, Examples include butyl acrylate, methyl methacrylate, acrylonitrile, and the like.

Furthermore, partially modified rubbery substances can also be used,
Examples include hydroxy- or carboxy-terminated polybutadiene, partially hydrogenated styrene-butadiene block copolymer, partially hydrogenated styrene-isoprene block copolymer, and the like.

Preferred are epoxy-modified polyolefins, such as ethylene, propylene, butene-1, pentene-1,4-methylpentene-1, imbutylene, 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene,
5-ethylidenenorbornene, 5-ethyl-2,5-norbornadiene, 5-(i'-propenyl)-2-
At least one selected from norbornene and styrene
This is an epoxy-modified polyolefin obtained by introducing a monomer component having an epoxy group into a polyolefin obtained by radical polymerization of a seed olefin.

Commercially, it can be obtained, for example, as Bond First E (trademark, Custom Chemical 1!I/J@>).

Furthermore, the resin composition of the present invention contains additives that can be normally added to resin compositions, such as inorganic fillers, fillers such as glass fibers, carbon fibers, talc, and kaolin, flame retardants, plasticizers, and pigments. can be included.

The composition of the invention can be prepared in various known ways. For example, it is possible to uniformly mix the raw materials in advance using a mixer such as a tumbler or Henschel mixer, feed the raw materials to a single-screw or twin-screw extruder, melt and knead them at 230 to 400°C, and then form them into pellets. can.

(Example) The following examples illustrate the invention in more detail.

In addition, in the following examples, the following resins and compounds were used.

PPS: T4 (trademark, manufactured by Toprene) Phosphate ester compound: TPP (triphenyl phosphate) 4CR733S
(trademark, phenylresorcin polyphosphate, manufactured by Daihe Kagaku ■) Optional components: PPE: Norso 1 (trademark, manufactured by Japan GE Plastics ■) Epoxy group-modified PPE: Produced as follows.

(Production method) PPE [poly(2,6-cymethyl-1,4-phenylene ether)] with an intrinsic viscosity of 0.46 in a dry flask.
Part iooam was dissolved in 1500 parts by weight of epichlorohydrin.

Next, 15 parts by weight of 33.3% caustic soda solution was added, heated to 100° C. with stirring, and reacted at this temperature for 4 hours. Next, the polymer was filtered and washed with methanol, water, and methanol in this order, and then dried under reduced pressure at 150° C. for 8 hours to obtain PPE having an epoxy group at the terminal group.

PA6: 8.4xlO-5T-ru/9(7) terminal 7mi/group! :1.8X 10" Polyamide-6 with a molecular weight of 13,000 and a terminal carboxyl group of 5 mol/9
was used.

GF (glass fiber): MA404 (trademark, manufactured by Asahi Fiberglass ■) RPS-1005 (trademark, oxazolinyl group-containing styrenic copolymer, manufactured by Nippon Shokubai ■) Kraton G1651 (trademark, 5EBS rubber, manufactured by Shell Chemical ■) Bond First E (trademark, epoxy group-containing ethylene copolymer, manufactured by Order Kagaku II) 1 to 3 and 1 to 2 Each component was blended in the weight ratio shown in Table 1, and heated at 300°C for 15 minutes.
Melting mixture was performed in a twin-screw extruder set at 0 rE)I to create a pellet.

The obtained pellets were injection molded using an injection molding machine under the following conditions: cylinder temperature set at 320°C, mold temperature 60°C, molding cycle 23 seconds (injection time 8 seconds, cooling time 15 seconds), and test pieces were obtained. It was created.

Using this test piece, the heat distortion temperature was measured according to ASTM 0648. Furthermore, the crystallization temperature (Tc) of the molded product was measured using a differential calorimeter (DSC). The crystallization rate was determined by roughly measuring the crystallization energy.

The crystallization temperature was measured using a differential calorimeter by heating a sample that had been previously melted and then rapidly cooled in a nitrogen stream at a heating rate of 20° C./min. The lower the Tc value, the higher the crystallization rate and the better the crystallinity.

Moreover, the crystallization rate was determined as follows. First, the crystallization energy of only PPS before molding was measured. That is, 320°C at a heating rate of 20°C/min in a nitrogen stream.
The temperature was raised to 32()°C, held for 3 minutes, then lowered at a cooling rate of 40°C/min, and the crystallization energy (A>) at the time of cooling was measured.In general, this PPS-only sample The temperature was lowered to room temperature (25°C), and the temperature was increased again at 20°C/min for 32
No crystallization peak was observed when the temperature was raised to 0°C. Next, the crystallization energy of the test piece was measured. That is, the temperature is raised at a temperature increase rate of 20°C/min in a nitrogen stream, and the PPS in the part that has not yet crystallized after molding is
The crystallization energy of was measured. This is taken as the crystallization energy (B) (the B value is a value converted by PPS content and ratio).

From this, the crystallization rate was determined using the following formula: (A-8>/A X100.The A value measured here was 41
．． It was 2 J/9. The crystallization rate is a value that indicates how much PPS has crystallized during molding. The larger the value of the crystallization rate, the more crystallization is promoted during molding, and the higher the degree of crystallization of the molded product.

The results are shown in Table 1.

1 Example Comparative Example 1 3 1 2 Component (parts by weight) PPS 10G 70 70 100
701PP 10 5 CR733S --5 GF -3030-30 Thermal characteristics Tc"("C) 96 98 107 125
125 Crystallization rate (%) 97 98 86 4
2 4B degree of thermal thermal deformation ('C) 4.6 and Q load 1250 270 270 88 9
618.6K 130 260 252 8B
93 Table 1 shows that in the Examples in which a phosphate ester compound was added to PPS, the crystallization temperature of the molded articles was low and the crystallization rate was high, indicating that the resin composition had good crystallinity. On the other hand, in the comparative example, the crystallization temperature was high and the crystallization rate was low.

In addition, the molded products of the examples show clearly higher heat distortion temperatures than the comparative examples, even though they were molded in a low-temperature mold of 60°C.

, 4 to 10 and 3 to 9 Pellets of resin compositions were prepared in the same manner as in Examples 1 to 3, except that the components shown in Table 2 were used in the amounts shown in Table 2, and the pellets were further molded. A test piece was prepared. Using this, the crystallization temperature and heat distortion temperature (18,6 KO load) were measured in the same manner as in Examples 1 to 3. Furthermore, flame retardancy was evaluated according to LJL 94 using the same test piece. The smaller the value of ■, the more flame retardant =
The results are shown in Table 2.

As can be seen from Table 2, even in polymer blends of PPS and other resins, the molding amount of the resin composition of the present invention is
It can be seen that in both cases, the crystallization temperature of PPS is low and the crystallinity is good.

Further, the molding amount of the example shows a clearly higher heat distortion temperature than that of the comparative example, even though the molding was performed using a low temperature mold of 60°C. Incidentally, flame retardancy is also improved by adding a phosphoric acid ester compound.

(Effects of the Invention) Since the PPS resin composition of the present invention has improved crystallinity of PPS, it has a high degree of crystallinity even when molded at low temperatures and has excellent heat resistance.

Claims (1)

[Scope of Claims] A resin composition containing a polyphenylene sulfide resin, which contains 0.01 to 40 parts by weight of a phosphoric acid ester compound based on 100 parts by weight of the polyphenylene sulfide resin. Composition.