JPH0321665A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition suitable for electric parts, etc., having improved heat resistance and mechanical properties by blending a resin composition comprising a polyarylene sulfide and a polyarylene sulfide ketone with a specific amount of an epoxy compound. CONSTITUTION:100 pts.wt. resin comprising (A) a polyarylene sulfide and (B) a polyarylene sulfide ketone is blended with (C) 0.1-15 pts.wt., preferably 0.3-10 pts.wt. epoxy compound (preferably novolak type epoxy resin) and (D) 0-30 pts.wt. olefin compound polymer modified with carboxyl group or derivative group thereof and/or polyamide.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a resin composition comprising polyarylene sulfide and polyarylene sulfide ketone that has improved heat resistance and mechanical properties. Such composites are used as various injection molding materials, compression molding materials, and extrusion molding materials, and are particularly preferably used for electronic parts that require solder resistance.

(Prior Art and Problems to be Solved by the Invention) Polyarylene sulfide is well known as an engineering plastic with excellent heat resistance, chemical resistance, flame retardance, and mechanical and electrical properties. However, the melting point is about 2
Since the temperature is 80℃, the short-term heat resistance temperature is 260-270℃.
is the upper limit, and there are restrictions on its use in applications that require higher heat resistance. On the other hand, polyarylene sulfide ketone, which has been attracting attention recently, has extremely high heat resistance compared to polyarylene sulfide.
According to Publication No. 3-113020, the melting point of polyarylene sulfide ketone is 340°C. Therefore, it is conceivable that heat resistance can be improved by mixing polyarylene sulfide ketone with polyarylene sulfide.

However, simply mixing them has problems such as not only not being able to obtain the expected heat resistance but also low mechanical strength.

(Means for Solving the Problems) In view of the above-mentioned circumstances, the present inventors have made efforts to ensure that a composition containing both polyarylene sulfide and polyarylene sulfide has higher heat resistance and mechanical properties. As a result of investigation, it was discovered that the problem could be solved by using an epoxy compound together with polyarylene sulfide and polyarylene sulfide getone, leading to the present invention.

That is, the present invention provides (A) polyarylene sulfide and (B)
) Resin 100 consisting of polyarylene sulfide ketone
Contains (C) 0.1 to 15 parts by weight of an epoxy compound and (D) 0 to 30 parts by weight of an olefin compound polymer and/or polyamide modified with a carboxylic acid group or its derivative group based on the weight part. This invention relates to a resin composite article characterized by:

The polyarylene sulfide in the present invention can be obtained by various known methods. For example, methods for producing it include polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide, sodium bisulfide and sodium hydroxide, hydrogen sulfide and sodium hydroxide, or sodium acetate in a polar solvent. Methods include polymerization in the presence of p-noalkanoate, self-condensation of p-chlorothiophenol, etc., but polymerization in amide solvents such as N-methylpyrrolidone and dimethylacetate, and sulfonic solvents such as sulfolane, etc. A common method is to react sodium sulfide with p-dichlorobenzene. At this time, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization.

On the other hand, polyarylene sulfide ketone is produced by using the monomer p-dichlorobenzene or p-chlorothiophenol in the production method of polyarylene sulfide.
4,4'-dichlorobenzophenone or 4,(4-
It can be similarly obtained by replacing chlorobenzoyl)thiophenol. Furthermore, even if the copolymerization component H of polyarylene sulfide or polyarylene sulfide ketone contains alkyl groups, nitro groups, amino groups, phenyl groups, alkoxy groups, carboxylic acid groups, or carboxylic acid gold, the crystallinity of the polymer It doesn't matter as long as it doesn't significantly affect. When a trifunctional or more functional phenyl, biphenyl, naphthyl sulfide bond, etc. is selected for copolymerization, the amount is preferably 3 mol% or less, more preferably 1 mol% or less.

These polyarylene sulfide and polyarylene sulfide ketone may be thermally or oxidatively crosslinked or non-crosslinked.

In the present invention, the weight ratio of polyarylene sulfide and polyarylene sulfide ketone can be adjusted as desired. Generally, polyarylene sulfides 1 to 99
% by weight.

The epoxy compound of the present invention is a compound containing at least one, preferably two or more epoxy groups, and includes various liquid or solid epoxy resins. for example,
Bisphenol A, resorcinol, hydroquinone,
Birocatechol, bisphenol F1 saligenin, 1,
3.5-} IJ hydroxybenzene, bisphenol S, trihydroxydiphenyldimethylmethane, 4,
Glycidyl ethers of bisphenols such as 4-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis(4-hydroxyphenyl)hexane, halogenated bisphenols in place of bisphenol, and dibutanediol Glycidyl ethers such as glycidyl ether, glycidyl esters such as phthalic acid glycidyl ester, N
- Glycidyl epoxy resins such as glycidyl amines such as glycidylaniline; linear non-glycidyl epoxy resins such as epoxidized polyolefins and epoxidized soybean oil; and cyclic non-glycidyl epoxy resins such as vinyl cyclohexene dioxide and dicyclopentadiene dioxide; Examples include tris(hydroxyphenyl)methane and polyglycidyl ether epoxy modified silicone oil.

An example of a particularly preferred epoxy compound in the present invention is a novolac type epoxy resin. Novolac-type epoxy resin contains two or more epoxy groups, and is obtained by reacting a novolak-type phenol resin with epichlorohydrin. Novolac type phenolic resin is obtained by a condensation reaction between phenols and formaldehyde. There are no particular restrictions on the phenols used as this raw material, but they include phenol, O-cresol, m-cresol, p-cresol, and p-cresol.
Cresol, bisphenol A, resorcinol, p-tert-butylphenol, bisphenol F1, bisphenol S, and mixtures thereof are particularly preferably used. Furthermore, epoxidized products of poly p-vinylphenol and halogenated products of these epoxy resins can also be used in the same manner as the novolac type epoxy resin.

These epoxy resins may be used alone or as a mixture of two or more. The amount of the epoxy resin added is 0.00 parts by weight per 100 parts by weight of the polyarylene sulfide and polyarylene sulfide ketone. 1 to 15 weight, preferably 0.
It is 3 to 10 parts by weight. If the amount added exceeds 15 parts by weight, it is not preferable because the thermal stability of the product decreases.
0. If it is less than 1 part by weight, heat resistance and mechanical properties will not be sufficiently improved.

In the present invention, an olefin compound polymer and/or polyamide modified with a carboxylic acid group or its derivative group can be added together with the epoxy compound. This makes it possible to further improve mechanical properties, particularly crack resistance.

In the olefin compound polymer modified with a carboxylic acid group or its derivative group, the olefin compound polymer before modification is a polymer or copolymer obtained by polymerizing one or more types of olefin compounds. The copolymer includes a copolymer of an olefin compound and a vinyl aromatic compound. Examples of olefin compounds include monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, 3-methylpentene-1, 4-methylpentene-1, isobutylene; butadiene, isoprene-1.3 - Conjugated diolefins such as pentadiene; non-conjugated diolefins such as 1,4-hexadiene and norbornene-norbornene derivatives. On the other hand, examples of vinyl aromatic compounds include styrene, α-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, and ethylbulbenzene.

A method for modifying an unmodified olefin compound polymer with a carboxylic acid group or its derivative group involves adding an unsaturated carboxylic acid or its derivative to the unmodified olefin compound polymer in a solution state or a molten state using or using a radical initiator. It is common to add it without removing it. When a conjugated diolefin is used as part or all of the olefin compound in the unmodified olefin compound polymer, aliphatic double bonds are introduced. However, in order to maintain the thermal stability of the composition of the present invention, it is preferable to hydrogenate at least 80% or more to reduce the double bonds. Preferred specific examples of unsaturated carboxylic acids or derivatives thereof include maleic acid, fumaric acid, maleic anhydride, itaconic anhydride, citraconic anhydride, maleic acid imide, itaconic acid ξ-do, and citraconic acid iodide. In particular, maleic anhydride, itaconic anhydride, and maleic acid ξ-ide can be preferably used.

The amount of graft reaction of unsaturated carboxylic acid monomer is 0.01
-10% by weight, preferably 0.05-5% by weight. If the grafting reaction amount of the unsaturated carboxylic acid monomer is less than 0.01% by weight, the improvement in crack resistance will not be sufficient, and if it exceeds 10% by weight, PPS
Either case is undesirable, as the heat resistance of the product is impaired. Preferred representative examples of olefin compound polymers modified with carboxylic acid groups or derivative groups thereof include acid-modified polyethylene, acid-modified polypropylene, acid-modified polyethylene/propylene, acid-modified polymethylpentene, acid-modified polyptene, and acid-modified polyethylene. /butene-1, acid-modified polyisobrene, acid-modified polyisobutylene, acid-modified hydrogenated polyptadiene, acid-modified hydrogenated polyacrylonitrile/butadiene, and copolymers of these with styrene, as well as metal ion crosslinked products (ionomers), etc. However, it is not necessarily limited to these.

Furthermore, bolyamides include nylon 6, nylon 66, nylon 11, nylon 12, nylon 10, nylon 6,9
, nylon 4.6, and aromatic polyamide. Aromatic polyamides include poly p-terephthalamide, poly p-isophthalamide and copolymers.

The amount of these olefin compound polymers or polyamides modified with carboxylic acid groups or derivative groups thereof is preferably 0 parts by weight of Q-3 per 100 parts by weight of the total of polyarylene sulfide and polyarylene sulfide ketone. . If the amount exceeds this range, the heat resistance will be greatly reduced.

The compounds of the present invention include fibrous reinforcing agents such as glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, ceramic fiber, metal fiber, and silicon nitride; barium sulfate, calcium sulfate, kaolin, clay, and light, bentonite, sericite, zeolite, mica,
Mica, nephelinsinite, talc, akulbulgite, wollastonite, PMF (processed mineral fiber), ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum dioxide, graphite, gypsum, glass beads,
Inorganic fillers such as glass balloons, glass flakes, glass powder, and quartz powder; organic reinforcing agents such as aramid fibers can be contained up to 80% by weight in the composition. When adding these reinforcing agents or fillers, known silane coupling agents can be used. The composition of the present invention may also contain small amounts of mold release agents, colorants, heat stabilizers, ultraviolet stabilizers, foaming agents, and corrosion inhibitors (for example, ZnO + T) as additives within the scope of the purpose of the present invention.
- alumina, dolomite, etc.).

The composition of the present invention can be prepared by various known methods. For example, the raw materials are mixed uniformly in advance using a mixer such as a tumbler or Henschel mixer, and then fed to a single-screw or twin-screw extruder where they are melt-kneaded at 230 to 400°C.
A method of pelletizing can be used. Further, when extrusion-kneading, the reaction between PPS and the epoxy compound can be promoted by dividing the epoxy compound into two or more portions and performing the extrusion operation two or more times. Furthermore, the addition of the epoxy compound can be carried out by pre-preparing a composite of polyarylene sulfide, polyarylene sulfide ketone and, in some cases, an olefin compound polymer and/or polyamide modified with carboxylic acid groups or derivative groups thereof. It is also possible to implement it later.

(Effects of the Invention) The present invention has the effect of improving the heat deformation resistance and mechanical properties of a combination of polyarylene sulfide and polyarylene sulfide ketone by adding an epoxy compound; It is presumed that this is due to interaction with the epoxy compound.

(Example) Example 1, Comparative Example 1.

ASTM 0123B-74 (315.5℃, 5
000g load) measured at a melt flow rate of 10
20 g/10 minutes 80 parts by weight of nylene sulfide and ASTM 01238-74 (360°C, 5000 g
Melt flow rate measured at 1150 g
/10 minutes repeating unit sulfide ketone 20
Weight parts and Novolafuku type epoxy resin, Epicron N-6
95 (manufactured by Dainippon Ink & Chemicals KK) was mixed in a Henschel ξ mixer, melted and kneaded into pellets using a twin-screw extruder at 350°C, and then measured for physical properties at a cylinder temperature of 350°C using an injection molding machine. I created a test piece for this purpose.
As shown in the results in Table 1, significant improvements in heat distortion temperature, bending strength, and impact strength were observed compared to Comparative Example 1 in which no epoxy compound was added. Examples 2 to 4 Example 1 except for changing the amount and type of epoxy compound and adding acid-modified olefin compound polymer or boria ξ-do
An experiment was conducted in the same manner. The results are shown in Table 1.

Example 5, Comparative Examples 2 to 4 24 parts by weight and 16 parts by weight of polyphenylene sulfide and polyphenylene sulfide ketone used in Example 1, respectively.
parts by weight, further 30 parts by weight of glass fiber, 3 parts by weight of calcium carbonate
After mixing 0 parts by weight of the epoxy compound and 2 parts by weight of the epoxy compound in a Henschel mixer, a Tetos piece for measuring physical properties was prepared in the same manner as in Example 1. As shown in Table 1, compared to Comparative Example 2 in which no epoxy compound was added, heat distortion temperature, bending strength,
Significant improvement in impact strength is observed. Even when compared with Comparative Example 3.4, which lacked polyphenylene sulfide or polyphenylene sulfide ketone, improvements in physical properties that were unexpected from the results of both cases were observed.

Claims (1)

[Claims] 1. 0.1 to 15 parts by weight of (C) an epoxy compound and (
D) A resin composition comprising 0 to 30 parts by weight of an olefin compound polymer and/or polyamide modified with a carboxylic acid group or a derivative group thereof.