JPH11130961A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide resin compsn. which is excellent in adhesion to an adhesive such as an epoxy resin adhesive while further improving the excellent properties inherent in a polyarylene sulfide resin. SOLUTION: This compsn. comprises a polyarylene sulfide resin (A), a particulate silicon compd. (B) (pref. a reactive particulate silicon compd. having functional groups), a polycarbodiimide resin (C) and/or a polymeric silane coupling agent (D), and an inorg. filler (E). Based on 100 pts.wt. sum of ingredients A, B, C, and D, 0.1-30 pts.wt. ingredient B, 0.1-5 pts.wt. ingredient C and/or D, and 1-400 pts.wt. ingredient D are contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyarylene sulfide (hereinafter sometimes referred to as PAS) resin composition. More specifically, the present invention relates to a PAS resin composition having good adhesion to an adhesive such as an epoxy resin.

[0002]

2. Description of the Related Art Polyarylene sulfide resins are engineering plastics having excellent heat resistance, flame retardancy, electrical properties and various mechanical properties. Therefore, polyarylene sulfide resins are used in various fields such as mechanical fields, electric and electronic fields. Use is expected. By the way, the PAS resin is sometimes used alone by taking advantage of its excellent characteristics. However, in order to further improve the performance, the PAS resin is bonded to another resin or another material such as ceramics or metal, or the performance is improved. Different P
As a material obtained by laminating AS resins, it is sometimes used for a wide range of applications.

In such a case, an epoxy resin is usually used as an adhesive between the PAS resin and another material such as a resin or ceramics or metal, or as an adhesive between a certain PAS resin and another PAS resin having different performance. However, since the PAS resin itself has poor adhesiveness, sufficient adhesive strength may not be obtained. In this case, in order to improve the adhesive strength, for example,
Prior to applying the adhesive, a special treatment such as forming a fine groove on the surface of the base material by mechanical means such as friction or increasing the surface area by corrosion is performed. Also,
In some cases, a chemical primer was applied to the surface of the substrate to improve the adhesion of the substrate to the adhesive.

However, these methods require extra steps, and furthermore, the effect may not be expected depending on the type of the base material. For example, PAS resin and epoxy resin, silicon resin, urethane resin, etc. There has been a strong demand for a technique capable of expressing good adhesiveness with an adhesive.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has been made to further improve the good properties of PAS resin while improving the adhesiveness with an adhesive such as an epoxy resin. Another object of the present invention is to provide an excellent polyarylene sulfide resin composition.

[0006]

Means for Solving the Problems The present inventors have previously prepared a composition (Japanese Patent Application No. 9-016741) in which a polyarylene sulfide resin is blended with a polycarbodiimide resin or a polycarbodiimide precursor, and a polyarylene sulfide resin. A composition in which a polyethylene naphthalate resin, a polycarbodiimide resin or a polycarbodiimide precursor is blended with the resin (Japanese Patent Application No. 9-179634) has been proposed.

As a result of further intensive studies on the above object, the present inventors have found that the above object can be more effectively achieved by a polyarylene sulfide resin composition having a specific composition. The present invention has been made based on such findings. That is, the present invention provides the following polyarylene sulfide resin composition. (1) Polyarylene sulfide resin (A), particulate silicon compound (B), preferably reactive particulate silicon compound (B) having a functional group, polycarbodiimide resin (C) and / or polymer silane A polyarylene sulfide resin composition comprising a coupling agent (D), wherein when the total amount of (A) to (D) is 100 parts by weight, the particulate silicon-based compound (B) is 0.1 to 30. A polyarylene sulfide resin composition comprising 0.1 to 5 parts by weight of a polycarbodiimide resin (C) and / or a polymer type silane coupling agent (D). (2) polyarylene sulfide resin (A), particulate silicon compound (B), preferably reactive particulate silicon compound having a functional group (B) polycarbodiimide resin (C) and / or polymer silane cup A polyarylene sulfide resin composition comprising a ring agent (D) and an inorganic filler (E), wherein when the total amount of (A) to (D) is 100 parts by weight, the particulate silicon-based compound (B ) Is 0.1 to 30 parts by weight, the polycarbodiimide resin (C) and / or the polymer silane coupling agent (D) is 0.1 to 5 parts by weight, and the inorganic filler (E) is 1 to 30 parts by weight. A polyarylene sulfide resin composition of about 400 parts by weight.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the polyarylene sulfide resin composition of the present invention will be specifically described for each component. 1. Polyarylene sulfide resin (component (A)) Polyarylene sulfide (PA) used in the present invention
S) and (A) are polymers containing a repeating unit represented by the structural formula -Ar-S- (where Ar is an arylene group) in an amount of 70 mol% or more, and a typical substance is the following structural formula (I)

[0009]

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(Wherein R ¹ is an alkyl group having 6 or less carbon atoms, an alkoxy group, a phenyl group, a carboxylic acid / metal salt,
A substituent selected from an amino group, a nitro group, a halogen atom such as fluorine, chlorine, and bromine, and m is an integer of 0 to 4. N is an average degree of polymerization and is in the range of 1.3 to 30), and is a polyphenylene sulfide having a repeating unit represented by at least 70 mol%.

According to the production method, PAS is generally known to have a substantially linear molecular structure having no branched or cross-linked structure and a PAS having a branched or cross-linked structure. It is also effective for Preferable PAS for use in the present invention includes a homopolymer or copolymer (hereinafter abbreviated as PPS) containing 70 mol% or more, more preferably 80 mol% or more of paraphenylene sulfide units as repeating units. If this repeating unit is less than 70 mol%, the original crystallinity, which is a characteristic of a crystalline polymer, tends to be low, and sufficient mechanical properties tend not to be obtained, which is not preferable. Examples of the copolymerizable structural unit include a metaphenylene sulfide unit, an orthophenylene sulfide unit, p,
p'-diphenylene ketone sulfide unit, p, p'-
Diphenylene sulfone sulfide unit, p, p'-biphenylene sulfide unit, p, p'-diphenylene ether sulfide unit, p, p'-diphenylene methylene sulfide unit, p, p'-diphenylene cumenyl sulfide unit, naphthyl And sulfide units. Further, as the polyarylene sulfide of the present invention, in addition to the above-mentioned substantially linear polymer, a branched or cross-linked polyarylene sulfide polymerized by using a small amount of a monomer having three or more functional groups as a part of the monomer is also used. Further, a blended polymer obtained by blending the above-mentioned linear polymer with the above-mentioned linear polymer can also be used. Further, functional groups such as -SH group and -NH ₂ group,
P having a group such as —COOH group or —OH group in its skeleton
AS is more preferably used. The position where such a functional group is present is not limited to the terminal of the PAS, but may be anywhere.
Also, for example, PAS modified with an acid such as maleic acid or fumaric acid can be used.

The PAS resin can be obtained, for example, by subjecting a dihalo aromatic compound and a sulfur source to a polycondensation reaction in a polar organic solvent by a method known per se. As a preferred example of the PAS resin, for example, polyphenylene sulfide represented by the following structural formula (II) (hereinafter, referred to as polyphenylene sulfide)
It may be called PPS. ) Resins.

[0013]

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2. Particulate Silicon Compound (Component (B)) Silicon compounds refer to ordinary organopolysiloxanes, because silicon resins having a three-dimensional network structure have heat resistance and are unlikely to cause so-called sink marks during molding. It is preferably used. The particle size is not particularly limited as long as it is in the form of particles. The bulk density is preferably between 0.4 and 0.5 g / ml,
The true specific gravity is preferably about 1.5.

The reactive particulate silicon-based compound refers to a compound obtained by introducing a functional group such as an epoxy group, a methacryl group or an amino group into the particulate silicon-based compound. The amount of the introduced functional group is not particularly limited. In particular, when a polycarbodiimide-based resin is used as the component (C), a reactive particulate silicon-based compound obtained by introducing a functional group, particularly an epoxy group, into the particulate silicon-based compound is preferably used. 3. Polycarbodiimide-Based Resin (C) In the present invention, a polycarbodiimide-based resin may be used as the component (C). The polycarbodiimide-based resin is a polycarbodiimide-based resin itself, a polycarbodiimide precursor, or a mixture thereof. Can be used.

The polycarbodiimide resin has a carbodiimide group (-N = C = N-) in its molecule. The number of carbodiimide groups present in the molecule is not particularly limited.
Those having one carbodiimide group per 0 to 1000, preferably 200 to 600 are used. The form used may be liquid or powder. In the case of a liquid, its viscosity is not particularly limited. In the case of powder, the particle size is not particularly limited, but usually, the average particle size is 5 to 1500 µm in consideration of ease of handling, easy mixing with the resin portion, and the like.

In the molecule, a carbodiimide group (-N = C =
Any compound having N-) may be used, and may have another functional group other than the carbodiimide group. For example,
The polycarbodiimide-based resin preferably having an isocyanate group (-NCO) at the terminal is usually used.
It can be prepared from an organic polyisocyanate in the presence of a catalyst that promotes the carbodiimide of the isocyanate.

As the polycarbodiimide resin, specifically, 2,4-tolylene diisocyanate, 2,6-
Tolylene diisocyanate, 4,4,4-triphenylmethylene triisocyanate, and the like. Also,
The polycarbodiimide precursor is a mixture of a catalyst and an organic polyisocyanate used for producing a polycarbodiimide-based resin from an organic polyisocyanate, or a phenol, an isocyanate group of the organic polyisocyanate.
A mixture of a catalyst blocked with a monofunctional active hydrogen compound such as aniline and the above catalyst.

The catalyst for promoting the carbodiimide of isocyanate from the organic polyisocyanate includes various catalysts. For example, 1-phenyl-3-methyl-3-phospholene-1-oxide, 1-ethyl-3 −
Methyl-3-phospholene-1-oxide, 1-phenyl-3-phospholene-1-oxide and the like can be mentioned. 4. Polymer type silane coupling agent (D) In the present invention, a polymer type silane coupling agent may be used as the component (D). The polymer type silane coupling agent is a polydimethylsiloxane on the side chain,
For example, a group (X) having reactivity with an inorganic substance such as an alkoxy group, a group (Y) having reactivity with an organic substance such as an epoxy group or a hydroxyl group, and a group (Y) having a reactivity with an organic substance such as a polyether group or an alkyl group. Thus, a compound having three units of a group (Z) that enhances compatibility with an organic substance in one molecule.

Specifically, X is an alkoxy group, Y is an epoxy group and Z is a polyether group, or X is an alkoxy group, Y is a hydroxyl group, and Z is a poly group. Those which are ether groups are exemplified. 5. Inorganic filler (C) Various inorganic fillers such as fibrous, granular, and powdery materials are used. For example, examples of the material of the fibrous inorganic filler include glass fiber, carbon fiber, whisker, and the like.

As the material of the granular or powdery inorganic filler, for example, talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate,
Calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate,
Examples include tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, and glass beads. Among such inorganic fillers, in particular, glass fillers such as glass powder, glass flake,
Glass beads, glass filaments, glass fibers, glass lobing, and glass mats are preferred.

Further, as the inorganic filler, a material which has been subjected to a surface treatment with a coupling agent or the like in order to improve the adhesiveness with a resin may be used. As the coupling agent, a silane coupling agent, a titanium coupling agent, or any conventionally known coupling agent can be arbitrarily selected and used. Among them, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Aminosilanes such as silane, epoxysilane, and isopropyl tri (N-amidoethyl, aminoethyl) titanate are preferred.

Further, a film-forming substance (film former) can be used in combination with the above-mentioned coupling agent. As the film-forming substance, conventionally known substances can be used without any particular limitation. System, epoxy system, polyether system and the like are preferably used. Such an inorganic filler may be used alone, but may be used in combination of two or more if necessary. 6. Mixing ratio of each component The total amount of the polyarylene sulfide resin (A), the particulate silicon-based compound (B), the polycarbodiimide-based resin (C) and / or the polymer type silane coupling agent (D) was set to 100 parts by weight. At this time, the amount of the particulate silicon compound (B) is 0.1 to 30 parts by weight, preferably 0.1 to 20 parts by weight, and more preferably 1 to 20 parts by weight. If the amount is less than 0.1 part by weight, the effect of addition may not be exhibited. If the amount exceeds 30 parts by weight, mechanical properties characteristic of polyarylene sulfide resin may be impaired.

Regarding the polycarbodiimide resin (C) and / or the polymer type silane coupling agent (D),
When the total amount of the polyarylene sulfide resin (A), the particulate silicon-based compound (B), the polycarbodiimide-based resin (C) and / or the polymer type silane coupling agent (D) is 100 parts by weight, 0.1 to It is 5 parts by weight, preferably 0.5 to 3 parts by weight, more preferably 1 to 2 parts by weight. If the amount is less than 0.1 part by weight, the effect of addition may not be exhibited, and an oil film may be formed on the surface of the molded article exceeding 5 parts by weight, which may lower the adhesiveness. When the polycarbodiimide-based resin (C) is used alone or when the polymer-type silane coupling agent (D) is used alone, the quantitative compounding ratio is as described above, but the polycarbodiimide-based resin (C) and the polymer When the silane coupling agent (D) is used in combination, the mixing ratio is as described above with respect to the total amount of both.

Similarly, for the inorganic filler (E), a polyarylene sulfide resin (A), a particulate silicon compound (B), a polycarbodiimide resin (C) and / or a polymer type silane coupling agent (D) The total amount of
1 to 400 parts by weight, preferably 00 parts by weight,
The content is 10 to 200 parts by weight, more preferably 30 to 100 parts by weight. If the amount is more than 400 parts by weight, the viscosity of the composition may increase and molding may be difficult. If the amount is less than 1 part by weight, the effect of adding the inorganic filler itself may not be sufficiently obtained. 7. Other Components In addition to the above components, other components may be added to the polyarylene sulfide resin composition of the present invention, if necessary, as long as the object of the present invention is not impaired. Other components include, for example, antioxidants, heat stabilizers,
Various additives such as lubricants, coloring agents, plasticizers, and conductivity-imparting agents, thermoplastic resins and / or thermosetting resins such as polyamide, epoxy resin, polyolefin, polyethersulfone, and polyphenylene ether, and hydrogenated SB
S, hydrogenated NBR, rubbers such as fluororubber, pigments and the like. The content of other components can be appropriately selected within a range that does not impair the purpose of the present invention. 8. Preparation of Polyarylene Sulfide Resin Composition The polyarylene sulfide resin composition of the present invention can be prepared by blending each of the above components and kneading them, for example.

The above-mentioned melt-kneading can be carried out by a commonly known method. In any case, the above-mentioned components are uniformly mixed and dispersed in a resin, so that a predetermined resin composition is obtained. I do. For the melt-kneading, a twin-screw extruder, a single-screw extruder or the like can usually be suitably used.

The conditions for the melt-kneading are not particularly limited. However, in order to limit the decomposition or foaming of other components added as necessary, an extremely high temperature or an extremely long residence time should be avoided. Is preferred. The specific temperature is usually 280 to 350 ° C, preferably 285 to 330 ° C. The polyarylene sulfide resin composition thus prepared is usually granulated or cut into a shape and size suitable for a material for secondary processing such as pellets, in particular, a material for injection molding, and is appropriately provided for each application. Is done.

[0028]

EXAMPLES Hereinafter, the polyarylene sulfide resin composition of the present invention will be described more specifically with reference to examples. [Examples 1-3, Comparative Examples 1-3] <Preparation of sample> Twin screw extruder (TEM3 manufactured by Toshiba Machine Co., Ltd.)
5) Using a Henschel mixer to uniformly mix the following polyphenylene sulfide resin (PPS resin) and other components at the mixing ratios shown in Table 1 and setting the cylinder temperature to 310 to 350 ° C. The mixture was melt-kneaded to produce pellets. <Preparation of component (A) (linear type PPS)> A polymerization vessel equipped with a stirrer was charged with hydrous sodium sulfide (Na ₂ S · 5H).
₂ O) 833 mol, lithium (LiCl) 830 mol of NMP500 liter chloride was added to a 1 hour dehydrated while maintaining the 145 ° C. under vacuum. Then, set the reaction system to 45.
After cooling to ℃, 905 mol of dichlorobenzene (DCB) was added, and polymerization was carried out at 260 ° C for 3 hours. 5 times the contents with hot water,
1 N-methyl-2-pyrrolidone (NMP) at 170 ° C
Washed three times with water and dried at 185 ° C. to obtain PPS. <Other components blended in the PPS resin> (B) component Particulate silicon-based compound manufactured by Dow Corning Toray Co., Ltd., trade name DC4-705
1 Reactive particulate silicon compound having an epoxy group (powder having an average particle size of several tens of μm) (C) Component Carbodiimide polymer: Nisshinbo Co., Ltd. brand name Carbodilite HMV-8CA
(Carbodiimide equivalent = 278, average particle size = 1000μ)
(D) Component (D) Polymer-type silane coupling agent Product name MAC-2301 manufactured by Nippon Unicar Co., Ltd. A product comprising an alkoxy group (X), a hydroxyl group (Y) and a polyether group (Z) on the side chain of polydimethylsiloxane. It has three units in one molecule, and has an alkoxy group equivalent of 248 and a hydroxyl group equivalent of 1200. (E) Ingredients ・ Glass fiber manufactured by Asahi Fiber Glass Co., Ltd., trade name JAFT591 <Method for evaluating physical properties> ・ Adhesiveness A test piece (2.5 cm wide, 10 cm long) obtained by injection molding the composition shown in Examples or Comparative Examples. ) 2 pieces, adhesion area is 2.4c
Bonding was performed using an epoxy-based resin adhesive or a silicon-based resin adhesive so as to obtain m ^2, and both ends of each were pulled to cause breakage.

Strength (MPa): The strength was determined from the stress at the time of breaking. Destruction form: Obtained by visually observing the part where the destruction occurred. (i) "Material destruction" refers to a state in which the bonded surface has not been destroyed but has been destroyed in the material portion, indicating that strong adhesion has been achieved. (ii) “Interfacial peeling” refers to a state in which peeling has occurred at the interface between the adhesive and the adherend, indicating that the adhesion is weak.

(Iii) The term "cohesive failure" refers to a state in which the adhesive phase has been broken, but not at the interface between the bonded surfaces, indicating that the bonding itself was strong. <Evaluation Results> The evaluation results are shown in Table 1.

[0031]

[Table 1]

[0032]

As described above, the present invention provides a polyarylene sulfide resin composition which further improves the good properties of the PAS resin and has excellent adhesiveness with an adhesive such as an epoxy resin. be able to.

Claims (3)

[Claims] 1. A polyarylene sulfide resin (A),
A polyarylene sulfide resin composition comprising a particulate silicon-based compound (B), a polycarbodiimide-based resin (C) and / or a polymer-type silane coupling agent (D), and the total amount of (A) to (D) Is 100 parts by weight, the particulate silicon compound (B) is 0.1 to 30 parts by weight, and the polycarbodiimide resin (C) and / or the polymer silane coupling agent (D) are 0.1 part by weight. A polyarylene sulfide resin composition in an amount of up to 5 parts by weight. 2. A polyarylene sulfide resin (A),
A polyarylene sulfide resin composition comprising a particulate silicon compound (B), a polycarbodiimide resin (C) and / or a polymer silane coupling agent (D), and an inorganic filler (E), wherein (A) ) To (D), when the total amount of the particles is 100 parts by weight, the amount of the particulate silicon compound (B) is 0.1 to 30 parts by weight, and the polycarbodiimide resin (C) and / or the polymer type silane coupling are used. A polyarylene sulfide resin composition comprising the agent (D) in an amount of 0.1 to 5 parts by weight and the inorganic filler (E) in an amount of 1 to 400 parts by weight. 3. The polyarylene sulfide resin composition according to claim 1, wherein the particulate silicon compound (B) is a reactive particulate silicon compound having a functional group.