WO2007058332A1

WO2007058332A1 - Polyarylene sulfide resin composition and molded article jointed with epoxy resin

Info

Publication number: WO2007058332A1
Application number: PCT/JP2006/323054
Authority: WO
Inventors: Yoko Todaka; Katsuhei Onishi
Original assignee: Polyplastics Co., Ltd.
Priority date: 2005-11-17
Filing date: 2006-11-14
Publication date: 2007-05-24
Also published as: JP2007137996A

Abstract

Disclosed is a polyarylene sulfide resin composition which shows excellent adhesion to an epoxy resin without the need of being provided with an adhesion pretreatment and also shows improved adhesion after annealing. Specifically, the composition comprises (A) 100 parts by weight of a polyarylene sulfide resin, (B) 6 to 20 parts by weight of a fatty acid ester of a polyhydric alcohol, and (C) 0 to 400 parts by weight of an inorganic filler.

Description

Description Polyarylen sulfide resin composition and molded product joined with epoxy resin

The present invention relates to a polyarylene sulfide resin composition and a molded article excellent in adhesion to an epoxy resin. Background art

Polyphenylene sulfide (hereinafter abbreviated as PPS) Polyarylene sulfide represented by resin (hereinafter abbreviated as PAS) Resin has high heat resistance, mechanical properties, chemical resistance, and dimensional stability Because of its properties and flame retardancy,

Widely used for electronic parts materials, automotive equipment parts materials, chemical equipment parts materials, etc. Especially for electronic components, electrical insulation, maintenance of mechanical strength, temperature and float.

Protection from the external environment such as free impurities is indispensable for maintaining the performance, and so-called “sealing”, in which sealing is performed using a synthetic resin, is generally performed. As such a sealing resin material, an epoxy resin is exclusively used, but it is necessary to closely incorporate or fix it in a support such as a substrate or a container for supporting and fixing the resin. As a substrate material for holding or incorporating a strong epoxy resin body, first of all, it has excellent adhesiveness with epoxy resin and can withstand harsh usage environments, heat resistance, flame resistance, mechanical properties, etc. However, it is a fact that a resin material having sufficient performance has not been obtained yet. PAS resin has excellent mechanical properties, heat resistance, chemical resistance, and flame resistance when blended with an appropriate reinforcing material or filler, and is suitable as a protective material. Adhesion was poor. The adhesion of PAS resin is slightly improved by chemical treatment such as mechanical roughening of the adhesive surface of the molded product, plasma treatment, etc .: physical treatment, chemical etching, etc. This is not only economically unfavorable, but also its adhesion is not always sufficient. In addition, the molded PAS resin is generally annealed to provide heat resistance, mechanical properties, etc. that can withstand harsh usage environments, but the adhesion of PASS resin that has undergone this treatment is reduced. Therefore, there is a problem that the required adhesive strength cannot be sufficiently satisfied. ■

Methods for improving the adhesion between PAS resin and epoxy resin include, for example, a method in which an epoxy resin is blended with PAS Kitsuki (JP-B 6-1 047 7 3), a method in which a specific polyester is blended (JP -B 3 1 73 1 9 2) and methods of blending talc (JP-B 2 80 1 7 88) have been proposed, but these methods are not mentioned at all regarding the adhesion during annealing. . '

In addition, a method of blending _α -olefin fin copolymer, epoxy resin, glass fiber and silane compound mainly composed of hyolein and α, | 3-unsaturated alkynole esterolate

(JP-A 2002- 2 3500 2) has been proposed, but there was a problem that the surface easily peeled off, and it did not contribute sufficiently.

Furthermore, a method (JP-A 58-74 7 5 1 JP-A 8-23 1 8 50) in which a fatty acid ester having a relatively low concentration is blended has also been proposed, but the adhesive performance required for PAS resin is sufficient. Not satisfied with Disclosure of the invention

An object of the present invention is to provide a PAS resin composition and a molded product that solve the above-mentioned problems of the prior art, have excellent adhesion to an epoxy resin without performing pre-adhesion treatment, and have improved adhesion after annealing. To do.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a PAS resin is mixed with a predetermined proportion of a fatty acid ester of a polyhydric alcohol and, if necessary, an inorganic filler, thereby adhering to an epoxy resin. The present inventors have found that a PAS resin composition and a molded product having improved properties can be obtained, thereby completing the present invention.

That is, the present invention

(A) For 100 parts by weight of polyarylene sulfide resin,

(B) Polyhydric alcohol fatty acid ester 6-20 parts by weight (C) Inorganic filler 0-400 parts by weight

A polyarylene sulfide resin composition comprising:

A molded article joined with an epoxy resin, which is obtained by injection molding the polyarylen sulfide resin composition. '' Detailed description of the invention

Hereinafter, the constituent components of the present invention will be described in detail. The PAS resin as the component (A) used in the present invention is a polymer compound mainly composed of-(Ar-S)-(where Ar is an arylene group) as a repeating unit, and is generally known in the present invention. PAS resin with a molecular structure can be used.

Examples of the arylene group include, for example, p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p′-diphenylene norephone group, p , p'-biphenylene group, p, p'-diphenylene ether group, p, p'-diphenylene carbonyl group, naphthalene group and the like. The PAS resin may be a homopolymer consisting only of the above repeating units, or a copolymer containing the following different types of repeating units may be preferable from the viewpoint of processability.

As the homopolymer, PPS using an arylene group and L-p-phenylene group and having a p_phenylene sulfide group as a reversing unit is preferably used. As the polymer, among the arylene sulfide groups comprising the above-mentioned arylene groups, two or more different combinations can be used, and among them, p-phenylene sulfide groups and m-phenylene sulfide groups are used. Combinations including are particularly preferred. In this, p- phenylene sulfide group of 70 mole ⁰ /. As mentioned above, those containing 80 mol% or more are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties.

Further, among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound can be preferably used. In addition to PAS resin with a structure, a small amount of monomers such as polyhaloaromatic compounds having 3 or more halogen functional groups are used for condensation polymerization. In addition, a polymer having a partially branched structure or a crosslinked structure can be used, and a low-molecular-weight linear structure polymer is heated at high temperature in the presence of oxygen or an oxidant to form an oxidation bridge or a thermal bridge. Polymers with increased melt viscosity and improved moldability or mixtures thereof can also be used. 'Further, the PAS resin used in the present invention, the linear PAS resin (310 ° C' viscosity at Li speed OOsecf ¹ is 10~300Pa. S) as a main component, a portion (30 wt ^_0/0 , preferably 2 to 25 wt / _0), a relatively high viscosity (300~3000Pa · s, preferably 500 ~ 2000 Pa -. it may be a s) mixed system of branched or crosslinked PAS resin. In addition, the PAS resin used in the present invention is preferably a polymer obtained by purifying by removing acid by-product impurities and the like by performing acid washing, hot ice washing, organic solvent washing (or a combination thereof) after polymerization.

Next, the component (B) used in the present invention is a fatty acid ester of a polyhydric alcohol and is not particularly limited. If one of the hydroxyl groups is a fatty acid ester, the fatty acid ester of the polyhydric alcohol of the present invention Become. The formula (1) X preferably has the structure of (2). Particularly, in the formula (1) or (2), ^X: group ~X average 70 mol% or more of ^4, the average more than 70 mole% of some stomach γ ΐ~γ ³ is represented by the following formula (The rest are —Η, 1Ο, alkyl group or aryl group.) Especially preferably, X i X ⁴ Y] to Υ ³ are fatty acids of a polyhydric alcohol in which all of the groups are represented by the following formulae: Ester.

0

II

— 0— C— R wherein R represents an alkyl or aryl group having 2 to 30 carbon atoms, preferably an alkyl group having 8 to 24 carbon atoms.

Typical examples of fatty acid esters of polyhydric alcohol represented by the formula (1) include pentaerythritol monostearate, pentaerythritol tristearate, pentaerythritol distearate, pentaerythritol monostearate. Etc. Typical examples of the fatty acid ester of the polyhydric alcohol represented by the formula (2) include glycerin tristearate, glycerin distearate, and glycerin monostearate. The amount of component (B) is 6 to 20 parts by weight, preferably 6 to 16 parts by weight, based on 100 parts by weight of (A) polyarylene sulfide resin. If the amount is less than 6 parts by weight, the effect of improving the adhesion to epoxy resin is not sufficient, and if it exceeds 20 parts by weight, bleeding occurs and the mechanical properties of the molded product cause problems, which is not preferable. '' The resin composition of the present invention can be blended with an inorganic filler (C) to improve performance such as mechanical strength, heat resistance, dimensional stability (deformation resistance, warpage) and electrical properties. Depending on the purpose, fibrous, powdery, or plate-like fillers are used.

Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica 'alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, Examples include inorganic fibrous materials such as metallic fibrous materials such as titanium, copper, and brass. Particularly typical fibrous fillers are glass fiber or carbon fiber. High melting point organic fiber materials such as polyamide, fluororesin, and acrylic resin can also be used. On the other hand, granular fillers include carbon black, silica, quartz powder, glass beads, glass powder, oxalic acid, calcium, aluminum oxalate, kaolin, tanolec, clay, diatomaceous earth, and wollastonite Metal oxides such as salts, iron oxides, titanium oxides, zinc oxides, aluminas, metal carbonates such as calcium carbonate and magnesium carbonates, sulfates of lithium, sulfates of metals such as barium sulfate, other silicon carbides, Examples include silicon nitride, boron nitride, and various metal powders. Examples of the plate-like filler include My strength, glass flakes, and various metal foils. These inorganic fillers can be used alone or in combination of two or more.

When using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. Examples of this are functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds. These compounds may be added at the same time as the power to be used after surface treatment or convergence treatment, or material preparation.

The amount of the inorganic filler (C) used is not particularly limited, but is generally 400 parts by weight or less, preferably 10 to 300 parts by weight, per 100 parts by weight of the component (A) PAS resin. If it is too small, the mechanical strength is slightly inferior. If it is too large, the molding operation becomes difficult, and there is a problem with the mechanical strength.

In the resin composition of the present invention, a silane compound can be blended for the purpose of improving burrs and the like within a range not impairing the effects of the present invention. As the silane compound, T includes various types such as bur silane, methacryloxy silane, epoxy silane, amino silane, mercapto silane, and the like. Examples include, but are not limited to, trimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyl-trimethoxysilane, and the like.

The resin composition of the present invention can be used in combination with a small amount of other thermoplastic resins in addition to the above components depending on the purpose. Other thermoplastic resins include, for example, polyphenylene ether, polyphenylene sulfone, polysulfone, polycarbonate, polyacetal, etc., as well as liquid crystalline polymers, polyarylate, polyethylene terephthalate, polybutylene terephthalate. Ester resins such as Polyethylene, Polypropylene, Poly 4-methylpentene-1, etc. Resin resins; Nylon 6, Nylon 6 6, Amid resins such as aromatic nylon; Polymethyl (meth) acrylic Rate, polyacryloylstyrene (AS resin), polystyrene, norbornene resin, etc. (^ cyclic olefin resin etc.) These thermoplastic resins can be used in combination of two or more.

Further, the resin composition of the present invention generally contains known substances generally added to thermoplastic resins, that is, stabilizers such as antioxidants, flame retardants, dyes * colorants such as pigments, lubricants and crystallization acceleration. Agents, crystal nucleating agents, etc. can be added as appropriate according to the required performance.

The resin composition of the present invention can be prepared by facilities and methods generally used for preparing a synthetic resin composition. In general, necessary components can be mixed, melt kneaded using a single or twin screw extruder, and extruded to form a pellet. It is also a preferred method to melt-extrude the resin component and add and mix an inorganic component such as glass fiber in the middle.

The material pellets obtained in this way are injection molded, extruded, vacuum formed, and compressed. Although generally known thermoplastic resin molding methods such as molding can be used for molding, injection molding is most preferred.

Since the PAS resin composition of the present invention is excellent in adhesiveness to an epoxy resin, it is suitably used for a molded product joined with an epoxy resin. The composite molded product supporting or interiorizing the epoxy resin of the present invention is set with, for example, a functional part to be supported on a substrate or container molded with a PAS resin composition, and a thermosetting epoxy resin as described below is set on this. It is manufactured by injecting and curing, encapsulating functional parts with epoxy resin, and simultaneously fixing the PAS resin composition molded product. In addition, an epoxy resin body that has been encapsulated with epoxy resin and cured in advance is set in a mold, inserted into the mold by an injection molding method, and the exterior support is molded with a PAS resin composition. Shapes may be formed.

The PAS resin composition of the present invention (1) The molded product is a practically sufficient epoxy resin without any special surface treatment such as mechanical roughening, physical treatment such as plasma treatment, chemical treatment such as chemical etching, etc. Adhesiveness can be obtained, but of course, such surface treatment may be used in combination when particularly strong adhesiveness is required, and further effects can be obtained. .

The epoxy resin to be bonded to the PAS resin composition molded product of the present invention is not particularly limited, and is a curable epoxy resin used as a sealant or adhesive for ordinary functional parts, paint, etc. In general, an organic compound having an epoxy group obtained by reaction of an active hydrogen compound such as bisphenol A with epichlorohydrin or oxidation of a double bond compound in the presence of a curing agent or a catalyst. It is a substance that reacts and cures when it is left or heated at room temperature, and can be used with various viscosities depending on the purpose. Further, the PAS resin composition molded article of the present invention has an effect on the adhesiveness even when applied with the epoxy paint as described above. In addition, the PAS resin composition molded article of the present invention is preferably subjected to annealing treatment in order to impart heat resistance, mechanical properties, etc. that can withstand more severe use environments. The annealing conditions are optimally selected depending on the application or shape of the molded product. An annealing temperature of 100 to 260 ° C and an annealing time of 0.5 to 10 hours are preferable, and particularly preferable. Annealing temperature is 120 ~ 240 ° C, annealing time is 1 ~ 8 hours. The degree of annealing is determined by the annealing temperature and annealing time. However, if the annealing degree is too low, the desired properties cannot be sufficiently provided. There is.

Further, in general molded PAS resin, the adhesive strength is lowered by the annealing treatment a for the above-mentioned purpose, but the PAS resin composition molded product of the present invention is improved in the adhesion strength by annealing treatment. It also has an effect. Example

Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these.

Examples 1-6, Comparative Examples 1-5

(A) Add components (B) and (C) to the polyphenylene sulfide resin in the amounts shown in Table 1, mix for 5 minutes with a Henschel mixer, and then add this to the twin-screw extrusion at a cylinder temperature of 320 ° C. The resin composition pellets were made.

Next, from this pellet, an injection molding machine was used to mold a test piece (width 10 mm, thickness 4 mm) according to IS 0 3 1 6 7 under the conditions of a cylinder temperature of 320 ° C and a mold temperature of 140 ° C. The following tests were conducted. The results are shown in ¾ 1. '

[Measurement of adhesive strength with epoxy resin]

The above ISO test piece is cut at the center, washed with acetone, and then an epoxy resin adhesive (XN1244 manufactured by Ciba Chemtex Co., Ltd.) is applied to the specified area (0.7 mm x 0.7 mm). After bonding and curing at 120 ° C for 1 hour and leaving at 23 ° C for 1 day, the peel strength was measured in the direction perpendicular to the bonding surface, and the adhesive strength was measured (Device name: TENSILON UT -I- 25 00 / TOYO BALDWIN).

In addition, the adhesive strength was measured in the same manner as described above for samples that were washed with acetone and then annealed at 240 ° C for 6 hours in an air dryer.

The specific substances (A) to (C) used in Examples and Comparative Examples are as follows. (A) Polyph:!: Nylene sulfide (PPS) Resin Co., Ltd. Kureha, Fort mouth KPS (310 ° C, melt viscosity 140Pa · s at OOsecf ¹ )

(B) Polyhydric alcohol fatty acid ester

• (B-1) Pentaerythritol tetrastearate (manufactured by NOF Corporation, Unistar H- 4 76)

• (B-2) Glycerin tetrastearate (Riken Vitamin Co., Ltd., Poem S— 9 5)

• (Β'- 1) Glycerin (Katayama Chemical Co., Ltd., special grade reagent)

(0 Inorganic filler

-Non-strength re-glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS 03 Τ-7 1 7

Claims

The scope of the claims

1. (A) 100 parts by weight of polyarylene sulfide resin

(B) Polyhydric alcohol fatty acid ester 6-20 parts by weight

(0 inorganic filler 0-400 parts by weight

A polyarylene sulfide resin composition comprising

2. The polyylene sulfide resin composition according to claim 1, wherein (B) is a fatty acid ester of a polyhydric alcohol represented by the following formula (1).

CH ₂ X ²

CHzX ¹ — C— CH ₂ X ³ (1)

CH ₂ X ⁴

(However, ~ ⁴ is at least one

O

II

—O—C consists of C-R groups, and the remainder consists of —H, —OH, alkyl groups or aryl groups. R represents an alkyl group having 2 to 30 carbon atoms or an aryl group. )

3. The polyarylen sulfide resin composition according to claim 1, wherein (B) is a fatty acid ester of a polyhydric alcohol represented by the following formula (2).

CH2Y ¹

CHY ² (2) formula

CH ₂ Y ³

(However, at least one of Y ^{1 to} Y ³ is

0

II

— Ο— C One R The rest consists of 1 H, _OH, an alkyl group or an aryl group. R represents an alkyl group having 2 to 30 carbon atoms or an aryl group. )

4. In the fatty acid esters of polyhydric alcohols represented by the formula (1), 70 mol Xi～X ⁴ sac Chi average. /. More than

O

II

The polyarylene sulfide resin composition according to claim 2, which is ————— C—R group (wherein R is as described above). -,

.

5. In the fatty acid ester of polyhydric alcohol represented by the formula (2), an average of 70 mol% or more of Yi Y ³

0

II

4. The polyarylene sulfide resin composition according to claim 3, which is —O—C 1 R group (wherein R is as described above).

6. A molded article joined with an epoxy resin, which is obtained by injection molding the polyarylen sulfide resin composition according to any one of claims 1 to 5.