JPH06340809A - Polyarylene sulfide resin composition with improved adhesion - Google Patents

Abstract

(57) [Summary] [Structure] Polyarylene sulfide modified with epoxy resin or other epoxy group-containing compound (P
AS) or P consisting of the modified PAS and unmodified PAS
A PAS resin composition with improved adhesion, comprising 100 parts by weight of an AS component and 0.01 to 30 parts by weight of a styrene / maleic anhydride copolymer. [Effect] It is possible to obtain a molded product that maintains the excellent properties such as heat resistance, chemical resistance, and rigidity that the PAS resin originally has, and that has excellent adhesiveness with an adhesive.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin composition capable of forming a molded article having excellent adhesiveness with an adhesive. More specifically, the present invention relates to a polyarylene sulfide resin composition containing an epoxy-modified polyarylene sulfide, which is capable of forming a molded article having excellent adhesiveness with an epoxy adhesive. INDUSTRIAL APPLICABILITY The polyarylene sulfide resin composition of the present invention is useful as various engineering plastics, particularly as a structural material, a sealing material for mechanical parts and electronic parts, and the like.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as
Polyarylene sulfide (hereinafter referred to as "PAS") represented by "PPS" has excellent heat resistance, chemical resistance, rigidity, etc., and is used as various molding materials, but its crystallinity is extremely high. Since it is extremely high and does not have a functional group in the main chain, it has poor affinity with many adhesives including epoxy adhesives when formed into molded products. Therefore, in the case of a structure using an adhesive, the strength of the bonded portion of the PPS portion remains uneasy.

In order to solve the above problems, it is known to mix an epoxy resin into PPS (Japanese Patent Laid-Open No. 1-1999).
65171 and JP-A-1-69657). However, the affinity of the PPS resin composition mixed with the epoxy resin with the adhesive is not sufficient, and it has been difficult to obtain a structural material, a mechanical part, or the like having excellent adhesive strength.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of the prior art and to maintain the original good heat resistance, chemical resistance and rigidity of PAS. It is an object of the present invention to provide a PAS resin composition capable of obtaining a molded article which is extremely excellent in adhesiveness with an adhesive and, by extension, has a remarkably high adhesive strength.

[0005]

The present invention is directed to a polyarylene sulfide modified with an epoxy resin or other epoxy group-containing compound (hereinafter referred to as epoxy-modified PAS).
Say. ) Or the epoxy-modified PAS and unmodified PAS
And a styrene / maleic anhydride copolymer in an amount of 0.01 to 30 parts by weight, the PAS resin composition having improved adhesiveness.

The PAS component preferably comprises at least 5% by weight of the epoxy-modified PAS. Further, the PAS resin composition of the present invention preferably contains 70 parts by weight or less of a filler with respect to 30 parts by weight of the PAS component.

In the PAS used for producing the unmodified PAS and the epoxy-modified PAS used in the present invention, the skeleton is composed of an arylene sulfide bond represented by the following formula (I), or the arylene sulfide bond (I) is a main component. age,

[0008]

[Chemical 1]

An ether bond represented by the following formula (II), a sulfone bond represented by the following formula (III), a biphenyl bond represented by the following formula (IV), and a substituted phenyl represented by the following formula (V). A sulfide bond (provided that R ¹ represents an alkyl, nitro, phenyl, alkoxy, carboxyl or amino group in the formula (V)) and a trifunctional bond represented by the following formula (VI) are exemplified. A bond derived from such a copolymerization component may be contained as a poor component. However, the copolymerization component is preferably less than 30 mol%.

[0010]

[Chemical 2] The PAS having the skeleton as described above is obtained, for example, by reacting an alkali metal sulfide (typically sodium sulfide) with a dihalide. here,
Examples of the dihalide used as a raw material include dihalogenated benzene represented by the following formula.

[0011]

[Chemical 3] (In the formula, R ² represents each group of alkyl or alkoxy having 1 to 3 carbon atoms, nitro, phenyl, carboxyl or amino, n represents an integer of 0 to 3, and X represents a halogen atom).

Specific examples of such dihalogenated benzene include compounds represented by the following formula. However, in these formulas, X ₁ is a halogen atom, and examples thereof include Cl or Br. These dihalogenated benzenes are generally used in the form of a mixture,
It is preferable that para dihalide is contained in this mixture in an amount of 85 mol% or more.

[0013]

[Chemical 4]

In the reaction between the alkali metal sulfide and the dihalide, if necessary, a trihalide such as trichlorobenzene may be added to the reaction system within a range of 5 mol% or less based on the dihalide. The polymerization reaction may be carried out in a polar solvent, preferably an amide solvent such as N-methyl-2-pyrrolidone (NMP) or dimethylacetamide, or a sulfone solvent such as sulfolane. At this time, in order to control the degree of polymerization, it is desirable to add an alkali metal salt of carboxylic acid or sulfonic acid, alkali hydroxide or the like. The temperature and time for the preferred polymerization reaction are approximately 120 to 300 ° C. and 2 to 10 hours. It is desirable to carry out the reaction in an inert gas atmosphere. After completion of the reaction, the solid product is filtered off, washed thoroughly with deionized water and dried to obtain a PAS resin.

PAS can be crosslinked by heating in an oxygen atmosphere after polymerization, or by adding a crosslinking agent such as peroxide and heating to make it higher in molecular weight before use.

As the PAS used in the present invention, various types of PAS can be widely used as described above. PAS purified by a conventional method after the polymerization is deionized or purified by a conventional method. It is possible to use one in which the PAS is made to have a high molecular weight as described above and further deionized to reduce the content of sodium or other alkali metal to 900 ppm or less. Alternatively, after the polymerization, PAS purified by a conventional method is deionized to reduce the content of sodium or other alkali metal to 900 ppm or less, and then a cross-linking agent is added to heat and cross-link to increase the molecular weight. it can.

An acid treatment method may be mentioned as the deionization treatment method. A typical method of acid treatment is to immerse PAS in an acid or its water solubility. Upon acid treatment,
It is also possible to appropriately stir or heat. A specific example of the acid treatment method is a method in which the PAS powder is immersed in an acetic acid aqueous solution having a pH of 4 and stirred for about 30 minutes. The acid-treated PAS needs to be washed several times with water or warm water to remove residual acid or salt.
The water used for washing is preferably distilled water or deionized water so as not to impair the denaturing effect of the acid treatment. PAS
The acid used for the acid treatment is not particularly limited as long as it has no action of decomposing PAS, and specific examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propionic acid. Of these, acetic acid and hydrochloric acid are preferable, and nitric acid is not preferable because it decomposes and deteriorates PAS.

The epoxy-modified PAS used in the present invention is produced by reacting the PAS produced as described above with an epoxy resin or another epoxy group-containing compound (hereinafter referred to as an epoxidizing agent).

Specific examples of the epoxy resin used for the modification of PAS include conjugated or non-conjugated dienes, epoxidized compounds such as conjugated or non-conjugated cyclic dienes and unsaturated carboxylic acid esters having conjugated or non-conjugated dienes, and aliphatic compounds. Polyglycidyl ethers obtained by reacting diols, aliphatic polyhydric alcohols, bisphenols, phenol novolacs, cresol novolacs, etc. with epichlorohydrin or β-methylepichlorohydrin, dicarboxylic acids with epichlorohydrin or β-methylepichlorohydrin The obtained polyglycidyl ester etc. are mentioned.

Further, as the epoxy group-containing compound other than the epoxy resin used for the modification of PAS, the following general formula (VII):

[Chemical 5] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms, Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, and m is 1 to 4
Represents the integer) of the glycidyl compound.

Preferred glycidyl compounds include those represented by the following general formula (VIII).

[Chemical 6] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms.)

Such a glycidyl compound can be produced by the following method, as disclosed in, for example, JP-A-60-130580. First, an aromatic hydrocarbon having at least one phenolic hydroxyl group, N-methylolacrylamide or N-methylolmethacrylamide, or an alkyl ether derivative of N-methylolmethacrylamide (hereinafter, these are referred to as N-methylolacrylamides). By condensation using an acid catalyst, the following general formula (IX):

[Chemical 7] (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms, and Ar ′ is 6 to 6 carbon atoms having at least one hydroxyl group.
20 is an aromatic hydrocarbon group, and n represents an integer of 1 to 4. ) Is produced.

The above-mentioned aromatic hydrocarbon having at least one phenolic hydroxyl group is not particularly limited,
For example, phenol, o-cresol, m-cresol,
p-cresol, 2,6-xylenol, 2,4-xylenol, o-chlorophenol, m-chlorophenol, o-phenylphenol, p-chlorophenol,
Phenolic compounds such as 2,6-diphenylphenol, polyphenolic compounds such as hydroquinone, catechol and phloroglucinol, polycyclic hydroxy compounds such as 1-naphthol, 2-naphthol and 9-hydroxyanthracene, 2,2-bis Examples thereof include bisphenols such as (4-hydroxyphenyl) propane (bisphenol-A) and bis (4-hydroxyphenyl) methane.

Then, the hydroxyl group of the compound represented by the general formula (IX) is glycidylated to give the compound represented by the general formula (VII
) The glycidyl compound represented by this can be obtained.
This glycidylation is preferably carried out by performing an addition reaction between the compound represented by the general formula (IX) and epihalohydrin, and then dehydrohalogenating with caustic alkali. As the above-mentioned epihalohydrin, epichlorohydrin, epibromhydrin, epiiodohydrin, etc. can be used.

The addition reaction with epihalohydrin is carried out using a phase transfer catalyst. As the phase transfer catalyst, for example, a quaternary ammonium salt such as tetrabutylammonium bromide, trioctylmethylammonium chloride or benzyltriethylammonium chloride, or a quaternary phosphonium salt such as tetraphenylphosphonium chloride or triphenylmethylphosphonium chloride is used. be able to.

The amount of the phase transfer catalyst used is represented by the general formula (I
If the compound represented by X) is 100 mol%, 0.01
It is preferably in the range of ˜100 mol%. A particularly preferable amount of the phase transfer catalyst used is 0.05 to 10 mol%. The reaction temperature and the reaction time are 50 to 120 ° C. and 5
Minutes to 2 hours, more preferably 10 to 3 at 80 to 110 ° C
0 minutes.

The addition of epihalohydrin is followed by dehydrohalogenation with caustic. As the caustic alkali, caustic soda, caustic potash, lithium hydroxide and the like can be used. These can be used as solids or as aqueous solutions. As the dehydrohalogenation catalyst, the same one as the above-mentioned phase transfer catalyst can be used. Further, a catalyst other than the above phase transfer catalyst can also be used, and as such a catalyst, crown ethers,
Examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycol.

The amount of the caustic alkali used is represented by the general formula (I
It is preferred to use an equimolar amount to the compound represented by X). More preferably, 1.1 to 1.5 times the molar amount is used. The reaction temperature and reaction time are 20 to 90 ° C. and 10 minutes to 3 hours, and more preferably 40 to 70 ° C. and 30 minutes to 20 hours.

In carrying out the reaction between PAS and the epoxidizing agent, the charging ratio of both reaction components is 0.1 parts by weight or more, preferably 1 to 10 parts by weight of the epoxidizing agent with respect to 100 parts by weight of PAS.
0 parts by weight. If the amount of the epoxidizing agent is less than 0.1 part by weight, the object of the present invention cannot be achieved.

The polar organic solvent used as a reaction catalyst for the reaction between PAS and the epoxidizing agent is, for example, N-
Methyl-2-pyrrolidone (NMP), dimethylacetamide, dimethylformamide, dimethylsulfoxide may be mentioned. Reaction temperature and reaction time are generally room temperature to 3
00 ° C, preferably 100 ° C to 280 ° C and 10 minutes to
You can choose within a range of 20 hours.

After completion of the reaction, the slurry is filtered, and the obtained cake is washed with a solvent capable of dissolving an epoxidizing agent such as acetone or NMP, and then dried. When washed with a high boiling organic solvent such as NMP, it is desirable to further wash with ion-exchanged water or the like in order to facilitate drying.

When carrying out the reaction between PAS and the epoxidizing agent, if necessary, a curing agent for the epoxy resin or a curing agent for the epoxy resin,
A catalyst that accelerates the reaction between PAS and the epoxidizing agent may be present. The curing agent is PA according to the reaction according to the invention.
Since it has an action of promoting the binding between the S-bonded epoxidizing agent and another epoxidizing agent, it serves to increase the amount of the epoxidizing agent bonded to PAS. As a curing agent,
Amines, acid anhydrides, imidazoles, polysulfides, phenol resins and the like which are generally used as a curing agent for epoxy resins can be added. A curing accelerator may be used in combination with these curing agents. Tertiary amines and phosphines are preferably used as the catalyst for promoting the reaction between PAS and the epoxidizing agent. Specific examples thereof include triethylamine, tributylamine, dimethylbenzylamine, tris (dimethylaminomethyl) phenol, tributylphosphine, triphenylphosphine and the like.

The weight average molecular weight of the epoxy-modified PAS is preferably 5,000 to 100,000. When the PAS and the epoxidizing agent are reacted according to the present invention,
It is considered that the terminal glycidyl group of the epoxidizing agent reacts with -SH and / or -SNa of PAS to bond,
Furthermore, the hydroxyl group generated by this bond may react with the glycidyl group of another epoxidizing agent.

The PAS component in the PAS resin composition of the present invention is composed of the epoxy-modified PAS alone as described above or a mixture of the epoxy-modified PAS and unmodified PAS. The composition of the mixture is such that the epoxy-modified PAS is 5% by weight or more, 1
It is preferably less than 00% by weight and the unmodified PPAS is 95% by weight. If only the unmodified PAS is used as the PAS component without using the epoxy-modified PAS, a PAS molded article having a high adhesive strength, which is the object of the present invention, cannot be obtained.

As the styrene / maleic anhydride copolymer to be mixed with the PAS component, a copolymer of styrene and maleic anhydride and, if necessary, a monomer copolymerizable therewith is used. The ratio f (%) of maleic anhydride residues in the copolymer consisting of styrene and maleic anhydride is preferably f = 0.1 when f (%) = [n / (n + m)] × 100. ˜50%, more preferably f = 1 to 40%. In the above formula, m is the number of moles of the repeating unit derived from styrene [represented by the following formula (a)], and n is the number of repeating units derived from maleic anhydride [represented by the following formula (b)]. Is a number.

[0036]

[Chemical 8] Further, in the case of a copolymer composed of styrene, maleic anhydride and a monomer copolymerizable therewith, when the number of moles of repeating units derived from the copolymerizable monomer is p, the following formula f ' (%) = [N / (n + m + p)] × 100 The maleic anhydride residue ratio f ′ (%) in the copolymer is preferably 0.1 to 50%, more preferably 1 to 40%.

The amount of the styrene / maleic anhydride copolymer blended with the PAS component is 0.01 to 30 parts by weight, preferably 0.1 to 100 parts by weight of the PAS component.
15 parts by weight. If the blending amount of the styrene / maleic anhydride copolymer is less than 0.01 part by weight, a PAS molded article having a high adhesive force, which is the object of the present invention, cannot be obtained, and
If the blending amount of the copolymer exceeds 30 parts by weight, a molded product having the original good characteristics of the PAS resin cannot be obtained.

A fibrous or particulate filler is added to the PAS resin composition of the present invention containing the above PAS component and a styrene / maleic anhydride copolymer for the purpose of imparting various properties depending on its use. It can be used by mixing in an appropriate amount. Examples of such fillers include glass fibers, carbon fibers, metal fibers, aramid fibers, fibrous potassium titanate, asbestos and fibrous inorganic and organic fillers such as various whiskers such as silicon carbide and silicon nitride. , Graphite, calcium carbonate, mica, silica,
Boron Nitride, Barium Sulfate, Calcium Sulfate, Kaolin, Clay, Vylophyllite, Bentonite, Sericite, Zeolite, Mica, Nepheline Cinite, Ferrite, Attapulgite, Wollastonite, Calcium Silicate, Magnesium Carbonate, Dolomite, Antimony Trioxide Inorganic particulate fillers such as magnesium oxide, zinc oxide, titanium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass powder, glass beads, quartz, quartz glass, iron, zinc, copper, aluminum and nickel. To be
These fillers may be used alone or in combination of two or more.

For use as a sealing material for structural materials, mechanical parts and electronic parts, it is preferable to use a combination of glass fiber and calcium carbonate as a filler, especially 20 to 80% by weight of glass fiber and 80 to 80% of calcium carbonate. 20
Fillers consisting of wt% are preferred.

The blending amount of the filler and the PAS component is preferably 30 parts by weight or more of the PAS component and 70 parts by weight or less of the filler, more preferably 40 to 80 parts by weight of the PAS component, based on 100 parts by weight of the total amount of both. The filler is 60 to 20 parts by weight.

In addition to the filler, the PAS resin composition of the present invention has other additives such as a heat stabilizer, a light stabilizer, a flame retardant, a plasticizer, an antistatic agent, and a foaming agent for the purpose of modifying the filler. Agent,
A nucleating agent or the like can be added.

The PAS resin composition of the present invention comprises a PAS component, a styrene / maleic anhydride copolymer, and various additives optionally added, and a single screw extruder, a twin screw extruder, a Banbury mixer, and a kneading machine. 250 using a kneader such as a roll or Brabender Plastograph (registered trademark)
It can be prepared by kneading in a molten state at ˜350 ° C., preferably 280˜340 ° C.

[0043]

EXAMPLES Hereinafter, the production method and characteristics of the PAS resin composition of the present invention will be specifically described with reference to Examples. A synthetic example of epoxy-modified PPS will be described prior to Examples.

Synthesis of Epoxy Modified PPS Synthesis Example 1 1.0 g of epoxy resin (Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd.) was added to 1.0 g of PPS having a Na ion content of 800 ppm and N-methyl-2-pyrrolidone (NM).
A solution dissolved in 10 ml of P) was added, and the reaction was carried out at 180 ° C. for 3 hours. After the reaction, it was cooled to room temperature and then filtered. The obtained cake was washed with acetone and vacuum dried at 150 ° C to obtain an epoxy-modified PPS. The addition rate of the epoxy resin was 17% by weight.

Synthesis Example 2 The epoxy resin used was Epotote YD manufactured by Tohto Kasei Co., Ltd.
Epoxy modification of PPS was performed in the same manner as in Synthesis Example 1 except that -019 was used. Addition rate of epoxy resin is 2.4% by weight
Met. Synthesis Example 3 The epoxy resin used was Epotote YD manufactured by Tohto Kasei Co., Ltd.
PPS epoxy modification was performed in the same manner as in the synthesis example except that CN-704 was used. Addition rate of epoxy resin is 5.4% by weight
Met.

Synthesis Example 4 Except that the PPS used was replaced with T-4AG manufactured by Topren,
Epoxy modification of PPS was performed in the same manner as in Synthesis Example 3. The addition rate of the epoxy resin was 2.1% by weight. Synthetic Example 5 PPS was epoxidized in the same manner as in Synthetic Example 3, except that the PPS used was replaced with T-1 made by Toprene. The addition rate of the epoxy resin was 3.5% by weight.

In the above synthesis example, the addition rate of the epoxy resin was measured as follows. The addition rate [(weight of bound epoxy resin / weight of PPS resin) × 100 (%)] was determined from the IR spectrum of the product obtained as follows.
Using a calibration curve prepared in advance by blending PPS before reaction used for modification with epoxy resin used for modification at various ratios, 1520 cm ^-1 and PPS of CPS based on C = C stretching vibration of epoxy resin The addition rate was calculated from the absorbance ratio at 1400 cm ⁻¹ based on C = C stretching vibration.

The raw materials and additives used in the examples (including the comparative examples) are as follows. [1] Polyarylene sulfide (a) Poly (p-phenylene) sulfide (T-1 manufactured by Topren Co., Ltd.) [2] Epoxy-modified polyarylene sulfide Epoxy-modified PPS synthesized according to Synthesis Example 5

[3] Styrene / maleic anhydride copolymer (a) SMA2000 manufactured by Arco Chemical, styrene / maleic anhydride (molar ratio = 2/1) copolymer, average molecular weight 1,700 (b) manufactured by Arco Chemical SMA1000, styrene / maleic anhydride (molar ratio = 1/1) copolymer, average molecular weight 1,600 (c) Sekisui Plastics Co., Ltd. Dailark # 232, styrene / maleic anhydride (weight ratio = 20 / 80) G) copolymer, MFR = about 3 g / 10 min. (230 ° C,
2,160g load)

[4] Filler (a) Glass fiber (b) Calcium carbonate [5] Epoxy adhesive manufactured by Nagase Ciba Co., Ltd. XNR3101 (main agent) XNH3101 (hardening agent)

Examples 1 to 13 Raw materials [1] to [4] are shown in Table 1- (1) and Table 1- (2).
Are mixed at the ratio shown in, and the mixture is 20 mmφ and L / D = 2.
A thermoplastic PPS resin composition was prepared by kneading with a No. 0 twin-screw extruder at 300 ° C. and 400 rpm. The obtained resin composition was injection-molded and the tensile shear adhesive strength was measured according to JIS K6850. (The adhesive curing time is 10
It is 0 ° C. for 1 hour. ) The results are also shown in Table 1.

Comparative Examples 1 to 12 Resin compositions were prepared in the same manner as in Examples using the raw materials [1] and [2] or [1] and [3], and the tensile shear adhesive strength was evaluated. The results are also shown in Table 1.

[0053]

[Table 1]

As is clear from Table 1, the molded articles obtained from the thermoplastic PPS resin composition of the present invention are excellent in tensile shear strength. It is considered that this is due to the compatibility effect of the epoxy-modified PPS. A system in which epoxy-modified PPS is blended with PPS and a styrene / maleic anhydride copolymer is not blended (Comparative Examples 4 to 6) and a system in which styrene / maleic anhydride copolymer is blended with PPS without epoxy-modified PPS. Comparative Examples 7 to 12 are clearly inferior in tensile shear strength as compared with the composition of the present invention.

[0055]

Since the thermoplastic PAS resin composition of the present invention contains epoxy-modified PAS and styrene / maleic anhydride copolymer, molded articles obtained from this composition are adhesives, especially epoxy-based adhesives. Excellent adhesion to agents. INDUSTRIAL APPLICABILITY The thermoplastic PAS resin composition of the present invention is useful as various engineering plastics, particularly as a structural material, a mechanical component, a sealing material for electronic components, and the like.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadao Ikeda 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (2)

[Claims] 1. A polyarylene sulfide modified with an epoxy resin or another epoxy group-containing compound, or 100 parts by weight of a polyarylene sulfide component composed of the modified polyarylene sulfide and an unmodified polyarylene sulfide, and styrene / maleic anhydride. A polyarylene sulfide resin composition having improved adhesion, which comprises 0.01 to 30 parts by weight of a copolymer. 2. The polyarylene sulfide resin composition according to claim 1, further comprising 70 parts by weight or less of a filler with respect to 30 parts by weight of the polyarylene sulfide component.