JPH06104773B2 - Polyphenylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a polyphenylene sulfide resin composition having improved adhesiveness, and more specifically to a specific polyphenylene sulfide resin. The present invention relates to a polyphenylene sulfide resin composition having improved adhesiveness by containing a thermosetting epoxy resin.

<Prior art> Polyphenylene sulfide (hereinafter referred to as PPS) has excellent chemical resistance, heat resistance, electrical insulation, and other excellent properties as an engineering plastic, mainly for injection molding. Used for purposes.

Conventionally, PPS resin compositions containing an epoxy resin include JP-B-54-39856 and JP-A-59-51944 and 59-59.
-51945.

Further, adding a silane compound to PPS for the purpose of improving adhesiveness is disclosed in JP-A-57-158256 and 59-31503.

<Problems to be Solved by the Invention> PPS is used in various applications because it has excellent properties as described above, but it has a drawback that it has poor adhesiveness to other materials. May cause a problem, and higher adhesiveness is required. For example, PP
When S is used for the purpose of encapsulating electronic parts by taking advantage of its characteristics, it has a poor adhesiveness with metal, so that there is a problem that the performance of electronic parts deteriorates due to moisture penetrating from the interface with the lead frame. ing. In addition, when using PPS as a copper clad circuit board, there is a problem that the adhesive strength with the copper foil is low.

In order to meet these demands for improving the adhesiveness, a method by adding a silane compound as described above has been proposed, but it has not yet reached a satisfactory level.

Further, the above-mentioned blending of the epoxy resin is intended to increase the melt viscosity of PPS, and even if the epoxy resin is blended with ordinary PPS, no improvement in adhesiveness is observed.

Therefore, the present inventors, in view of the above situation, as a result of diligent study to obtain a PPS resin having improved adhesion, by blending a thermosetting epoxy resin to the PPS resin subjected to a specific treatment, Finding that this problem is solved,
The present invention has been achieved.

<Means for Solving Problems> That is, the present invention provides (1) 60 to 99.95% by weight of deionized PPS resin.
At least one selected from glycidyl ethers of bisphenols, glycidyl esters of phthalic acid or its hydrogenates, novolac type epoxy resins and cyclic non-glycidyl epoxy resins, thermosetting containing two or more epoxy groups A PPS resin composition comprising 0.05 to 40% by weight of an epoxy resin.

(2) The PPS resin composition according to claim (1), wherein the deionization treatment is an acid treatment followed by washing with water.

(3) The PPS resin composition according to claim (1), wherein the deionization treatment is hot water treatment followed by washing with water.

(4) The PPS resin composition according to claim (1), wherein the deionization treatment is washing with an organic solvent and then washing with water.

PPS used in the present invention is a structural formula 70 mol% or more of the repeating unit represented by, more preferably
A polymer containing 90 mol% or more, wherein the repeating unit is 70
If it is less than mol%, heat resistance is impaired, which is not preferable.

PPS is generally a polymer having a relatively small molecular weight obtained by the production method represented by JP-B-45-3368, and an essentially linear polymer obtained by the production method represented by JP-B-52-12240. In the polymer obtained by the method described in JP-B-45-3368, the polymer obtained by the method described in JP-B-45-3368 can be heated in an oxygen atmosphere after the polymerization or cross-linked with a peroxide or the like. It is also possible to increase the degree of polymerization by adding an agent and heating, and in the present invention, PPS obtained by any method can be used.

Further, PPS can comprise less than 30 mol% of its repeating unit with a repeating unit having the following structural formula.

It is essential that the PPS used in the present invention has been subjected to acid treatment, hot water treatment or washing with an organic solvent.

The case of performing acid treatment is as follows. The acid used for the acid treatment of PPS in the present invention is not particularly limited as long as it has no action to decompose PPS, and acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid,
Examples thereof include silicic acid, carbonic acid, and propyl acid. Among them, acetic acid and hydrochloric acid can be more preferably used, but nitric acid such as nitric acid can be used.
It is not preferable to decompose or degrade PPS.

In the present invention, it is necessary to treat PPS with an acid, and salts, alkalis and the like are not preferable because preferable chemical modification of PPS is not performed.

The acid treatment method includes a method of immersing PPS in an acid or an aqueous solution of an acid, and if necessary, it is possible to appropriately stir or heat. For example, when using acetic acid, pH4
Immerse PPS powder in the solution heated to 80-90 ℃,
A sufficient effect can be obtained by stirring for 0 minutes. The acid-treated PPS needs to be washed several times with water or warm water in order to physically remove the residual acid or salt.

The water used for washing is preferably distilled water or deionized water in the sense that the preferred chemical modification effect of PPS by acid treatment is not impaired.

The case of performing hot water treatment is as follows.

In the hot water treatment of PPS used in the present invention,
It is important that the temperature of the hot water is 100 ° C. or higher, more preferably 120 ° C. or higher, even more preferably 150 ° C. or higher, particularly preferably 170 ° C. or higher. It is not preferable because it is small.

The water to be used is preferably distilled water or deionized water in order to exert the preferable effect of chemically modifying PPS by the hot water washing of the present invention. The operation of hot water treatment is usually
It is carried out by adding a predetermined amount of PPS to a predetermined amount of water, heating and stirring in a pressure vessel. The ratio of PPS to water is preferably as much as possible, but usually 1 part of water is PP
A bath ratio of S200g or less is selected.

In addition, since the decomposition of the terminal group is not preferable for the treatment atmosphere, an inert atmosphere is preferably used to avoid this. Further, it is preferable to wash the PPS after the hot water treatment operation with hot water several times in order to physically remove the remaining components.

The procedure for washing with an organic solvent is as follows.

The organic solvent used for washing PPS in the present invention is not particularly limited as long as it does not have an action of decomposing PPS, and examples thereof include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and 1,3-dimethylimidazolidinone. , Hexamethylphosphoramide, nitrogen-containing polar solvents such as piperazinones, sulfoxide / sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone and sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone, dimethyl ether, dipropyl ether , Ether solvents such as dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, Halogen solvents such Rubenzen, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, alcohol such as polyethylene glycol, polypropylene glycol
Examples thereof include phenol solvents, aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, it is particularly preferable to use N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like. Further, these organic solvents are used alone or as a mixture of two or more kinds.

As a method of washing with an organic solvent, PPS in an organic solvent is used.
There is a method of immersing it in, and if necessary, it is possible to appropriately stir or heat.

The washing temperature when washing PPS with an organic solvent is not particularly limited, and an arbitrary temperature from normal temperature to 300 ° C can be selected. The higher the cleaning temperature is, the higher the cleaning efficiency tends to be, but normally, the cleaning temperature of room temperature to 150 ° C. is sufficient to obtain the effect.

It is also possible to wash under pressure at a temperature above the boiling point of the organic solvent in a pressure vessel. Also, the washing time is not particularly limited. Although it depends on the washing conditions, in the case of the batch type washing, a sufficient effect is usually obtained by washing for 5 minutes or more. It is also possible to wash in a continuous manner.

It is sufficient to wash the PPS produced by the polymerization with an organic solvent, but in order to further exert the effect of the present invention,
It is preferably combined with water washing or warm water washing. Further, when a high-boiling point water-soluble organic solvent such as N-methylpyrrolidone is used, it is preferable to wash the organic solvent and then wash with water or warm water to easily remove the residual organic solvent. Water used for these washings is preferably distilled water or deionized water.

In the present invention, it is essential that PPS is subjected to acid treatment, hot water treatment or washing with an organic solvent, but it is also possible to combine two or more of these treatments, and the order thereof is not particularly limited.

In the present invention, it is preferable that the PPS to be subjected to the acid treatment, the hot water treatment or the washing with the organic solvent is a granular material in terms of treatment / washing efficiency. Since PPS produced by a generally known method is obtained in the form of powder or granules, it is preferable to treat and wash them without pelletizing them.If necessary, they may be classified or crushed before use. It is possible.

Further, PPS having a sodium content of 900 ppm or less can be used in the present invention. The Na content is more preferably 70
0 ppm or less, more preferably 500 ppm or less, and particularly preferably 300 ppm or less is used. Sodium content
Use of PPS in excess of 900 ppm is not preferable because the epoxy resin cannot achieve a remarkable effect of improving the adhesiveness.

The PPS obtained by the known method contains 1000 to 1500 ppm or more of sodium.

As an effective means for reducing the sodium content of PPS to 900 ppm or less, the above-mentioned acid treatment, hot water treatment, or washing with an organic solvent can be used.

Further, PPS used in the present invention, within a range that does not impair the effects of the present invention, an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent,
It is possible to add usual additives such as an anti-UV agent and a coloring agent and a small amount of various polymers. Furthermore, for the purpose of controlling the degree of crosslinking of PPS, a conventional peroxide and JP-A-59-
Crosslinking accelerators such as thiophosphinic acid metal salts described in JP 131650 or JP-A-58-204045, JP-A-58-204045.
It is also possible to add a crosslinking inhibitor such as dialkyltin dicarboxylate or aminotriazole described in JP-A-58-204046.

As the epoxy resin used in the present invention, a liquid or solid resin containing two or more epoxy groups can be used. For example, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin,
1,3,5-trihydroxybenzene, bisphenol S,
Trihydroxy-diphenyldimethylmethane, 4,4'-
Glycidyl ethers of bisphenols such as dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, dihydroxy-diphenyl sulfone, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, halogenated bisphenol, etc. Examples thereof include glycidyl ester of phthalic acid or its hydrogenated product, novolac type epoxy resin, and cyclic non-glycidyl epoxy resin such as vinylcyclohexene dioxide and dicyclopentadiene oxide. However, thermoplastic epoxy-containing polyolefins such as glycidyl methacrylate polymers are excluded from the scope of the present invention because they do not provide the effects of the present invention. These thermosetting epoxy resins may be used alone or as a mixture of two or more kinds.

There is no particular limitation on the proportion of PPS thermosetting resin and epoxy resin compounded, but if the thermosetting epoxy resin content is less than 0.05% by weight, the desired effect is difficult to obtain, and if it exceeds 40% by weight.
Not only may the strength, rigidity, and heat resistance of PPS be impaired, but gelation may occur during melt-kneading, and extrusion stability,
Moldability may be impaired, which is not preferable.

Thermosetting epoxy resins are generally amines, acid anhydrides,
It is molded by blending with a curing agent such as multi-stream compound, phenol resin, etc. In the present invention, the curing agent is not used at all, or even if it is used, the active hydrogen group has a molar ratio of less than half of the epoxy group component. Is desirable. When used in combination with a normal amount of curing agent, a thermosetting epoxy resin
This is because the reaction with PPS is inhibited.

As an effect of using a curing agent together, it can be expected to prevent deterioration of bleeding property and thermal properties due to addition of thermosetting epoxy resin.

In the present invention, the fibrous and / or granular reinforcing agent is not an essential component, but if necessary, it may be blended in a range not exceeding 300 parts by weight with respect to 100 parts by weight of the total of PPS and the thermosetting epoxy resin. It is possible to improve the strength, rigidity, heat resistance, dimensional stability, etc., by compounding in the range of 10 to 300 parts by weight.

Examples of such fibrous reinforcing agents include inorganic fibers such as glass fibers, shirasu glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, right ko fibers, metal fibers, and carbon fibers.

Further, as the granular reinforcing agent, silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, and alumina silicate, metal oxides such as alumina, silicon chloride, magnesium oxide, zirconium oxide, and titanium oxide. Examples thereof include calcium carbonate, magnesium carbonate, dolomite and other carbonates, calcium sulfate, barium sulfate and other sulfates, glass beads, boron nitride, silicon carbide, saloyan, silica and the like, which may be hollow. . These reinforcing agents can be used in combination of two or more kinds, and if necessary, they can be used after pretreatment with a coupling agent such as silane type and titanium type.

The method for preparing the composition of the present invention is not particularly limited, but a method in which PPS, a thermosetting epoxy resin, and a reinforcing agent are melt-kneaded in an extruder at a temperature equal to or higher than the melting point of PPS and then pelletized is typical. .

The melt-kneading temperature is preferably 280 to 340 ° C. If it is less than 280 ° C, melting of PPS may be insufficient, and if it exceeds 340 ° C, the epoxy resin may be thermally deteriorated and gelled. .

Hereinafter, the present invention will be described in more detail with reference to examples.

<Example> Reference Example 1 (Polymerization of PPS) 3.26 kg of sodium sulfide (including 25 mol and 40% of water of crystallization), 4 g of sodium hydroxide, 1.36 kg (about 10 mol) of sodium acetate trihydrate and N in an autoclave. -Methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 7.9 kg was charged, and the temperature was gradually raised to 205 ° C with stirring to remove about 1.5 l of distilled water containing 1.36 kg of water. To the remaining mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added, and the mixture was stirred at 265 ° C for 4 hours.
Heated for hours. The reaction product was washed 5 times with hot water at 70 ° C,
It is dried under reduced pressure at 80 ℃ for 24 hours and melt viscosity is about 2500 poise
About 2 kg of powdered PPS at 0 ° C. and a shear rate of 1000 sec ⁻¹ ) was obtained.

The total sodium content in this PPS powder was 1,180 ppm.

The same operation was repeated and used in the examples described below.

Example 1 About 2 kg of the PPS powder obtained in Reference Example 1 was heated to 90 ° C.
Pour into 20 liters of pH 4 acetic acid aqueous solution, continue stirring for about 30 minutes, wash with deionized water at about 90 ° C until the pH of the solution reaches 7, and dry under reduced pressure at 120 ° C for 24 hours to obtain a powder. I took it.

The total content of matrium in this PPS was 274 ppm.

This powder was dry-blended with a Sumitomo Chemical Co., Ltd. (NOVA) type epoxy resin ESCN220-HH at a ratio shown in Table 1, and then melt-kneaded by a Brabender Plastograph set at 290 to 310 ° C. After crushing the obtained block sample, the adhesive strength with 42 alloy (Fe-Ni alloy) was measured by a T-type peeling test according to the method of JIS K6854.

As is clear from Table 1, the composition of the present invention had extremely high adhesive strength with 42 alloy.

Example 2 About 2 kg of the PPS powder obtained in Reference Example 1 and 10 l of deionized water were charged into an autoclave, and the autoclave was sealed at normal pressure, then at 175 ° C.
The temperature was raised to 30 minutes, the temperature was maintained for about 30 minutes while stirring, and then the mixture was cooled. The contents were taken out, PPS was further immersed in about 10 liters of deionized water at 70 ° C., stirred, and the operation was repeated 5 times.

The total sodium content in this PPS was 288 ppm.

The obtained PPS powder was blended with an epoxy resin, melt-kneaded, and pulverized in exactly the same manner as in Example 1.

The obtained powder was evaluated in the same manner as in Example 1 and the adhesive strength with 42 alloy was as shown in Table 1.

Example 3 NMP20l obtained by heating about 2 kg of the powder obtained in Reference Example 1 to 100 ° C.
Pour in and stir for about 30 minutes, then pass, then about 90
It was washed with ion-exchanged water at ℃.

The total sodium content in this PPS was 315 ppm.

The obtained PPS powder was blended with an epoxy resin, melt-kneaded, and pulverized in exactly the same manner as in Example 1.

The adhesive strength of the obtained powder with 42 alloy evaluated in the same manner as in Example 1 is as shown in Table 1.

Comparative Examples 1 and 2 PPS obtained in Reference Example 1 was used as it is (Comparative Example 1) and treated with acetic acid in the same manner as in Example 1, washed and dried (Comparative Example 2). The adhesive strength with 42 alloy evaluated in the same manner as in Example 1 for the powder that was melt-kneaded and pulverized without compounding is as shown in Table 1.

Comparative Examples 3 and 4 The PPS obtained in Reference Example 1 was treated with hot water in the same manner as in Example 2, washed and dried (Comparative Example 3), and treated with NMP in the same manner as in Example 3. The washed, dried (comparative example 4) melt-kneaded and pulverized powder without blending the epoxy resin was evaluated in the same manner as in Example 1 and the adhesive strength with 42 alloy is shown in Table 1. As described in.

Examples 4 and 5 The PPS obtained in Reference Example 1 was treated with acetic acid in the same manner as in Example 1, and the novolak-type epoxy resin and the glass fiber (3 mm chipped fiber) were mixed in the proportions shown in Table 1. Were mixed, and melt-kneaded and pulverized in the same manner as in Example 1 (Example 4). Also, using the same acetic acid treated PPS, a novolak type epoxy resin, fused silica and glass fiber (3mm chip fiber)
The ingredients were blended in the proportions shown in the table, melt-kneaded and pulverized in the same manner as in Example 1 (Example 5).

The adhesive strength of each of the obtained powders to 42 alloy evaluated in the same manner as in Example 1 is as shown in Table 1.

Comparative Examples 5 and 6 At all, except that the PPS powder obtained in Reference Example 1 was used as it was, instead of using the PPS powder obtained in Reference Example 1 after acetic acid treatment. Epoxy resin (Comparative Example 5) and glass fiber (Comparative Example 6) were blended, melt-kneaded, and pulverized in the same manner as described in Table 1.

The adhesive strength of the obtained powder with 42 alloy evaluated in the same manner as in Example 1 is as shown in Table 1.

PPS treated with acetic acid, hot water or NMP in this way
In comparison with Examples 1 to 5 of the present invention, in which PPS only washed with water is used, the adhesive strength with 42 alloy of this comparative example is significantly inferior. The improvement in strength is minimal.

Example 6, Comparative Example 7 The PPS obtained in Reference Example 1 was used as it is (Comparative Example 7) and treated with acetic acid, washed and dried in the same manner as in Example 1 (Example 6), and an epoxy resin was used. The epoxy resin was blended and melt-kneaded in exactly the same manner as in Example 1, except that instead of the novolak type epoxy resin, Epicoat 872, which is a bisphenol A diglycidyl ether type epoxy resin, manufactured by Ciel Co., Ltd. (manufactured) was used. Crushed.

The adhesive strength of the obtained powder with 42 alloy evaluated in the same manner as in Example 1 is as shown in Table 1.

Example 7, Comparative Example 8 The PPS obtained in Reference Example 1 was used as it is (Comparative Example 8) and treated with acetic acid in the same manner as in Example 1, washed and dried (Example 7), and used as an epoxy resin. The epoxy resin was compounded in exactly the same manner as in Example 1 except that the resin was changed to Novolac-type epoxy resin, and bisphenol S diglycidyl ether-based epoxy resin, Nagase Chemical Industry Co., Ltd. Denacol EX-251A was used. , Melt kneading, and crushing.

The adhesive strength of the obtained powder with 42 alloy evaluated in the same manner as in Example 1 is as shown in Table 1.

Example 8 Example 2 was repeated except that the temperature at the time of hydrothermal treatment of the PPS powder obtained in Reference Example 1 was changed to 175 ° C. in Example 2 to the temperature shown in Table 1. It was washed and dried by the same method.

The total sodium content in this PPS was 450 ppm.

The obtained PPS powder was blended with an epoxy resin, melt-kneaded, and pulverized in exactly the same manner as in Example 1.

The adhesive strength of the obtained powder with 42 alloy evaluated in the same manner as in Example 1 is as shown in Table 1.

Example 9 The same procedure as in Example 3 was carried out except that dimethylformamide was used instead of NMP for washing the PPS powder obtained in Reference Example 1 in Example 3 with an organic solvent. Obtained.

The adhesive strength of the obtained powder with 42 alloy evaluated in the same manner as in Example 1 is as shown in Table 1.

Example 10 The same operation as in Example 1 was carried out except that hydrochloric acid having a pH of 4 was used instead of using acetic acid when the PPS powder obtained in Reference Example 1 was acid-treated in Example 1. Got

The adhesive strength of the obtained powder with 42 alloy evaluated in the same manner as in Example 1 is as shown in Table 1.

<Effects of the Invention> According to the present invention, a polyphenylene sulfide resin composition having extremely excellent adhesiveness can be obtained. This resin composition is suitable for injection molding applications, especially for electronic component encapsulation applications.

Continuation of the front page (56) Reference JP 62-153343 (JP, A) JP 62-153344 (JP, A) JP 62-153345 (JP, A) JP 61-228023 (JP , A) JP 62-36425 (JP, A) JP 59-51944 (JP, A)

Claims (4)

[Claims] 1. A deionized polyphenylene sulfide resin of 60 to 99.95% by weight is added to a glycidyl ether of a bisphenol, a glycidyl ester of phthalic acid or its hydrogenated product, a novolac type epoxy resin and a cyclic non-glycidyl epoxy resin. At least one kind of thermosetting epoxy resin selected from the inside, containing two or more epoxy groups
A polyphenylene sulfide resin composition comprising 0.05 to 40% by weight. 2. The polyphenylene sulfide resin composition according to claim 1, wherein the deionization treatment is an acid treatment followed by washing with water. 3. The polyphenylene sulfide resin composition according to claim 1, wherein the deionization treatment is hot water treatment followed by washing with water. 4. The polyphenylene sulfide resin composition according to claim 1, wherein the deionization treatment is washing with an organic solvent and then washing with water.