JP2888835B2 - Polyphenylene sulfide polymer alloy - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to heat resistance, flame retardancy, solvent resistance, moldability,
The present invention relates to a polyphenylene sulfide-based polymer alloy having excellent mechanical strength and impact resistance.

[Conventional technology]

Hitherto, polyphenylene sulfide, polyether sulfone, polysulfone, polyarylate, polyetherimide, and the like have been known as resins having excellent heat resistance and the like.
Molded products made of these materials take advantage of their properties,
It is useful in the fields of electronics and automotive parts. However, polyethersulfone, polysulfone, polyarylate, polyetherimide and the like are excellent in heat resistance but are not good in moldability.

In addition, non-reinforced polyphenylene sulfide has good flow characteristics due to its crystallinity and is excellent in water resistance, so it is used as a sealing material in the electronic field, but when used as another molding material, It has drawbacks inferior in extrusion stability and molding stability and also has drawbacks inferior in impact resistance as a molding material, so that it is difficult to use it for various molded articles (particularly large molded articles).

For this reason, many attempts have been made to blend or alloy polyphenylene sulfide with various resins, various thermoplastic elastomers and the like in order to solve these disadvantages of polyphenylene sulfide. For example, Japanese Patent Publication No. 56-34032 proposes a resin composition comprising polyphenylene oxides and polyphenylene sulfides and having excellent moldability and flame retardancy. Japanese Patent No. 27740 discloses a polyarylene sulfide or another engineering resin and a hydrogenated block copolymer modified with a derivative of an α, β-unsaturated carboxylic acid, and has excellent impact resistance and interfacial peeling resistance. A modified block copolymer composition has been proposed, and furthermore, Japanese Patent Application Laid-Open No. 58-4035, also proposed by the present applicant.
Japanese Patent Publication No. JP-A No. 0-90139 discloses a thermoplastic graft having excellent impact resistance comprising a hydrogenated block copolymer and an epoxy group-containing polymer modified with polyphenylene sulfide or other engineering resin and a derivative of α, β-unsaturated carboxylic acid. There is a copolymer composition. JP-A-58-154757 discloses polyarylene sulfide and α-olefin / α, β
-A polyarylene sulfide resin composition comprising a glycidyl ester copolymer of an unsaturated acid and having excellent moldability has been proposed, and JP-A-59-207921 discloses polyphenylene sulfide and unsaturated A composition having excellent impact resistance comprising a polyolefin obtained by graft copolymerizing a carboxylic acid or an anhydride thereof or a derivative thereof and an epoxy resin has been proposed.
No. 3343, JP-A-62-153344, JP-A-62-1533
No. 45 discloses a specific polyphenylene sulfide and α-
There has been proposed a polyphenylene sulfide resin composition comprising an olefin / α, β-unsaturated acid glycidyl ester copolymer and having excellent impact resistance. Further, JP-A-62-169854, JP-A-62-172056,
Japanese Patent Application Laid-Open No. 62-172057 also proposes a polyphenylene sulfide resin composition excellent in impact resistance, comprising a polyolefin obtained by graft copolymerizing a specific polyphenylene sulfide and an unsaturated carboxylic acid or an anhydride or a derivative thereof.

[Problems to be solved by the invention]

However, among these proposals, Japanese Patent Application Laid-Open No. 58-154757
JP-A-59-207921, JP-A-62-153343, JP-A-62-153344, JP-A-62-153345, JP-A-62-169854, and JP-A-62-169854 Japanese Patent Application Laid-Open Nos. 62-172056 and 62-172057 disclose a polyphenylene sulfide resin composition having excellent impact resistance, but a non-reinforced product containing no filler such as glass fiber has heat resistance (high load). Only a resin composition whose thermal deformation temperature) is about the same as the polyphenylene sulfide of the matrix resin is given, and it is not an improved polymer alloy with respect to heat resistance. Further, as disclosed in JP-B-56-34032, a composition comprising polyphenylene ether and polyphenylene sulfide gives a resin composition excellent in processability as compared with the case where polyphenylene ether is used alone, but the obtained composition is Substantially delamination is remarkable. Particularly, in the composition mainly composed of polyphenylene sulfide, heat resistance (thermal deformation temperature) is not improved, and the impact resistance is poor, and although it is not a polymer alloy, it is unsuitable as a molding material. It is the present situation. Japanese Patent Application Laid-Open No. 58-27740 discloses an impact resistance, an impact resistance and a hydrogenation block copolymer comprising a polyarylene sulfide or another engineering resin and a hydrogenated block copolymer modified with a derivative of an α, β-unsaturated carboxylic acid. A modified block copolymer composition excellent in interfacial releasability and the like has been proposed, and a modified block copolymer composition that can simultaneously contain polyphenylene sulfide and another engineering resin is disclosed. However, there is no example in the prior art of a specific composition containing polyphenylene sulfide and another engineering resin at the same time, and there is no description of any substantial effect by including these two or more resin components. Further Japanese Patent
No. 58-40350 also discloses a thermoplastic resin containing polyphenylene sulfide or other engineering resin, and α, β.
-A thermoplastic graft and copolymer composition comprising a hydrogenated block copolymer modified with an unsaturated carboxylic acid derivative and an epoxy group-containing polymer has been proposed, and polyphenylene sulfide and other engineering components have been proposed as thermoplastic resin components. Disclosed are thermoplastic graft copolymer compositions that allow for the simultaneous inclusion of a resin. However, there is no example of a specific composition containing polyphenylene sulfide and another engineering resin at the same time in this prior art, and there is no description of any substantial effect by including these two or more resin components.

Thus, although these prior arts make it possible to simultaneously include polyphenylene sulfide and other engineering resins, the resulting resin composition containing polyphenylene sulfide and other engineering resins simultaneously has a resin compatibility. At present, it is not a polymer alloy which is inferior in heat resistance and impact resistance in terms of heat resistance and impact resistance and has sufficient performance as a molding material.

[Means for solving the problem]

The present inventors have been made to solve the problems of the conventional molding materials and the conventional techniques described above, and particularly to a polyphenylene sulfide-based polymer alloy, which has high heat resistance and has high moldability. And, in pursuit of a molding material having excellent impact resistance.As a result, polyphenylene sulfide is combined with a specific amorphous thermoplastic resin and a specific styrene-glycidyl group-containing unsaturated compound copolymer. It has been found that this can be achieved by forming a polymer alloy.

That is, the first invention of the present invention relates to a resin composition comprising (a) 10 to 90 parts by weight of polyphenylene sulfide and (b) 90 to 10 parts by weight of a non-crystalline thermoplastic resin having a glass transition temperature (Tg) of 120 ° C. or more. (C) styrene-glycidyl methacrylate copolymer,
One or more styrene-glycidyl group-containing unsaturated compounds selected from rubber-reinforced styrene-glycidyl methacrylate copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer, rubber-reinforced styrene-acrylonitrile-glycidyl methacrylate copolymer 1 to 50 parts by weight of the copolymer is blended.
TM D648) [Unit ° C] ≥ High load heat distortion temperature of polyphenylene sulfide alone (ASTM D648) [Unit ° C] -30 ° C
It is intended to provide a polyphenylene sulfide-based polymer alloy characterized by the following.

The second invention of the present invention relates to a resin composition 100 comprising (a) 10 to 90 parts by weight of polyphenylene sulfide and (b) 90 to 10 parts by weight of an amorphous thermoplastic resin having a glass transition temperature (Tg) of 120 ° C. or more. (C) styrene-glycidyl methacrylate copolymer,
One or more styrene-glycidyl group-containing unsaturated compounds selected from rubber-reinforced styrene-glycidyl methacrylate copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer, rubber-reinforced styrene-acrylonitrile-glycidyl methacrylate copolymer Modified block copolymer obtained by grafting a copolymer and (d) a vinyl aromatic compound-conjugated diene block copolymer or a hydrogenated block copolymer which is a hydrogenated product of this block copolymer with a glycidyl group-containing unsaturated compound. The combined or modified hydrogenated block copolymer is blended in an amount of 1 to 50 parts by weight as a total amount of the component (c) + the component (d).
D648) [unit: ° C] ≧ high-load thermal deformation temperature (ASTM D648) of polyphenylene sulfide alone (unit: ° C) −30 ° C. The present invention provides a polyphenylene sulfide-based polymer alloy.

 Hereinafter, the present invention will be described in detail.

The polyphenylene sulfide (hereinafter abbreviated as PPS) used as the component (a) in the present invention has a bonding unit represented by the following general formula: Is a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the formula, and a copolymer containing a repeating unit having the following structure in a range of 30 mol% or less of the repeating unit. is there.

The above-mentioned method for producing PPS is usually a method of polymerizing a halogen-substituted aromatic compound, for example, p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrogen sulfide and sodium hydroxide in a polar solvent. Or polymerization in the presence of hydrogen sulfide and sodium hydroxide or sodium aminoalkanoate; self-condensation of p-chlorothiophenol; and amide solvents such as N-methylpyrrolidone and dimethylacetamide, and sulfolane. The method of reacting sodium sulfide with p-dichlorobenzene in a sulfone-based solvent is suitable. These production methods are not particularly limited as long as they can be obtained by known methods.For example, U.S. Patent No. 2513188, Japanese Patent Publication No. 44-27671, Japanese Patent Publication No. 45-3368, and JP-B-52-12240, JP-A-61-225217 and U.S. Pat.
It can be obtained by the methods described in the specification, British Patent No. 1160660, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29439, and the prior art methods exemplified in these patents.

The PPS used in the present invention can have a melt viscosity at 320 ° C. (shear rate 1,000 / sec) of 100 to 10,000 poise, and the structure of the PPS may be linear or branched. Or a mixture thereof.

Further, PPS used as the component (a) used in the present invention
May be an acid-modified PPS in addition to the above-mentioned PPS.

Here, the acid-modified PPS is obtained by modifying the above PPS with an acid compound. Examples of the acid compound include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid. , Methyl maleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid, maleic anhydride, monomethyl maleic anhydride, itaconic anhydride, unsaturated carboxylic acids represented by citraconic anhydride and the like, and the like. In addition, saturated aliphatic carboxylic acids and aromatic-substituted carboxylic acids can also be mentioned. Acetic acid, hydrochloric acid, sulfuric acid,
An acid compound of an inorganic compound represented by phosphoric acid, silicic acid, carbonic acid and the like can also be mentioned as the acid compound. Among the acid compounds, organic acid compounds are preferable, and unsaturated carboxylic acids or anhydrides thereof are more preferably used.

Further, the acid modification refers to the above PPS and the above oxide,
0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, more preferably 0.2 to 5 parts by weight of PPS with respect to 100 parts by weight of PPS in a molten or non-molten state, and this means that PPS is contact-mixed. However, when denatured in such a non-molten state, the denaturation may be performed in the presence of water, a solvent, or the like.

In addition, these acid modifications can be carried out usually at room temperature to 350 ° C. in the presence or absence of a radical generator,
The method is not particularly limited, for example, PPS
Method of immersing and stirring in an aqueous solution of an inorganic acid in a powder state,
A method in which PPS is heated and melted and directly mixed with an organic acid is used.

Next, the amorphous thermoplastic resin having a glass transition temperature (Tg) of 120 ° C. or more used as the component (b) of the present invention is:
The heat resistance of the polyphenylene sulfide-based polymer alloy obtained by the present invention is determined by the following equation: Heat distortion temperature under high load (ASTM D648) [unit ° C] ≧ Heat distortion temperature under high load of polyphenylene sulfide alone (ASTM D64)
8) [Unit ℃] is an essential component to -30 ℃, for example, amorphous glass transition temperature (Tg) is 120 ℃ or more measured by a known method such as differential scanning calorimetry (DSC) Any thermoplastic resin may be used.

Specific examples of the amorphous thermoplastic resin that can be easily obtained on the market include polycarbonate, polysulfone, polyarylate, polyphenylene ether, polyetherimide, and polyether sulfone.

These amorphous thermoplastic resins may be used alone or in combination of two or more.

Further, the following specific styrene-glycidyl group-containing unsaturated compound copolymer used as the component (c) of the present invention comprises polyphenylene sulfide as the component (a) and (b)
The glass transition temperature (Tg) of the component improves the compatibility of the amorphous thermoplastic resin of 120 ° C or higher, and the heat resistance performance of the polyphenylene sulfide-based polymer alloy of the present invention is increased by the high load heat distortion temperature (ASTM D648) [unit ℃] ≧ High-load heat distortion temperature of polyphenylene sulfide alone (ASTM D64
8) [Unit ° C] It is an essential component for improving the temperature to -30 ° C, and copolymerizes 0.1 to 20 wt%, preferably 0.5 to 15 wt% of a glycidyl group-containing unsaturated compound (random copolymerization, block copolymerization, grafting). (Copolymerized). When the glycidyl group-containing unsaturated compound is 0.1% by weight or less, the compatibility between the component (a) and the component (b) is not sufficient, and the obtained composition is delaminated, and the high load heat deformation temperature (ASTM D648) is lowered. It is not preferable because it does not show a certain value, and even if it exceeds 20% by weight, the compatibility of the components (a) and (b) does not significantly increase the effect of increasing this amount.

Examples of the styrene-glycidyl group-containing unsaturated compound copolymer include styrene-glycidyl methacrylate copolymer, rubber-reinforced styrene-glycidyl methacrylate copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer, and rubber-reinforced styrene-acrylonitrile-glycidyl. 1 selected from methacrylate copolymer
One or two or more styrene-glycidyl group-containing unsaturated compound copolymers are used.

Next, in the second invention of the present invention, the component (d) used in combination with the component (c) is a vinyl aromatic compound-conjugated diene block copolymer or water which is a hydrogenated product of this block copolymer. It is a modified block copolymer or a modified hydrogenated block copolymer in which a glycidyl group-containing unsaturated compound has been grafted onto an addition block copolymer. Examples of such modified block copolymers and modified hydrogenated block copolymers include a styrene-conjugated diene (butadiene, isoprene, etc.) block copolymer (the amount of bound styrene is 5 to 95 wt%) or hydrogen of this block copolymer. A glycidyl methacrylate graft copolymer of an additive (a hydrogenated block copolymer having a bound styrene content of 5 to 95 wt%) is exemplified.

Among the thermoplastic elastomers containing a glycidyl group effective for improving the impact resistance of a polyphenylene sulfide-based polymer alloy, a vinyl aromatic compound containing less than 5 to 50% by weight of a vinyl aromatic compound-conjugated diene block is particularly preferred. Modified block copolymer or modified hydrogenated glycidyl group-containing unsaturated compound grafted onto a polymer (for example, a styrene-butadiene block copolymer) or a hydrogenated block copolymer which is a hydrogenated product of this block copolymer Block copolymers are exemplified.

Here, the block copolymer is a block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. Yes, for example, A
-B, ABA, BABA, (AB-) _4- Si, A
It is a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as -BABA. And
The hydrogenated block copolymer is obtained by hydrogenating the block copolymer.

The block copolymer and the hydrogenated block copolymer will be described in more detail below.

This block copolymer has a vinyl aromatic compound of 5 to
Containing less than 50% by weight, preferably 10-40% by weight,
A polymer block A mainly composed of a vinyl aromatic compound, which refers to a block structure, is a homopolymer block of a vinyl aromatic compound or a vinyl block containing a vinyl aromatic compound in an amount of more than 50% by weight, preferably 70% by weight or more. It has a structure of a copolymer block of an aromatic compound and a conjugated diene compound, and further, a polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a conjugated diene compound. Is contained in an amount of more than 50% by weight, preferably 70% by weight or more, and a structure of a copolymer block of a conjugated diene compound and a vinyl aromatic compound. In addition, the polymer block A mainly composed of a vinyl aromatic compound and the polymer block B mainly composed of a conjugated diene compound are used for the distribution of the conjugated diene compound or the vinyl aromatic compound in the molecular chain in each polymer block. May be random, tapered (the monomer increases or decreases along the molecular chain), partially block-shaped or in any combination thereof, and the polymer block mainly composed of the vinyl aromatic compound is When there are two or more, each of the polymer blocks may have the same structure or different structures.

As the vinyl aromatic compound constituting the block copolymer, for example, one or more selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, 1,1-diphenylethylene and the like are selected. Of which styrene is preferred. Further, as the conjugated diene compound, for example, one or two or more selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like, among which butadiene, isoprene and These combinations are preferred. The polymer block B mainly composed of a conjugated diene compound can arbitrarily select a microstructure in the block,
For example, in a polybutadiene block, the amount of 1,2-vinyl bond is 5 to 65%, preferably 10 to 50%.

The number average molecular weight of the block copolymer having the above structure is 5,000 to 1,000,000, preferably 10,000 to 800,
000, more preferably in the range of 30,000-500,000,
Molecular weight distribution [weight average molecular weight (Mw) and number average molecular weight (M
n) / (Mw / Mn)] is 10 or less. Further, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

The method for producing these block copolymers may be any method as long as it has the above-mentioned structure. For example,
According to the method described in JP 23798, a vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst.

The hydrogenated block copolymer is obtained by hydrogenating the above-mentioned vinyl aromatic compound-conjugated diene compound block copolymer, and the method for producing the hydrogenated block copolymer is as follows. For example,
No. 8704, it can be obtained by the method described in JP-B-43-6636, but in particular, the titanium-based hydrogenated hydrogenated block copolymer which exhibits excellent performance in weather resistance and heat deterioration resistance is obtained. Hydrogenated block copolymers synthesized using a catalyst are most preferred.For example, according to the methods described in JP-A-59-133203 and JP-A-60-79005, a titanium-based copolymer is used in an inert solvent. A hydrogenated block copolymer can be synthesized by hydrogenating a block copolymer having the above-described structure in the presence of a hydrogenation catalyst. At this time, at least 80% of the aliphatic double bond based on the vinyl aromatic compound-conjugated diene compound block copolymer is hydrogenated, and the polymer block mainly composed of the conjugated diene compound is morphologically converted into an olefinic compound polymer. You need to convert it to a block. Further, hydrogen of an aromatic double bond based on a vinyl aromatic compound copolymerized with a polymer block A mainly composed of a vinyl aromatic compound and, if necessary, a polymer block B mainly composed of a conjugated diene compound, is used. The rate of addition is not particularly limited, but the hydrogenation rate is preferably 20% or less. The amount of the non-hydrogenated aliphatic double bond contained in the hydrogenated block copolymer can be easily known by an infrared spectrophotometer, a nuclear magnetic resonance apparatus or the like.

As the glycidyl group-containing unsaturated compound essential for the components (c) and (d) of the present invention, a compound having an unsaturated group and a glycidyl group in a molecule can be used, but a preferable glycidyl group-containing unsaturated compound is used. Examples of the compound include compounds represented by the following general formulas (I) and (II).

(Wherein, R represents hydrogen, a lower alkyl group or a lower alkyl group substituted with a glycidyl ester group) (Wherein, R represents hydrogen, a lower alkyl group or a lower alkyl group substituted with a glycidyl ester group) Preferred specific examples are glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and allyl glycidyl ether. Among them, preferred glycidyl group-containing unsaturated compounds include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and the like.

In addition to these glycidyl group-containing unsaturated compounds, diglycidyl maleate, methyl glycidyl maleate, ethyl glycidyl maleate,
Isopropyl glycidyl maleate, t-butyl glycidyl maleate, diglycidyl fumarate, methyl glycidyl fumarate, isopropyl glycidyl fumarate, diglycidyl itaconate, methyl glycidyl itaconate, isopropyl glycidyl itaconate, 2-
Glycidyl group-containing unsaturated compounds such as methylene glutaric acid diglycidyl ester and 2-methylene glutaric acid methyl glycidyl ester can also be suitably used.

One or more of these glycidyl group-containing unsaturated compounds can be used.

(D) a modified block copolymer used in the present invention,
The modified hydrogenated block copolymer is obtained by grafting the glycidyl group-containing unsaturated compound to the block copolymer having the above structure or the hydrogenated block copolymer in the presence or absence of an organic peroxide. It is a product obtained by reaction, and the reaction can be carried out in either a molten state or a solution state.

Examples of organic peroxides that can be provided as necessary in the graft reaction of this modified block copolymer and modified hydrogenated block copolymer include, for example, dicumyl peroxide, di-tert-butyl peroxide, and tert-butyl peroxide. Butylcumyl peroxide, 2,5-dimethyl-2,5-di (te
rt-butylperoxy) hexane, 2,5-dimethyl-2,5
-Di (tert-butylperoxy) hexyne-3, n-butyl-4,4-bis (tert-butylperoxy) valerate, 1,1-bis (tert-butylperoxy) 3,3,5-trimethyl Cyclohexane and the like can be mentioned, and one or more can be suitably selected from these. In addition to these organic peroxides, as a radical initiator, 2,3-dimethyl-
2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-di (p-methylphenyl) butane, 2,3-dimethyl-2,3-di The graft reaction may be performed using a compound such as (bromophenyl) butane.

The above-mentioned organic peroxides and radical initiators that can be used in the graft reaction can be suitably used usually in the range of 0.01 to 5 parts by weight per 100 parts by weight of the block copolymer or the hydrogenated block copolymer.

Further, the unreacted glycidyl group-containing unsaturated compound may be completely removed from the modified block copolymer or modified hydrogenated block copolymer, or may remain as it is.

And the modified block copolymer, the production method of the modified hydrogenated block copolymer can be carried out by any known method,
For example, the modified block copolymer in a kneader such as an extruder,
When a modified hydrogenated block copolymer is obtained, the modified block copolymer and the modified hydrogenated block copolymer are subjected to a modification reaction of the block copolymer and the hydrogenated block copolymer using a vent extruder. The remaining unreacted glycidyl group-containing unsaturated compound may be removed by forced venting. Further, for example, the glycidyl group-containing unsaturated compound can be grafted in a state in which the block copolymer or the hydrogenated block copolymer is dissolved in a solvent or in a suspension state.

When performing these grafting reactions, it is also possible to coexist a vinyl monomer copolymerizable with the glycidyl group-containing unsaturated compound, and of course, the modified block copolymer obtained here, the modified hydrogenated block The copolymer can be suitably used as the component (d) of the present invention. As the copolymerizable vinyl monomer, for example, vinyl monomers such as styrene, acrylonitrile, acrylate and methacrylate can be suitably used.

Further, the amount of the grafted glycidyl group-containing unsaturated compound in the modified block copolymer or the modified hydrogenated block copolymer can be easily known by a known method, and specifically, an infrared spectrophotometer , NMR, etc., and titration analysis of epoxy value. Further, the residual amount of the unreacted glycidyl group-containing unsaturated compound contained in the modified block copolymer or the modified hydrogenated block copolymer can be easily measured by, for example, gas chromatography.

The present invention is a polymer alloy comprising the above specified components, wherein component (a) is 10 to 90% by weight and component (b) is
For 100 parts by weight of a resin composition consisting of 90 to 10% by weight,
A polyphenylene sulfide-based polymer alloy containing 1 to 50 parts by weight of the component (c). In the second invention, the component (a) is 10 to 90% by weight, and the component (b) is 90 to 10% by weight.
(C) component +
It is a polyphenylene sulfide polymer alloy containing 1 to 50 parts by weight of the total amount of the component (d).

If each of the components (a) and (b) is less than 10% by weight, a resin composition excellent in both processability and heat resistance cannot be expected, which is not preferable, and even when each component exceeds 90% by weight. A resin composition having both excellent processability and heat resistance cannot be expected, which is not preferable. The component (c) is replaced by the component (a) +
If the total amount of the component (b) is less than 1 part by weight based on 100 parts by weight, the polyphenylene sulfide of the component (a) and the non-crystalline thermoplastic resin having a glass transition temperature (Tg) of the component (b) of 120 ° C. or more are used. Insufficient compatibility causes delamination, which is not preferable, and when it exceeds 50 parts by weight, the effect of improving the compatibility of these components is not changed at all to 50 parts by weight, and the heat resistance of the obtained composition is rather reduced. Notably undesirable. Similarly, the total amount of the component (c) + the component (d) is equal to the component (a) +
If the total amount of the component (b) is less than 1 part by weight based on 100 parts by weight, the polyphenylene sulfide of the component (a) and the non-crystalline thermoplastic resin having a glass transition temperature (Tg) of the component (b) of 120 ° C. or more are used. Insufficient compatibility causes delamination, which is not preferable, and when it exceeds 50 parts by weight, the effect of improving the compatibility of these components is not changed at all to 50 parts by weight, and the heat resistance of the obtained composition is rather reduced. Notably undesirable.

As described above, the polyphenylene sulfide-based polymer alloy of the present invention comprises the components (a), (b), and (c):
Alternatively, it is composed of the components (a), (b), (c) and (d), but does not impair the properties of the polyphenylene sulfide-based polymer alloy of the present invention for the purpose of imparting impact resistance. Thermoplastic elastomers such as ethylene-propylene-ethylidene norbornene copolymer (EPDM rubber) and ethylene-butene 1 copolymer,
A styrene-based block copolymer elastomer such as a styrene-butadiene block copolymer or a styrene-isoprene block copolymer, or a hydrogenated product (hydrogenated block copolymer) of the styrene-based block copolymer elastomer is added. Needless to say, this is also a part of the embodiment of the present invention.

Further, if necessary, as inorganic fillers, metal oxides (silicon oxide, titanium oxide, zinc oxide, iron oxide, magnesium oxide, alumina, etc.), silicates (kaolin, clay, mica, bentonite, silica, talc) , Walsteinite, montmorillonite, etc.), iron hydroxide, hydrotalcite, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, boron nitride, silicon carbide,
Glass beads, glass fiber, alumina fiber, silica / alumina fiber, zirconia fiber, silicon nitride fiber, boron nitride fiber, asbestos fiber, silicon carbide fiber, calcium silicate, gypsum fiber, polyamide fiber, phenol fiber, silicon carbide whisker, titanium Potassium whisker,
And carbon fibers, various flame retardants, crystallization accelerators (nucleating agents), silane coupling agents such as mercaptosilane, vinylsilane, aminosilane, epoxysilane, antioxidants, and heat stabilizers. , UV absorbers, hindered amine light stabilizers, colorants, and PP
For the purpose of controlling the degree of crosslinking of S, a metal salt of thiophosphinic acid or a dialkyltin dicarboxylate or aminotriazole as a crosslinking inhibitor can be added as a crosslinking accelerator.

The polyphenylene sulfide-based polymer alloy of the present invention can be produced by various methods using the above-mentioned components. For example, a heat-melt kneading method using a single-screw extruder, a twin-screw extruder, a kneader, a Brabender or the like can be mentioned, and a melt-kneading method using a twin-screw extruder is most preferable. The kneading temperature at this time is not particularly limited, but can usually be arbitrarily selected from 280 to 400 ° C.

The polyphenylene sulfide-based polymer alloy of the present invention obtained as described above can be obtained by various conventionally known methods, including a printed wiring board, an electronic component sealing material, various connector components, a heat-resistant paint, a thin molded product, a fiber, and a sheet. It can be formed into molded products of various shapes such as films, tubes, etc., and processing methods such as injection molding, extrusion molding, foam molding, etc. are possible. Specific application fields include automobiles, electricity, electronics, machinery It can be widely used as a molding material having excellent heat resistance, flame retardancy, molding processability and impact resistance in the field of industrial materials.

For sealing electronic components, electronic components, for example,
ICs, transistors, diodes, coils, capacitors, resistors, varistors, connectors, various sensors,
Transducers, switches, etc. or parts made of these hybrids are mechanically protected with a resin composition, electrical insulation is maintained,
It is provided for sealing for the purpose of preventing property change due to an external atmosphere, etc., and when the polyphenylene sulfide-based polymer alloy of the present invention is used for sealing these electronic components, the melt viscosity at 320 ° C. is 1500 poise or less, Preferably, those having 1200 poises or less can be suitably used.

〔The invention's effect〕

The polyphenylene sulfide-based polymer alloy of the present invention provides a resin composition having excellent heat resistance, flame retardancy, moldability and impact resistance. It can also be used as a material to which toughness is imparted even in the use of an electronic component sealing material.

〔Example〕

The present invention will be described in more detail by way of examples.
It is not limited by these examples.

Preparation of Polyphenylene Sulfide (PPS) as Component (a) In a 10 L autoclave, 1750 g of N-methylpyrrolidone, 1153 g (8.8 mol) of 2.7 hydrate of hydrogen sulfide and 4.0 g (0.1 mol) of sodium hydroxide were charged, and 200 g of nitrogen was placed in a nitrogen atmosphere. The temperature was elevated to about 2 hours with stirring over about 2 hours, and 250 ml of water was distilled off. After cooling the reaction system to 150 ° C, 1176 g (8.0 mol) of p-dichlorobenzene and 800 g of N-methylpyrrolidone were added and reacted at 230 ° C for 1 hour and then at 260 ° C for 2 hours. The reaction vessel was cooled, and the obtained polymer was separated by filtration, washed with boiling water three times, washed with acetone twice, dried at 120 ° C., and dried in light gray brown powder PPS (320 ° C.).
At a shear rate of 1000 / sec. Of about 2600 poise).

This polymer is referred to as PPS.

(B) Preparation of an amorphous thermoplastic resin having a glass transition temperature (Tg) of 120 ° C. or more (b-1) Panlite L-12 as a polycarbonate
50 (manufactured by Teijin Chemicals) was used. This polymer is referred to as PC.
The PC had a Tg (glass transition temperature) of 148 ° C.

(B-2) 1: 1 (molar ratio) mixture of terephthalic acid and isophthalic acid From phthalic acid and bisphenol A, the intrinsic viscosity (phenol / tetrachloroethane = 60/40 weight ratio, 1
g / dl, measured at 25 ° C.) was 0.67.
This polymer is designated as PAR. The Tg (glass transition temperature) of this PAR was 191 ° C.

(B-3) udel-P1700 (manufactured by UCC) was used as polysulfone. This polymer is designated as PS. In addition, this PS
Had a Tg (glass transition temperature) of 186 ° C.

(B-4) ultram1000 (GE
(Manufactured by Sharp). This polymer is designated as PEI. The Tg (glass transition temperature) of this PEI was 215 ° C.

(B-5) After sufficiently replacing the inside of a stainless steel reactor having an oxygen inlet at the bottom of the reactor with a cooling coil and a stirring blade therein with nitrogen, 53.6 g of cupric bromide, di-n-
1110 g of butylamine, 20 liters of toluene, n-
In a mixed solvent of 16 liters of butanol and 4 liters of methanol, 8.75 kg of 2,6-xylenol was dissolved and charged into the reactor. Continue to blow oxygen into the reactor while stirring,
Polymerization was performed for 180 minutes. In addition, water was circulated through the cooling coil during polymerization in order to maintain the internal temperature at 30 ° C. After polymerization,
The precipitated polymer was separated by filtration, a mixed solution of methanol / hydrochloric acid was added, the remaining catalyst in the polymer was decomposed, and the polymer was sufficiently washed with methanol and dried, and light yellowish white powdery polyphenylene ether (reduced viscosity 0.57) I got This polymer PPE is used. The Tg (glass transition temperature) of this PPE was 208 ° C.

(C) Preparation of Styrene-Glycidyl Group-Containing Unsaturated Compound Copolymer After sufficiently replacing the inside of a stainless steel reactor equipped with a stirrer with nitrogen, 4500 g of styrene and 500 g of glycidyl methacrylate were obtained.
g, 100 g of sodium dodecylbenzenesulfonate, 25 g of t-dodecylmercaptan, and 15,000 g of ion-exchanged water were charged into a reactor, and hot water of 70 ° C. was circulated through the jacket.
When the temperature reaches ℃, potassium persulfate 27.5 g, ion-exchanged water
After adding 1,500 g of an aqueous solution and performing polymerization for 150 minutes, styrene 4,500 g, glycidyl methacrylate 500 g, sodium dodecylbenzenesulfonate 50 g, t-dodecyl mercaptan 25 g, ion-exchanged water 5,000 g and persulfuric acid 27.5 g, ion An aqueous solution of 500 g of exchanged water was added, and polymerization was further performed for 150 minutes. After completion of the polymerization, the polymer was coagulated with calcium chloride, washed sufficiently with water, and dried to obtain a styrene-glycidyl methacrylate copolymer containing 10% by weight of glycidyl methacrylate. This polymer is designated as SG-1. Further, the compositions of styrene and glycidyl methacrylate were changed in the same manner to obtain a styrene-glycidyl methacrylate copolymer containing 0.8% by weight and 5% by weight of glycidyl methacrylate, respectively. The respective polymers are referred to as SG-2 and SG-3.

(D) Preparation of a hydrogenated block copolymer graft-modified with a glycidyl group-containing unsaturated compound having a polystyrene-hydrogenated polybutadiene-polystyrene structure, a bound styrene content of 15%, a number average molecular weight of 83,000, and a molecular weight distribution of 1.04 A hydrogenated block copolymer having 41% of 1,2 bonds in the polybutadiene portion before hydrogenation and a hydrogenation rate of 99% was synthesized using a Ti-based catalyst described in JP-A-60-79005. . 5.0 parts by weight of glycidyl methacrylate per 100 parts by weight of the hydrogenated block copolymer, di-ter
Mixing 0.8 parts by weight of t-butyl peroxide, 170
The denaturation reaction was carried out while performing forced venting (degree of vacuum: 750 mmHg cage pressure) using a vacuum pump with a 45 mmφ vented twin-screw extruder set to ° C.

The resulting modified hydrogenated block copolymer was subjected to a reflux treatment for 20 hours with a Soxhlet extractor using acetone, and titration analysis of the epoxy value revealed that 2.6% by weight of glycidyl methacrylate was grafted. The polymer obtained here is designated as MHTR.

Examples 1 to 4 and Comparative Examples 1 to 8 Polyphenylene sulfide as component (a) obtained above, amorphous thermoplastic resin having a glass transition temperature (Tg) of 120 ° C. or higher for component (b), component (c) Styrene-glycidyl group-containing unsaturated compound copolymer and a hydrogenated block copolymer graft-modified with the glycidyl group-containing unsaturated compound as the component (d) are dry-blended with the composition shown in Table 1,
Using a co-rotating twin-screw extruder set at 290 to 360 ° C., the mixture was melt-kneaded at a screw rotation speed of 200 rpm, and the extruded strand was pelletized. 29 pellets obtained here
The test piece was supplied to a screw in-line type injection molding machine set at 0 to 360 ° C, and a test piece for a tensile test and a test piece for an Izod impact test were injection-molded at a mold temperature of 140 ° C. Using these test pieces, a tensile test (ASTM D-
638), the presence or absence of delamination of the composition was checked from the fracture surface, and the load (18.56 kg / cm ² ) heat deformation temperature (ASTM
D-648), Izod (with notch) impact strength (ASTM D
−256: 23 ° C.) and the results are shown in Table 1.

Comparative Example 6 is a single PPS, and has a high load heat distortion temperature of 111 ° C.
And Izod (with notch) impact strength is 2Kg · cm /
cm.

In the compositions composed of the two components (a) and (b) of Comparative Examples 1 to 5, and 7 and 8, the delamination phenomenon was remarkably observed, and the high-load heat distortion temperature of the heat resistance performance varied among the same samples. It did not show a large constant value.

On the other hand, (a), (b),
(C) a composition comprising three components, or (a)
In the composition composed of the four components (b), (c) and (d), no delamination phenomenon was observed and the heat distortion under high load was improved.

Continuation of the front page (56) References JP-A-61-171759 (JP, A) JP-A-61-53356 (JP, A) JP-A-62-218442 (JP, A) JP-A-59-155461 (JP) JP-A-59-164360 (JP, A) JP-A-63-183954 (JP, A) JP-A-62-218436 (JP, A) JP-A-62-218441 (JP, A) Patent 2701147 (JP, A) JP, B2) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08L 1/00-101/14

Claims (2)

(57) [Claims] (1) (a) polyphenylene sulfide 10 to 90
Parts by weight (b) 100 parts by weight of a resin composition composed of 90 to 10 parts by weight of an amorphous thermoplastic resin having a glass transition temperature (Tg) of 120 ° C. or more, (c) a styrene-glycidyl methacrylate copolymer,
One or more styrene-glycidyl group-containing unsaturated compounds selected from rubber-reinforced styrene-glycidyl methacrylate copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer, rubber-reinforced styrene-acrylonitrile-glycidyl methacrylate copolymer 1 to 50 parts by weight of the copolymer is blended.
TM D648) [Unit ° C] ≥ High load heat distortion temperature of polyphenylene sulfide alone (ASTM D648) [Unit ° C] -30 ° C
A polyphenylene sulfide-based polymer alloy, characterized in that: 2. (a) Polyphenylene sulfide 10 to 90
Parts by weight (b) 100 parts by weight of a resin composition composed of 90 to 10 parts by weight of an amorphous thermoplastic resin having a glass transition temperature (Tg) of 120 ° C. or more, (c) a styrene-glycidyl methacrylate copolymer,
One or more styrene-glycidyl group-containing unsaturated compounds selected from rubber-reinforced styrene-glycidyl methacrylate copolymer, styrene-acrylonitrile-glycidyl methacrylate copolymer, rubber-reinforced styrene-acrylonitrile-glycidyl methacrylate copolymer Modified block copolymer obtained by grafting a copolymer and (d) a vinyl aromatic compound-conjugated diene block copolymer or a hydrogenated block copolymer which is a hydrogenated product of this block copolymer with a glycidyl group-containing unsaturated compound. The combined or modified hydrogenated block copolymer is blended in an amount of 1 to 50 parts by weight as a total amount of the component (c) + the component (d).
D648) A polyphenylene sulfide-based polymer alloy characterized by having a high load thermal deformation temperature (ASTM D648) [unit ° C] -30 ° C of [unit ° C] ≧ polyphenylene sulfide alone.