JPH0362852A - Polyphenylene sulfide-based resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having improved compatibility and excellent appearance of molded article and mechanical strength by mixing specific amounts of polyphenylene sulfide-based resin, polyamide-based resin and specific compound. CONSTITUTION:(A) 95-10 pts.wt. polyphenylene sulfide-based resin is mixed with (B) 5-90 pts.wt. polyamide-based resin (e.g. nylon-4 or nylon-6) and 100 pts.wt. total of A+B is mixed with (C) 0.1-10 pts.wt., preferably 0.05-4 pts.wt. a compound [e.g. N-(2-aminoethyl) 3-aminopropyl methyl dimethoxysilane] having a group selected from amino group, epoxy group or mercapto group and chemical structure selected from X-O-C or X-OH, etc., (X is element selected from IIIA-group, IVA-group and VA-group, etc., in periodic table in a molecule to afford the aimed resin composition.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to polyphenylene sulfide (hereinafter referred to as PPS)
The present invention relates to a resin composition having excellent mechanical properties, including a polyamide-based resin (hereinafter also referred to as PA).

(Prior Art and Problems to be Solved by the Invention) Polyphenylene sulfide (PPS) @ resin has excellent heat resistance, flame retardance, rigidity, etc., but has the drawback of being brittle against impact. In order to improve this drawback, reinforcement with various ml fillers has been carried out.

However, the fragility against impact has not been sufficiently improved.

Although polyamide resins have excellent solvent resistance and toughness, they have drawbacks such as a decrease in mechanical properties due to moisture absorption, dimensional instability, and a decrease in rigidity at high temperatures above the glass transition temperature. In order to improve these defects, reinforcement by filling with various inorganic fillers has been carried out. However, these methods require various molding methods (e.g. injection molding, extrusion molding, etc.)
Molded products molded with this method suffer from "warping" and a decrease in impact resistance, and molded products with a good appearance cannot be produced.

Attempts have been made to combine the original excellent properties of PPS and PA by blending PPS and ordinary PA (powder @ single ratio 1 or less) (for example, in JP-A-53-6
9255). However, simple blending results in poor compatibility between PPS and PA, poor surface condition of the molded product, phase separation, and no product exhibiting satisfactory physical properties.

JP-A-59-155462 proposes an epoxy resin additive/Jl to improve the compatibility between PPS and PA, but it is not yet practically satisfactory and improvements are desired. There is.

Therefore, the present invention improves the compatibility between PPS and P,
The purpose of this invention is to provide a resin composition containing PPS and PA that has a good appearance of a molded product and satisfactory physical properties.

(Means for Solving the Problems) The present invention is based on the discovery that when PPS and PA are further added with a component (C) to be described later, the compatibility with PPS is significantly improved.

That is, the PPS composition of the present invention contains (A) 95 to 10 parts by weight of a polyphenylene fluoride resin, (B) 5 to 90 parts by weight of a polyamide resin, and (C) a group A niamino group in the molecule. A group selected from an epoxy group, a mercapto group, a halogen group, an isocyanato group, and a ureido group, and group 8;
-0-P, X-N1-1. X-N-CX-N=C,
X-CI, X-Br and X-I (where X
is an element selected from Group 38, Group 48, Group 5A, Group 3B, Group 4B, and Group 5B of the periodic table), 7JA chemistry also refers to compounds with -j inclusion. It is characterized by containing 0.01 to 10 parts by weight per 100 parts by weight of the combined amount of components (A) and '(B).

The feature of the present invention lies in the addition of component (C). Ingredient (C)
By adding PPS, an improvement in compatibility that could not be obtained by simply mixing PPS and PA can be seen.

First, the mole% of component (A) used in the present invention is PPS.
Those containing the above are preferred because they do not result in a composition with excellent properties. PPS can be polymerized by polymerizing p-dichlorobenzene in the presence of sulfur and sodium carbonate, or by polymerizing p-dichlorobenzene with sodium sulfide or sodium bisulfide and sodium hydroxide or hydrogen sulfide in a polar solvent. Examples include polymerization in the presence of sodium sulfide and self-condensation of p-chlorothiophenol. A suitable method is to react with chlorobenzene. At this time, in order to adjust the degree of polymerization, it is a preferable method to add an alkali metal salt of carboxylic acid or sulfonic acid, or to add alkali hydroxide. If it is less than 30% as a copolymerization component, it may affect the crystallinity of the polymer even if it contains meth, alkyl, phenyl, alkoxy, carboxylic acid, or a metal base of carboxylic acid. The copolymerization component is preferably 10 mol % or less, although it may be within a range that does not have a large effect. In particular, when trifunctional or more functional phenyl, biphenyl, naphdyl sulfide bonds, etc. are selected for copolymerization, the amount may be 3 mol % or less, more preferably 1 mol % or less.

Such PPS can be produced using common manufacturing methods, such as (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (see U.S. Pat. No. 2,513,188, Japanese Patent Publication No. 4427671 and Japanese Patent Publication No. 45-3368); (2) Condensation reaction of thiophenols in the presence of an alkali catalyst or copper salt (US Patent No. 3,274,165, British Patent No. 11)
60560), (3) Aromatic compounds are reacted with sulfur chloride in the coexistence of a Lewis acid catalyst with a 7/' condensation reaction (see Japanese Patent Publication No. 27255/1986, Belgian Patent No. 29437), etc. It can be selected arbitrarily depending on the purpose.

PPS is currently being supplied to the market by Philips Petroleum ■, Tosoh The Steel ■, Toprene and Kenbetsu Chemical. There are various grades depending on the crosslink density and viscosity, and the present invention uses P with less crosslinked structure.
PS is preferred.

Examples of the polyamide used in the present invention include nylon-4, nylon-6, nylon 6.6, nylon-6.
12, nylon-6,10, etc., but are not limited to these. In the present invention, it is preferable to use a polyamide in which the amount of terminal amine groups is larger than the amount of terminal carboxyl groups. Such a polyamide can be obtained by adding an extra compound having a group that reacts with a carboxyl group, such as a diamine, during the polymerization of the polyamide. Alternatively, it can also be obtained by polymerizing polyamide and then reacting it with a compound having a group that reacts with a carboxyl group.

In this case, the ratio of terminal amine group to terminal carboxyl group is preferably 1.01 or more, more preferably 1.01 or more.
It is 1 or more. In particular, the terminal base can be 1.3 or more.

In the resin silk ritual of the present invention, (A) PPS resin 9
(A) and (B) are blended at a ratio of 5 to 90 parts by weight of the PA resin (B) to 5 to 10 parts by weight. If the PA acid component is less than 5 parts by weight, impact resistance and brittleness will not be improved sufficiently, and if the PPS component is less than 10 parts by weight, judicial changes due to moisture absorption will be large and mechanical properties will deteriorate, which is undesirable. .

Next, the component (C) that characterizes the present invention will be described. As mentioned above, component (C) is a compound having a group selected from Group A and a chemical structure selected from Group B in its molecule. Such compounds include surface treatment agents for various fillers, coupling agents used as primers in adhesion and painting, such as silane coupling agents, titanate coupling agents, aluminum coupling agents, and phosphorus. A zircoaluminate type coupling agent, a zircoaluminate type coupling agent, etc. are used.

Among the above-mentioned coupling agents, specific examples of those that meet the conditions for component (C) include the following. As a silane-based coupling agent, N-(2-aminoethyl)3-aminopropylmebrodi-xysilane, N-(2-aminoethyl>3-aminopropyltrimethoxysilane, 3-aminopropyl) Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl>ethyltrimethoxysilane, 3-chloro[1p[1pyl] Methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-talolopropylmethyldichlorosilane, 3-chloropropylmethyljethoxysilane, 1.3-bis(ri[10methyl) -1,1,3,3-tetramethyldisilazane, 3-ureidopropyltriethoxysilane, 3-
Sardine anatopropyltriane 1-xysilane, etc.; Isopropyl tri(n-aminoethylaminoethyl) titanate; Tetra(triethanolamine) zirconate: Zircoal (contains amino group; water trapping Jffl (manufactured by IQ), zircoaluminate cup This is a coupling agent S (containing a mercapto group; manufactured by Kansui Kasei viJ).Furthermore, hydrolysates of these coupling agents can also be used as component (C).

A preferred component (C) is a case where X is 81 in Group B, and particularly preferred is 3-glynosidoxypropyl-1-lymer! ~Epoxysilane coupling agents such as xysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)J-del1-rime1hexysilane, N-(2-aminoethyl) 3-aminopropylmethyldime-1-xysilane, N
-(2-Amineethyl)3-aminopropyltrimethoxysilane, 3-aminopropyl-1-rea-1-xysilane, and other aminosilane coupling agents.

The above component (C) is contained in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 4 parts by weight, per 100 parts by weight of the combined components (A) and (B).

The composition of the present invention contains a rubber-like material as an optional component to dramatically improve the impact strength.
- For example, it can be contained in an amount of 80 parts by weight or less relative to 100 parts by weight.

Rubbery materials include natural and synthetic polymeric materials that are elastic at room temperature. Specific examples include natural rubber, butadiene polymer, styrene-isoprene copolymer, butadiene-styrene copolymer random copolymer,
Block copolymers, graph 1 - all copolymers included>, isoprene polymers, chlorobutadiene polymers,
Butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylic ester polymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, thiol rubber, Examples include sulfurized rubber, polyurethane rubber, polyether rubber (eg, polypropylene oxide, etc.), shrimp chlorohydrin rubber, and the like.

These rubbery substances can be produced using any polymerization method (e.g. emulsion polymerization, solution polymerization), any catalyst (e.g. peroxide,
It may also be made from trialgyl aluminum, lithium gunide, or nickel-based catalysts. Furthermore, those having various degrees of crosslinking, those having various ratios of microstructures (for example, cis structure, trans structure, vinyl group, etc.), or those having various average rubber particle sizes are also used.

Further, as the copolymer, any of various copolymers such as a random copolymer, a block copolymer, a graft copolymer, etc. can be used. Furthermore, in producing these rubbery substances, it is also possible to copolymerize with other monomers such as olefins, dienes, aromatic vinyl compounds, acrylic acid, acrylic esters, and methacrylic esters.

As for the copolymerization method, any means such as random copolymerization, block copolymerization, Graph 1 copolymerization, etc. can be used. Specific examples of these monomers include ethylene, propylene, styrene, chlorostyrene, α-methylstyrene, butadiene, isobutylene,
Examples include chlorobutadiene, butene, isobutylene, butyl acrylate, acrylic acid, ethyl acrylic acid, butyl acrylate, methyl methacrylate, acrylonitrile, and the like. In addition, partially modified rubbery substances can also be used, for example hydroxy or carboxy-
Examples include terminal-modified polybutadiene, partially hydrogenated styrene-butadiene block copolymer, and partially hydrogenated styrene-isoprene block copolymer.

Preferred rubbery materials are modified polyolefins, such as ethylene, propylene, butene-1, pentene-1
, 4-methylpentene-1, isobutylene, 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidenenorbornene, 5-ethyl-
A polyolefin obtained by radical polymerization of at least one olefin selected from 2,5-norbornadiene, 5-(1'-propenyl>-2-norbornene, and styrene) has a carboxylic acid group, a carboxylic acid ester group, and a carboxylic acid group. Acid metal base, power 4 A monomer component having at least one functional group selected from a rubonic acid anhydride group, an imide group, an epoxy group a3, and an oxazolinyl group (hereinafter referred to as a functional group-containing component)
This is a modified polyolefin obtained by introducing.

Examples of functional group-containing components include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, butylmaleic acid, methylfumaric acid, mezanic acid, citraconic acid, glutaconic acid, and these carboxylic acids. Metal salts, methyl hydrogen maleate, methyl hydrogen itaconate,
Medyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyedyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimyl maleate, itaconic acid Dimethyl, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo[1(2,2,1)-5-heptene-2,3-dicarboxylic acid, endobi'cyclo-(2
,2,1)-5-hebutene-2,3-dicarboxylic anhydride, maleimide, N-,I plummaleimide,
N-butylmaleimide, N-notylmaleimide, glycidyl methacrylate, glycidyl acrylate (~, vinyl glycidyl ether, glycidyl itaconate, glycidyl ether of hydroxyalkyl (meth)acrylate, polyalkylene glycol (meth)acrylate)
], glycidyl needle, vinyl oxazoline, etc.

There are no particular restrictions on the method of introducing these functional group-containing components, and methods such as mixing with the main component, copolymerization, or grafting them into polyolefin using a radical initiator can be used. . The amount of functional group-containing component introduced is 0.00 relative to the modified polyolefin body.
A suitable range is 1 to 40 mol%, preferably 0.01 to 35 mol%.

Specific examples of particularly useful modified polyolefins include ethylene/acrylic acid copolymers, ethylene/methacrylic acid copolymers, and carboxylic acid moieties in these copolymers in which some or all of the carboxylic acid moieties are replaced with sodium, lithium, potassium, or zinc. , JJIIF with calcium
Ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/edyl methacrylate copolymer, ethylene/ethyl acrylate-〇-maleic anhydride Acid copolymer (g represents graft, the same applies hereinafter), ethylene/methyl methacrylate-g-maleic anhydride copolymer, ethylene/acrylic acid nibble-〇-maleimide copolymer, 21-nidylene/acrylic acid copolymer q-N-noenylmaleimide copolymer and partially saponified products of these copolymers, ethylene/propylene-〇-maleic anhydride copolymer, ethylene/butene-1-q-maleic anhydride copolymer, ethylene/ Propylene/1,4-hekylydiene-0-maleic anhydride copolymer, Eblene/propylene/dicyclopentadiene-0-maleic anhydride copolymer, ethylene/propylene/2,5-norbornadiene-0-anhydride Maleic acid copolymer, ethylene/propyrene-(]-]N-phenylmaleimide copolymer, ethylene/butene-1-(]-]N-phenylmaleimide copolymer, ethylene/glycidyl(meth)acrylate copolymer , ethylene/acrylic acid/glycidyl (meth)acrylate copolymers, etc., and each of these can be used alone or in the form of a mixture.

Furthermore, 7JI of epoxy resin can be added to the resin composition of the present invention to further improve impact resistance. The epoxy resin contains one or more epoxy groups, and can be in liquid or solid form. Examples include epoxy resins such as glycidyl ether of bisphenol, and cyclic non-glycidyl epoxy resins such as dicyclopentadiene-monomoid. Epoxy resin is a combination of PA resin and PPS resin.
It is preferable to add it in an amount of 10 parts by weight or less based on the weight of the tail. When the amount of epoxy resin is more than 10 parts by weight,
This is not preferable because a crosslinking reaction due to epoxy occurs, resulting in a decrease in melt flow stability, a decrease in mechanical properties, etc.

Furthermore, the composition of the present invention can be filled with other polymers (e.g., styrene resins, lenoine resins, various types of elastomers, etc.), glass fibers, carbon fibers, talc, kaolin, etc. It may contain additives, combustion agents, plasticizers, pigments, etc.

The compositions of the present invention can be prepared by a known method - C↑IJ function. For example, the raw materials may be uniformly mixed in advance using a mixer such as a tumbler or Henschel mixer, fed to a 1111 or twin-screw extruder, melted and kneaded at 230 to 400°C, and then pelletized. can.

(Example) The present invention will be explained in more detail below with reference to Examples.

In addition, the following were used as each component.

Component (A): PPS...Rydon M2588 (trademark, manufactured by Toshi Phillips Petroleum) Component (B): P to 6-A...8.4X 10'mol/g terminal amino group, 1 .8X10' moles/9 terminal carboxyl groups, molecules! 13,000 of 9 A6 polyamide-6 B...4.6X 10'mol/g of terminal amino groups;7. Polyamide-6 having a terminal carboxyl group of Ox 10' mol/g and a molecular weight of 13 ooo Component (C): 3-glycidoxybyl 3-aminopropyl trime 1 - xysilane 3-mercaptopropyl 1 - rimethoxysilane isopropyl tri( n
-aminoethyl-aminoethyl) titanate Also, for comparison, methyltrimethoxysilane as a compound that does not have a unit corresponding to the Δ group in component (C): Tafmer MPO610 (trademark, maleic anhydride-modified polyolefin, Tsukiishura Chemical (manufactured in 1 U.S.) Examples 1 to 5 and Comparative Examples 1 to 3 Each component was mixed in the ratio shown in Table 1 (@Okibe) and heated in a twin-screw extruder at 300°C and 29 O rpm. A pellet was created by extrusion under the conditions of 0. From this pellet, a test piece for the Izot (~ impact strength test) was manufactured, and the Izo~1 ~ impact strength test was conducted using this. .

Note that the eye foot 1 to impact strength tests (1/8 notch 1 and no notch) were measured in accordance with ASrM D 256.

1 2 Examples 6 to 7 and Comparative Examples 4 to 5 Maleic anhydride-modified polyolefins and PA were listed in Table 2.
They were mixed in the proportions (parts by weight) shown below and pre-extruded using a 21'll extruder under conditions of 260'C1290rl)m to produce pellets.

Next, mix the other ingredients shown in the table in the proportions shown in the table,
This and the above pellets 1~ were heated to 300°C in a twin-screw extruder.
, 290 rl) m to produce pellets. A test piece for Izot impact strength test was produced from this pellet, and the Izot impact strength test was conducted using this test piece. The results are shown in Table 2.

3 Table component (A) PPS (B) PA6-A PA6-8 (C) 3-glycidoxypropyltrimethoxysilane Maleic anhydride modified polyolefin 0.5 Izot impact strength (without 1/8 notch) (Kg-cm /cm) Izot impact strength (with 1/8 notch) (Kg-cm/cm) 9.2 6.2 2.0 1.3 *NB indicates that NB was not destroyed.
NB * * 4 (Effects of the Invention) According to the present invention, it was possible to improve the compatibility between PPS and PA, and thus it was possible to improve the brittleness of the PPS resin against impact. Therefore, the PPS-based resin composition of the present invention has mechanical strength that is similar to that of PPS and PA without losing its properties.

5

Claims (1)

[Scope of Claims] (A) 95 to 10 parts by weight of polyphenylene sulfide resin, (B) 5 to 90 parts by weight of polyamide resin, and (C) Group A: amino group, epoxy group, mercapto group in the molecule. , a group selected from a halogen group, an isocyanato group and a ureido group, and group B; X-O-C, X-OH, X-H, X-O-P,
-NH, X-N-C, X-N=C, X-Cl, X-Br
and X-I (where X is Group 3A, Group 4 of the periodic table)
The total amount of components (A) and (B) is 10.
A polyphenylene resin composition comprising 0.01 to 10 parts by weight relative to 0 parts by weight.