JPS63312351A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition capable of giving molded articles of significantly improved surface characteristics, flexural strength and chemical resistance without impairing the characteristics of the respective components, by blending a thermoplastic resin containing polar group(s) such as amino group and two kinds of polyphenylene ether resin. CONSTITUTION:The objective composition can be obtained by blending (A) 5-95wt.% of a thermoplastic resin with a melting point 150-300 deg.C having at least one kind of terminal polar group selected from carboxyl, hydroxyl and amino groups, (B) 95-5wt.% of a polyphenylene ether resin having isocyanate group and/or urethane linkage (C) 0-90wt.% of a second polyphenylene ether resin not containing isocyanate group and/or urethane linkage and (D) 0-90wt.% of a styrene resin.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a thermoplastic resin composition, and more specifically, thermoplastic resins having poor compatibility are made to be compatible by blending a third component, and both resins are made to be compatible. The object of the present invention is to provide a thermoplastic resin composition which can improve the disadvantages of the invention and which can provide molded articles having excellent mechanical properties.

(Prior Art) Conventionally, many attempts have been made to solve the drawbacks of each thermoplastic resin by blending thermoplastic resins having different properties.

However, different polymers usually have poor compatibility and do not mix uniformly, forming a so-called "sea-island" structure, and this "sea-island" interface is extremely weak, making the resulting composition brittle and mechanically The disadvantage is that the mechanical strength and impact strength are reduced.

On the other hand, since blends of polymers with high compatibility have similar properties, characteristic properties cannot usually be expected. Therefore, in recent years, various modifications of polymers have been investigated in order to uniformly disperse incompatible polymers with different properties, and it has been found that blends in which modified olefin rubber is finely dispersed in a nylon matrix exhibit improved impact resistance. (Refer to Japanese Patent Application Laid-open No. 143061/1983). However, such blends also tend to deteriorate in other physical properties, and no characteristic properties other than impact resistance have been obtained.

(Problems to be Solved by the Invention) Polyphenylene ether resin has excellent mechanical properties, excellent electrical properties, heat resistance, and good monthly stability. Because of this, it is used in many applications as an engineering plastic, but it has major drawbacks such as poor moldability, impact strength, and chemical resistance. On the other hand, thermoplastic polyester resins (such as polyethylene terephthalate and polybutylene terephthalate) are used as engineering plastics with excellent chemical resistance.
or polyamide resin (for example, nylon 6 or nylon 6)
6th grade). The former thermoplastic polyester resin has a high melting point and excellent mechanical strength, but because its heat distortion temperature under load is extremely low, it is usually used as a molding material with a large amount of glass fiber mixed in. . However, thermoplastic polyester resins reinforced with glass fibers have poor surface properties, and orientation of the glass fibers occurs during molding, resulting in extremely large strength anisotropy and shrinkage anisotropy of the molded product. Therefore, it has the disadvantage that the molded product does not warp or deform.

In order to eliminate these drawbacks of polyphenylene ether and thermoplastic polyester resin, an attempt to melt and mix both has been proposed in Japanese Patent Publication No. 51-21664. However, the resulting compositions exhibit typical incompatible properties because the properties (expressed by, for example, SP value) derived from the molecular structures of the two are significantly different. That is, the mechanical properties are significantly lower than expected based on both values, and the molded product obtained from this composition is
The appearance is also worse than when it is used alone.

On the other hand, in order to improve the fluidity of polyphenylene ether, it was proposed to incorporate polyamide resin into it.
However, the compatibility between polyphenylene ether and polyamide is extremely poor, and the resulting resin composition is likely to have poor mechanical properties, with no characteristic properties other than improved fluidity. It has not been done.

(Means for Solving the Problems) The present inventors created a blend of thermoplastic resins with different properties and poor compatibility, and improved the drawbacks of both resins without reducing the excellent properties of both resins. As a result of intensive research, we have finally completed the present invention. That is, the present invention is directed to a polymer having a melting point of 150 to 3 and having at least one polar group selected from a carboxyl group, a hydroxyl group, and an amine group at the terminal.
00°C thermoplastic resin (A) 5-95% by weight, polyphenylene ether resin having isocyanate groups and/or urethane bonds + Bl 95-5% by weight, polyphenylene ether resin not containing isocyanate groups and/or urethane bonds A thermoplastic resin composition characterized by containing (C) 0 to 90% by weight and styrene resin (D) 0 to 90% by weight.

The thermoplastic resin (Δ) in the present invention is a thermoplastic resin having at least one polar group selected from a carboxyl group, a hydroxyl group, and an amine group at its terminal and having a melting point of 150 to 300°C, such as polyethylene. Terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polyoxyethoxybenzoate, polyethylene naphthalate, 1. Polyester components and other acid components and/or glycol components, such as isophthalic acid, P-oxybenzoic acid , adipic acid, sebacic acid,
Polyester copolymerized with acid components such as geltar acid, diphenylmethane dicarboxylic acid, and dimer acid, and glycol components such as hexamethylene glycol, diethylene glycol, neopentyl glycol, and bisphenol A1 neopentyl glycol alkylene oxide adduct, aromatic polyester polyester. Ether block copolymer, aromatic polyester/polylactone block copolymer, polyester in a broad sense such as polyarylate, nylon 6, nylon 6.6, nylon 6°9, nylon 6.1
0, nylon 6.12, nylon 676.6, polyxylylene adipamide, polyhexamethylene terephthalamide, polyphenylene phthalamide, polyxylylene adipamide/hexamethylene adipamide, polyester amide elastomer, polyether Examples include polyamides such as esteramide elastomer, polyetheresteramide elastomer, and dimer acid copolymerized polyamide;
It may also be a blend of 11 resins or a plurality of resins, or a copolymer thereof. In particular, those having a melting point of 200° C. or higher are preferred from the viewpoint of heat resistance. Usually, the polyester resin listed in I- is used as a phenol/tetrachloroethane mixed solvent (6
/4 weight ratio), the intrinsic viscosity measured at 30°C is 0.
It is preferably 4 or more, and particularly preferably 0.5 or more. Further, it is preferable that the polyamide usually has a relative viscosity (measured in 98% sulfuric acid according to JISK 6810-1970) of 1.8 or more -1 U,
Furthermore, it is particularly preferable that it is 2.0 or more.

The polyphenylene ether resin fcl not containing isocyanate groups and/or urethane bonds in the present invention is represented by the following general formula, where R,, R2, R3
and R4 is hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group, cyano group, alkoxy group, phenokine group, or nitro group, and n indicates the degree of polymerization. Specific examples of R, R2, R3 and R4 include hydrogen, chlorine, bromine, iodine, methyl, ethyl, propyl, allyl, phenyl, benzyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, ethoxy, phenoxy,
Examples include groups such as nitro. Specifically, for example, poly-2,6-dimethyl-1,4-phenylene ether,
Poly-2゜6-diethyl-1,4-phenylene ether, poly-2,6-diprobyl-1,4-phenylene ether, poly-2,6-simethoxy 1,4-phenylene ether, poly-2,8- Dichloromethyl-1,4-phenylene ether, poly-2,6-dichloro-1,4-poly-2,6-dipromemethyl-1,4-phenylene ether, poly-2,6-diphenyl-1,4-phenylene ether, Poly-2,6-dydolyl-1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether and poly-2,5-dimethyl-1°4-phenylene ether, poly2,6-dipendylene ether 1,4-
Phenylene ether etc. can be used.

A preferred polyphenylene ether resin is a polymer in which R4 and R5 in the general formula have an alkyl group, particularly an alkyl group having 1 to 4 carbon atoms, and n is usually preferably 50 or more.

In addition, the polyphenylene ether resin containing an isocyanate group and/or urethane bond in the present invention (
81 can be obtained by the method described below.

(+) First, the isocyanate group-containing polyphenylene ether resin fB+ is added to the polyphenylene ether resin to, methyl isocyanate methacrylate, cyanate, ethyl isocyanate methacrylate, probyl isocyanate methacrylate, methyl acrylate isocyanate, ethyl isocyanate acrylate. It is obtained by copolymerizing or graft copolymerizing isocyanate group-containing copolymerizable unsaturated monomers such as isocyanate, allyl-2-isoanato ethyl ether, and allyl isocyanate methyl ether. The content of the polymerizable unsaturated monomer is usually 0.1 to 5% by weight, preferably 0.3 to 4% by weight, based on the resin.

■Next, the urethane bonds of the polyphenylene ether resin fBl containing urethane bonds are bonds resulting from the masking of the isocyanate groups, and the polyphenylene bonds obtained by copolymerizing or graft copolymerizing the isocyanate group-containing copolymerizable unsaturated monomers Methyl alcohol to ether resin,
Monoalcohols such as ethyl alcohol, propyl alcohol, t-butyl alcohol, and 1so-propyl alcohol, and aliphatic compounds having hydroxyl groups such as diols such as ethylene glycol, and/or phenol, cresol, and bispheno-10- - Obtained by reacting an aromatic compound having a hydroxyl group as exemplified in Rule A, the amount of the aliphatic compound having a hydroxyl group and/or the aromatic compound having a hydroxyl group added is usually the isocyanate base and the copolymerizable unsaturated 1.0 to isocyanate groups contained in the polyphenylene ether resin copolymerized or graft copolymerized with monomers.
It is 1.1 times (molar ratio).

(3) Another method for obtaining polyphenylene ether resin fBl using an isocyanate foundation is to add acrylic acid, methacrylic acid, α-
Ethyl acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocys-bicyclo(2,2,1
) hept-5-ene-2,3-dicarboxylic acid (nasic acid@), methyl-endless-bicyclo(2,2,1)
Unsaturated carboxylic acids such as hept-5-ene-2,3-dicarboxylic acid (methylnadic acid@) or acid halides, amides, imides, acid anhydrides, and esters of the unsaturated carboxylic acids In addition to the polymer obtained by copolymerizing or graft copolymerizing a derivative of , ethane diisocyanate, propane diisocyanate, gotane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate.

Octane diisocyanate, nonane diisocyanate,
Decane diisocyanate, m-phenylene diisocyanate, P-phenylene diisocyanate), 1-chloro-
2,4-phenylene diisocyanate, 2,4-)ruene diisocyanate.

2.6-toluene diisocyanate, 7.5-naphthalene diisocyanate, 4.4',4''-) diisocyanate triphenylmethane, diphenylmethane-4,4'
-diisocyanate, 3,3'-dimethyl-4,4'-
It is obtained by reacting a diisocyanate compound and/or a triisocyanate compound exemplified by biphenylene diisocyanate.

Note that the polyphenylene ether resin f [31 having an isocyanate group obtained by the method (3) above is further reacted with the aliphatic compound having a hydroxyl group and/or the aromatic compound having a hydroxyl group to form a urethane bond. (on a polyphenylene ether resin having a polyphenylene ether resin).

Further, in the methods (1) to (3) for obtaining the polyphenylene ether fat fBl having an isocyanate group and/or urethane bond, the following operations can be adopted.

(a) A method in which a solution containing each component and, if necessary, a radical generator is stirred at a temperature of 40°C to 200°C for several tens of minutes to several hours.

(b) In a system that does not substantially contain a solvent, each component and, if necessary, a component containing a radical generator is heated at 150°C to 350°C.
°C for a period of 20 seconds to 30 minutes, preferably 40
Melt kneading method for seconds to 5 minutes.

etc.

In addition, the styrene resin fDl in the present invention includes homopolymers such as polystyrene, polychlorostyrene, and polyα-methylstyrene, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, and styrene-based acrylonitrile-acrylate copolymers. , styrene-acrylonitrile-butadiene copolymer, styrene-butadiene rubber-modified polystyrene, EPDM-based rubber-modified polystyrene, acrylic rubber-modified styrene-acrylonitrile copolymer, hydrogenated styrene-butadiene broth copolymer, and other polystyrene thermoplastics. Examples include elastomers.

The blending ratio of component (△), fBl, (C1, fD+) can be changed as appropriate depending on desired physical properties, purpose, cost, etc., but usually component (A) is 5% of the total composition.
~95% by weight, preferably 20-90% by weight, component c
l is 0 to 90% by weight, preferably 0.01 to 80% by weight
, component Bl is 95 to 5% by weight, preferably 10 to 80%
% by weight, and the component Dl is contained in an amount of 0 to 90% by weight, preferably 0.01 to 75% by weight.

If the amount of component (Δ) added is too small, disadvantages such as decreased chemical resistance will occur, and if component FB+ is too small, the amount of component (Δ) added will be too low.
The compatibility of Δ) with component C1 and/or component D+ is poor, resulting in a disadvantage that physical properties are deteriorated. Also (C1 and/
Alternatively, if the component D+ is too small, molding shrinkage increases, sink marks and warpage occur in the molded product, and surface properties deteriorate.

The composition of the present invention may further include ingredients (
Δ) Crystal nucleating agents such as talc, mica, titanium oxide,
Carbon black etc. and crystallization promoters, for example, when component (8) is an ethylene terephthalate polyester, polyoxyalkylene compounds compatible with the polyester, polyhydric alcohol derivatives, higher fatty acid esters,
Higher fatty acid metal salts, polyvalent carboxylic acid esters, high molecular weight aliphatic polycarboxylic acid salts, polyhydric alcohol esters, etc. may be blended. Usually, the amount of the crystal nucleating agent is up to 50% by weight of the composition, and the amount of the crystallization promoter is preferably up to about 10% by weight of the composition.

In addition, antioxidants, ultraviolet absorbers, stabilizers such as hydrolysis resistance improvers, plasticizers, lubricants, flame retardants, flame retardant aids, antistatic agents, coloring agents, conductivity imparting agents, and sliding properties. Modifiers (solid lubricating oils, liquid lubricating oils), polyfunctional crosslinking agents, impact modifiers (for example, rubber-like substances with a Tg of 0°C or lower, preferably -20°C or lower, preferably containing reactive groups) rubber),”
Inorganic fillers other than those listed in 1 above, fibrous reinforcing agents (e.g., glass braid, carbon fiber, graphite fiber, silicon carbide fiber, silicon nitride fiber, boron nitride fiber, potassium titanate whiskers, heat-resistant organic fiber), electrical conductivity Additives such as imparting agents (for example, metal fibers, polyacetylene fibers, metal powders, phosphorus, iron, carbon black, organic conductive polymers, etc.) can also be blended.

When blending inorganic fillers and inorganic fibers, a silane coupling agent, a titanium coupling agent, a zirfalinate coupling agent, etc. may be used in combination.

Additionally, other resins may be blended in amounts and types that do not detract from the objectives of the present invention.

The method for producing the composition of the present invention is not particularly limited, and any method may be used. For example, they can be blended by mechanical kneading using an extruder, roll mill, Banbury mixer, or the like.

Multi-stage kneading may be used in which the component (Δ) and the component Bl are kneaded and the ground component is kneaded.

The composition of the present invention can be widely used for molding various molded parts, films, articles such as plates, fibrous materials, tubular materials, containers, etc., as well as coating agents, adhesives, sealants, etc. It can also be used as a modifier for other resins. Also,
It can also be formed into films, fibers, etc., and further stretch-molded or made into secondary molded products.

(Operation) The composition of the present invention has a component (Δ) due to the presence of the component Bl.
is modified, the compatibility of the component Al with the component Cl and/or the component D+ is improved, a uniform blend is obtained, a molded article with excellent mechanical properties is obtained, and the component A) is modified. Features include reducing molding shrinkage, solving problems such as sink marks and warping, and producing molded products with excellent surface properties by 5 degrees, and improving the chemical resistance of component Cl and/or component D). has.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Note that % in the examples is based on weight, and various measurements in the examples were performed by the following methods.

(1) Heat distortion temperature according to ASTM D-E348, length 12611+1
1F1112.6, 18.6 on a 6.3-thick test piece
The test piece was heated at 2°C per minute with a bending stress of kg/CIfl applied, and the amount of deflection was 0.254111. The temperature when it reached was calculated.

■ Bending strength Measured according to ASTM, D-790.

(3) Surface properties The molded product was visually evaluated for sink marks, surface gloss, etc.

Synthesis Example 1 Synthesis of polyphenylene ether resin fBl having isocyanate groups.

100 parts of poly-2,6-dimethyl-1,4-phenylene ether powder with [η] of 0.58 (measured in chloroform at 30°C) and 2.5 parts of maleic anhydride were placed in a flask and heated under a nitrogen stream. It was dissolved in 450 parts of xylene at 130°C. On the other hand, a solution of 1.5 parts of dicumyl peroxide dissolved in 50 parts of xylene was gradually dropped into the flask using a dropping funnel, and after the dropwise addition was completed, the mixture was heated and stirred at 130°C for 5 hours. I reacted while doing so. After the reaction was completed, the reaction solution was allowed to cool to room temperature and poured into acetone to precipitate the produced polymer.

The precipitate was separated by filtration and dried under reduced pressure to obtain a sample. This sample had a characteristic absorption at 1785c+1-1 in the infrared absorption spectrum (IR), confirming that maleic anhydride was graft-bonded.

Furthermore, 100 parts of polyphenylene ether powder grafted with maleic anhydride and diphenyl-nylmethane were added.
3.0 parts of 4,4'-diisocyanate were placed in a flask, dissolved in 450 parts of xylene at 130°C under a nitrogen stream, and reacted with stirring at 135°C for 8 hours. After the reaction was completed, the reaction solution was allowed to cool to room temperature and poured into acetone to precipitate the produced polymer.

The precipitate was separated by 4·r and dried under reduced pressure to obtain a sample. This sample has an infrared absorption spectrum (IR) of 2275 cm-'
has a characteristic absorption of isocyanate groups, and 1725c
It was confirmed that 11' had a characteristic absorption of a maleimide group and that it contained an isocyanate group as a result of quantitative determination using the method described below.

The amount of isocyanate groups was determined by dissolving the polyphenylene ether in chloroform, reacting it with excess di-logotylamine, and back titrating the remaining di-n-butylamine with hydrochloric acid.

Synthesis Example 2 Polyphenylene ether resin t containing urethane bonds
Bl synthesis [η] is 0.58 (measured in chloroform at 30°C)
700 parts of poly-2,6-dimethyl-1,4-phenylene ether powder and 3.0 parts of ethyl isocyanate methacrylate were placed in a flask and dissolved in 450 parts of xylene at 130°C under a nitrogen stream. On the other hand, a solution of 1.5 parts of dicumyl peroxide dissolved in 50 parts of xylene was gradually dropped into the flask using a dropping funnel.
The reaction was carried out at ℃ for 5 hours while stirring while heating. After the reaction was completed, the reaction solution was allowed to cool to room temperature and poured into acetone to precipitate the produced polymer.

The precipitate was separated by filtration and dried under reduced pressure to obtain a sample. This sample had a characteristic absorption at 2275 cm'' in the infrared absorption spectrum (IR), and it was confirmed that ethyl isocyanate methacrylate was graft-bonded.

Furthermore, 100 parts of this isocyanate group-containing polyphenylene ether resin powder and 1.0 to 1.1 times (mole ratio) t-butyl alcohol to isocyanate groups were placed in a flask and dissolved in chloroform at 60°C under a nitrogen stream. Dissolved. The reaction was carried out at 60° C. for 5 hours while stirring, and after the reaction was completed, the reaction solution was allowed to cool to room temperature, and the reaction solution was poured into acetone to precipitate the produced polymer.

The precipitate was separated by filtration and dried under reduced pressure to obtain a sample. In this sample, the characteristic absorption based on the isocyanate group at 22750+l1-I in the infrared absorption spectrum (IR) disappeared and 1690
Since there was a characteristic absorption based on the urethane bond of cm', it was confirmed that the isocyanate group was masked.

Examples 1 to 6, Comparative Examples 1 to 3 Polyethylene terephthalate with [η] of 0.63 or polybutylene terephthalate with [η] of 1.2, [η]
Poly-
Powder of 2,6-dimethyl-1°4-phenylene ether and poly-2,6 containing isocyanate groups and/or urethane bonds obtained in Synthesis Example 1 or 2
-Cimethyl-1,4-phenylene ether powder and a predetermined amount of styrene resin are mixed in a blender,
The mixture was kneaded and extruded using an m-φ twin-screw extrusion machine (PCM-30, Ikegai Iron Works Co., Ltd.) at a cylinder temperature of 300° C. to form pellets. The obtained pellets were dried in a vacuum dryer at 120°C for 5 minutes.
After drying for a while, use an injection molding machine (Nissei Resin Co., Ltd., FS-75).
mold) into a molded product. The cylinder temperature at this time is 295
It was °C. The physical properties of each of the obtained molded products are
Shown in the table. Examples 7 to 9, Comparative Examples 4 and 5 Molding and molding were carried out in the same manner as in Example 1, except that the polyester in Example 1 was replaced with nylon 6 with a relative viscosity of 2.7, and the temperature in the cylinder was 270°C. The characteristics of the product were evaluated.

The results are shown in Table 2.

1) Polyethylene terephthalate 2) Poly-2,6-dimethyl-1,4-phenylene ether 3) High-impact polystyrene 4) Hydrogenated styrene-butadiene block copolymer 5) Polybutylene terephthalate (invention) As is clear from Tables 1 and 2, the composition of the present invention containing a polyphenylene ether resin containing isocyanate groups and/or urethane bonds has good surface properties and low bending strength. It can be seen that it is an excellent molded product and has an even higher heat distortion temperature.

Note that this composition was found to have advantages such as excellent chemical resistance.

Claims (1)

[Claims] At least one polar group selected from a carboxyl group, a hydroxyl group, and an amino group at the end and a melting point of 150 to 3
00°C thermoplastic resin (A) 5-95% by weight, polyphenylene ether resin (B) 95-5% by weight having isocyanate groups and/or urethane bonds, polyphenylene ether without isocyanate groups and/or urethane bonds A thermoplastic resin composition comprising 0 to 90% by weight of a resin (C) and 0 to 90% by weight of a styrene resin (D).