JPH0413771A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having improved impact resistance, cracking resistance, dropwise condensation resistance, antifogging property and heat-insulation without lowering the heat-resistance of the base resin by adding a specific high-molecular compound and a stabilizer to a resin at specific ratios. CONSTITUTION:The objective resin composition can be produced by compounding (A) 100 pts.wt. of a resin (e.g. polyphenylene ether) with (B) 1.0-100 pts.wt. (preferably 1.0-30 pts.wt.) of a high-molecular compound having an average molecular weight of >=10,000 and produced by reacting a polyalkylene glycol (preferably a glycol having an average molecular weight of >=100) with at least one kind of substance selected from polybasic carboxylic acid, polybasic carboxylic acid anhydride, polybasic carboxylic acid lower alkyl ester and organic polyisocyanate and (C) 0.001-2.0 pts.wt. of a stabilizer (e.g. benzoquinone).

Description

[Detailed description of the invention] [Purpose of the invention]

[Industrial Field of Application] The present invention relates to a resin composition, and more specifically, to a resin composition that is excellent in impact resistance, crack resistance, dew condensation prevention, antifogging property, heat retention property, and workability. [Prior Art] (1) Background Synthetic resins are used in a wide range of applications because they have excellent mechanical properties, electrical properties, dimensional stability, heat resistance, etc. In recent years, with the development of new applications and the setting of more severe usage conditions, further improvements in the above properties have been required.
In particular, it is strongly desired to improve impact resistance and crack resistance. In applications where impact resistance is important, for example, a large number of parts such as electrical parts are attached to a plastic housing, and it is generally well known that metal parts are embedded and attached using insert molding. It is being However, in this case, since metal and plastic have different thermal properties (for example, coefficient of expansion), accidents such as damage to the plastic part often occur. In addition, in the civil engineering field, plastics such as epoxy resins, urethane resins, and acrylics are used in large quantities, but because of their high hardness, they have high wear resistance and tensile strength, but have the disadvantage of being brittle. It is desired to improve impact resistance and crack resistance. On the other hand, many plastic films are used in greenhouse horticulture, and it is desired that their effects, such as anti-condensation, anti-fogging, and heat retention properties, be permanent. (2) Problems with the conventional technology Therefore, in order to improve the defects in impact resistance and crack resistance, for example, the combination of rubber-reinforced styrene resin (
JP-A No. 48-65249) Improvement method using styrene-butadiene block copolymer (Japanese Patent Publication No. 59-420)
No. 21) has been proposed. However, when a large amount of rubber component is blended according to these methods, although impact resistance and cracking resistance are improved, properties such as rigidity and processing fluidity are disadvantageously lowered. In addition, for the purpose of improving deficiencies in anti-condensation and anti-fogging properties, surface active resins such as water-soluble resins such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer resins, glycerin fatty acid esters, sorbitan fatty acid esters, etc. However, since polyvinyl alcohol and ethylene-vinyl alcohol co-polymerized mb have relatively high melting points and have hydroxyl groups in their resin skeletons, condensation reactions occur at high temperatures. Because it decomposes thermally, it is difficult to mold compared to general-purpose polyethylene, polypropylene, etc., and it is difficult to mold films such as blown film. Furthermore, resins containing water-soluble resins have problems such as poor compatibility between water-soluble resins and general-purpose resins, so it is difficult to expect a significant increase in the content of water-soluble resins and poor transparency. Since surfactants are generally low-molecular, there are problems such as, for example, when they are used as anti-condensation or anti-fogging films, they bleed out, making it impossible to expect long-lasting performance. [Problem to be Solved by the Invention] Therefore, the problem to be solved by the present invention is to develop a resin without degrading its excellent properties such as heat resistance, electrical properties, two-dimensional stability, processing fluidity, and rigidity. It is an object of the present invention to provide a resin composition having excellent impact resistance, crack resistance, anti-condensation properties, anti-fog properties, heat retention properties, and workability.

[Structure of the invention]

(1) [In order to solve the above-mentioned problems, the present invention provides (a) resin 1
00 parts by weight, (a) reacting polyoxyalkylene glycol with at least one selected from polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, polyvalent carboxylic acid lower alkyl esters, and organic polyisocyanates. Prepared high molecular weight compound 1 having an average molecular weight of 10.000 or more
．． 0 to 100 parts by weight and (c) stabilizer 0.01 to 2.0
The gist is a resin composition in which the weight part is contained in a resin. Incidentally, the average molecular weight used in the present invention refers to the 5 weight average molecular weight. Below, the various elements constituting the invention will be explained in terms of items. (2) High molecular weight compound Polyoxyalkylene glycol (hereinafter referred to as POAG), which is one component of the high molecular weight compound constituting the composition of the present invention, is obtained by addition-polymerizing alkylene oxide to an organic compound having two active hydrogen groups. Preferably, a glycol having an average molecular weight of 100 or more is used. Examples of the active hydrogen groups include alcoholic hydroxyl groups, amine groups, and phenolic hydroxyl groups. Specific examples of the organic compound having two active hydrogen groups include ethylene glycol, diethylenoglycol,
Propylene glycol, dipropylene glycol, 1,
Examples include 4-butanediol, 16-hexanediol, neopentyl glycol, bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, butylamine, octylamine, laurylamine, and cyclohexylamine. Examples of the alkylene oxide used in addition polymerization include ethylene oxide, propylene oxide, butylene oxide, and styrene oxide. The above addition polymerization is preferably carried out using an alkali catalyst such as sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, or an acid catalyst such as boron trifluoride, at a temperature of about 50 to 200°C for about 2 to It will be held for 30 hours. If the average molecular weight of the obtained POAG is less than 100,
The purpose of the invention is not achieved. Next, examples of the polyhydric carbonic acid, its anhydride, or its lower alkyl ester to be reacted with POAG include (a) malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid; acids, terephthalic acid, itaconic acid, trimellidic acid, pyromellitic acid or dimer acids; (b) anhydrides of the acids mentioned in (a); or; (C) Monomethyl ester, dimethyl ester, monoethyl ester, diethyl ester of (a). Examples include monopropyl ester, dipropyl ester, monobutyl ester, and dibutyl ester. When reacting POAG with a polyhydric carboxylic acid, its anhydride, or its lower alkyl ester, they are mixed in equal amounts in terms of functional group ratio by esterification reaction or transesterification reaction, and under reduced pressure conditions such as 120 to 250°C and 104 to 10 Torr. Do it below. Further, as the organic polyisocyanate to be reacted with POAG, for example, tolylene diisocyanate, 4,4°
-methylene-bis-(phenylisocyanate), hexamethylene diisocyanate. Examples include inphorone diisocyanate, xylylene diisocyanate, 4,4'-methylene-bis-(cyclohexyl isocyanate), 4,4'-isopropylidene-bis-(cyclohexyl isocyanate), and trimethylhexamethylene diisocyanate. When reacting POAG with organic polyisocyanate,
For example, both are mixed in the presence of a urethanization catalyst at a 10010R equivalent ratio of 1.5 to 0.5, and
Allow to react for ~5 hours. In any of the above cases, the average molecular weight of the obtained high molecular weight compound is preferably 10,000 or more; if the molecular weight is less than 10,000, the object of the present invention will not be achieved. (3) Stabilizer Stabilizers used in combination with high molecular weight compounds include benzoquinone, hydroquinone, g-hydroquinone, 2.5-di-t
-Butylhydroquinone. Butylhydroxyanisole, pyrogallol, hydrogen, hydrazine derivative, octadecyl-3-(3,5-dec-
Examples include shari-butyl-4-hydroxyphenol) propionate. (4) Target resin The resin in the resin composition of the present invention is not limited in any way, and includes, for example, polyphenylene ether, polystyrene, rubber-reinforced polystyrene, polyphenylene ether/polystyrene graft copolymer, polycarbonate, melamine resin, urea resin, polyamide, and phenol resin. , polyacetal, epoxy resin, polyurethane, polyvinyl chloride, polyester, polyethylene, polypropylene, polyacrylic, acrylonitrile-styrene copolymer, ethylene vinyl acetate, acrylonitrile-exposed butadiene-styrene copolymer, polyacrylate, silicone, fluorine, etc. It will be done. (5) Compounding ratio The resin composition of the present invention contains 1.0 to 100 parts by weight, preferably 1.0 parts by weight, of a high molecular weight compound per 100 parts by weight of resin.
~30 parts by weight and 0.001 to 2.0 parts by weight of stabilizer. When the content of the high molecular weight compound is less than 1.0 parts by weight per 100 parts by weight of the resin, the resulting resin composition has good impact resistance, anti-condensation properties, anti-fog properties, heat retention properties, and processing workability. On the other hand, if it is contained in an amount greater than 100 parts by weight, the mechanical strength of the resin tends to decrease. Furthermore, if the amount of the stabilizer is less than 0.001 parts by weight, the high molecular weight compound will deteriorate during molding, and if it is more than 2.0 parts by weight, it may cause coloring or be uneconomical. (8) Preparation of the composition The resin composition of the present invention can be prepared as long as the high molecular weight compound, the stabilizer, and the resin are mixed virtually uniformly, so there is no particular restriction on the preparation method, and the kneading method For example, means for melting and kneading using an extruder, roll mixer, Banbury mixer, kneader mixer, etc. can be employed. In addition, the composition of the present invention may contain a plasticizer, a lubricant, a colorant, a filler, a flame retardant, a surfactant, etc., if necessary. Furthermore, since the resin composition of the present invention has good film-forming properties, it can be processed into films, sheets, filaments, powders, molded products, and the like. Molding methods include extrusion molding, calendaring, compression molding, injection molding, transfer molding, blow molding, profile extrusion, rotational molding, lamination, casting,
Any method such as inflation is possible. [Function] Because the resin composition of the present invention contains a high molecular weight compound made from a specific polyoxyalkylene glycol and a stabilizer, the resin composition maintains the inherent heat resistance, mechanical properties, dimensional stability, and appearance of the resin. It is a resin material with improved impact resistance, processing fluidity, crack resistance, anti-condensation properties, anti-fog properties and heat retention properties. Furthermore, this property remains stable over a long period of time. [Examples] The modes and effects of implementing the invention will be described below using Examples and Comparative Examples. However, the examples are merely for illustration purposes and are not intended to limit or limit the idea of the invention. , parts and % represent parts and % by weight. Example 1 100 parts of polyethylene glycol with an average molecular weight of 5,000 and 3.88 parts of dimethyl terephthalate in a vacuum kneader
parts, flaky potassium hydroxide (10% aqueous solution) 0.1
of the mixture, and the temperature was raised to 200°C under a reduced pressure of 1 Tarr.
A high molecular weight compound was obtained by reacting for 3 hours while removing methanol. When the molecular weight of the obtained high molecular weight compound was measured by high performance liquid chromatography, the average molecular weight was 130.0.
It was 00. 3 parts of the high molecular weight compound obtained above, parts of hydroquinone o and ooe as stabilizers, and 100 parts of a commercially available polystyrene resin were uniformly mixed and kneaded in a twin-screw extruder to obtain pellets. This pellet was injection molded using an in-line screw injection molding machine set at a cylinder temperature of 200° C. to obtain a test piece. Table 1 shows the results of measuring the physical properties of this test piece. Comparative Example 1 Physical properties were measured in the case where the high molecular weight compound and the stabilizer were not mixed in Example 1. The results are shown in Table-1. Example 2 50 parts of poly(2,8-dimethyl-1,4-phenylene) ether and 50 parts of rubber-reinforced polystyrene containing 8% polybutadiene, octadecyl-3-(3
, 5-ditertiary-butyl-4-hydroxyphenol) propionate and a terminally graded polypropylene glycol (average molecular i 4,000) and hexamethylene diisocyanate at an NC010H equivalent ratio of 1.0. (Average molecular weight 200,00
A test piece was obtained using an in-line screw injection molding machine with a cylinder temperature of 290°C. The results are shown in Table-1. Comparative Example 2 The physical property measurement results obtained in Example 2 when the high molecular weight compound and the stabilizer were not mixed are shown in the table. Example 3 100 parts of a commercially available polycarbonate resin, 0.1 part of 1,000 omega as a stabilizer, and an ethylene oxide adduct of bisphenol A (average molecular weight 3,000) as a high molecular weight compound.
) and anhydride: a condensate of uccinic acid (average molecular weight 150,00
0) 5 parts were used in an injection molding machine at a cylinder temperature of 250°C to obtain a test piece. Table 1 shows the measurement results of physical properties. Comparative Example 3 Table 1 shows the results of physical property measurements in Example 3 when the high molecular weight compound and stabilizer were not mixed. Example 4 Polyethylene glycol (weight average molecular weight 20.000
) and hexamethylene diisocyanate NGOlo)l
5 parts of a high molecular weight compound (average molecular weight 200,000) obtained by reaction at an equivalent ratio of 1.0, 0.001 part of thiourea as a stabilizer, and 100 parts of polyethylene terephthalate.
The parts were sealed with nitrogen gas in an autoclave and heated to 285°C.
The mixture obtained by kneading for 10 minutes was formed into a Lee sheet by hot pressing. When Izod impact strength was measured using a test piece of this sheet, it was found that at 23°C it was 45 kg-c layer/c
and 15 without adding high molecular weight compounds and stabilizers.
A significant improvement in impact resistance was observed compared to kg-Cm/c■. (Leaving space below) Table 1 Book I JIS K7110 Book 2 JIS K7113 Example 5 After mixing 90 parts of low density polyethylene resin, 10 parts of the high molecular weight compound of Example 1, and 0.02 part of benzoquinone,
01/- was melted and pelletized using an extruder (extrusion temperature: 190°C). Next, use an inflation molding machine to make the Gui temperature 19
0℃, extrusion rate 5 kg/hF-, blow-up ratio 1.9
A film with a thickness of 40 mm was obtained under these conditions. The strength of this film is strength at break (ASTMI) 8B
Based on 2A law, the same applies hereinafter) 290kg/c■2. Elongation at break (according to ASTM0882A method, the same applies hereinafter) 69
The transparency haze (according to ASTM DI003, the same applies hereinafter) was 8.5%. Further, this film was sealed and covered above a 50° C. constant temperature water bath with an auxiliary tool tilted at 30° from the horizontal, and the durability of the antifogging effect and the wet state of the film surface were observed. As a result, the antifogging property was good, and the effect remained unchanged even after 3 months. On the other hand, one day after the film was formed, the film was placed in a constant temperature bath at 50° C. for one week, and then taken out and left for 18 days to observe the presence or absence of blooming. As a result, no blooming was observed. Example 6 A high molecular weight compound (average molecular weight 320, 000 ) 1
A film having a thickness of 30 wells was obtained in the same manner as in Example 5 using 0 parts of butylhydroxyanisole, 0.02 parts of butylhydroxyanisole, 90 parts of crystalline polypropylene, and 0.5 parts of sorbitan ester as an antifogging agent. The strength at break of this film is 305 kg/cm2. The elongation at break was 450%, and the transparency haze was 9.0%. In the same test as in Example 5, the antifogging effect, its persistence, and blooming were also good. Comparative Example 4 1.0 parts of sorbitan monolaurate as an antifogging agent was kneaded into 100 parts of low-density polyethylene, and a film with a thickness of 40 μm was obtained in the same manner as in Example 5. The antifogging effect of this film was lost within one week. In addition, there was a large amount of blooming, making it unusable.

【Effect of the invention】

The present invention imparts excellent impact resistance and crack resistance to the resin without reducing the resin's excellent mechanical properties such as heat resistance, electrical properties, dimensional stability, processing fluidity, and rigidity. It can contribute to expanding the field of use of resins by providing water scale, dew condensation prevention, antifogging properties, and heat retention properties.

Claims (1)

[Claims] 1 (a) For 100 parts by weight of the resin, (b) at least one type selected from polyoxyalkylene glycol and polyvalent carboxylic acid, polyvalent carboxylic acid anhydride, polyvalent carboxylic acid lower alkyl ester, and organic polyisocyanate. A resin composition comprising a resin containing 1.0 to 100 parts by weight of a high molecular weight compound having an average molecular weight of 10,000 or more, prepared by reacting the above, and (c) 0.001 to 2.0 parts by weight of a stabilizer. thing.