JPH05320472A - Molding thermoplastic composition endowed with improved mold release properties - Google Patents

Abstract

PURPOSE: To obtain molding thermoplastic compositions having improved mold release properties at high temperatures and good mechanical characteristics, by incorporating an impact resistant vinyl aromatic copolymer, an engineering polymer, a specified mold release agent, and a bis(alkyl-phenyl)pentaerythritol diphosphite.

CONSTITUTION: The composition is incorporated with (A) an impact resistant vinyl aromatic copolymer containing an ethylenically unsaturated nitrile, a vinyl aromatic monomer, and rubber; (B) an engineering polymer; (C) an effective amount of a mold release agent constituted by a synergistic mixture of (1) an ester of a 16-18C fatty acid with glycerin and (2) an ester of a saturated aliphatic monocarboxylic acid or the mixture of the monocarboxylic acid with a 10-20C polycarboxylic acid with an aliphatic alcohol having 4-6 OH groups; (D) a bis(alkyl-phenyl) pentaerythritol diphosphite; and possibly (E) a graft copolymer consisting of an elastomeric core and a vinyl monomer as a graft component.

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to a molding thermoplastic resin composition having improved release characteristics. More particularly, the present invention relates to molding thermoplastic resin compositions that impart improved release characteristics and improved physico-mechanical properties at high molding temperatures.

Impact-resistant aromatic vinyl copolymers (A) consisting of ethylenically unsaturated nitriles, aromatic vinyl monomers and rubbers, and engineering polymers (B) such as polycarbonates are described in Italian Patent No. 1,0.
00,431 and U.S. Pat. No. 4,526,926,
No. 4,624,986 and No. 4,906,689
No. The molding composition comprises a copolymer (A), an engineering polymer (B) and 10 of the above type.
It is also known to include a graft polymer (C) which has a secondary glass transition temperature (Tg) below 0 ° C. and which consists of an elastomer core grafted with vinyl monomer chains. These compositions are described in European Patent Application Nos. 216,065 and 199, published April 1, 1987.
No. 379,039 published Jul. 25, 2000, it has been utilized in many technical fields because of its optimal combination of mechanical, chemical-physical and thermal properties. ing. A disadvantage of these known compositions is their poor mold release properties when they are injection molded. As is well known, this drawback mainly results in damage to the molded product during the unloading stage. A known method of avoiding this drawback is to perform demolding at high temperature. However, this operation is mainly associated with the drawback that the molded product sticks on the surface of the mold and is deformed or damaged. To improve the releasability of the molded product from the mold,
The prior art has used release agents. However, these additives very often have a negative effect on the properties of the thermoplastic resin composition. For example, bis (stearyl- / palmitoyl-) ethylenediamine, which is widely used in ABS resins, improves the fluidity of the resin,
Although this improves the processability of the resin, it drastically lowers the thermal deformation stability (VICAT). In the case of the compositions according to the invention, such a decrease in mechanical properties with respect to heat is an important drawback, which leads to a drastic narrowing of the application range of the compositions. Release agents composed of long-chain aliphatic carboxylic acid esters of monohydric and polyhydric alcohols are also known. However, these release agents also deteriorate the mechanical properties of the resin when exposed to heat for a long time. Furthermore, these release agents are volatile at the molding temperature of the composition, which gives rise to major drawbacks during processing.

The present invention makes it possible to overcome all the above-mentioned drawbacks, has a release behavior suitable for all industrial applications, and uses any release agent. It is possible to provide a thermoplastic resin composition for molding which exhibits the same level of mechanical, physical and thermal properties as compared with a composition containing no

According to the present invention, a thermoplastic resin composition having the above characteristics is (i) 16-18.
An ester of glycerol with a fatty acid having carbon atoms, and (ii) an aliphatic alcohol having 4 to 6 hydroxyl groups and a saturated aliphatic monocarboxylic acid having 10 to 20 carbon atoms or 10 to 20 such monocarboxylic acid. Obtained by using an effective amount of a synergistic mixture of the two esters as a mold release agent, an ester with a mixture of polycarboxylic acids having carbon atoms. Accordingly, the subject of the present invention is (A) an impact-resistant aromatic vinyl copolymer consisting of ethylenically unsaturated nitrile, aromatic vinyl monomer and rubber; (B) an engineering polymer; and (C) (i) 16-18. An ester of glycerol with a fatty acid having carbon atoms and (ii) a saturated aliphatic monocarboxylic acid having 10 to 20 carbon atoms or a mixture of said monocarboxylic acid and a polycarboxylic acid having 10 to 20 carbon atoms; A thermoplastic resin composition for molding comprising an effective amount of a release agent composed of a synergistic mixture of an ester with an aliphatic alcohol having a hydroxyl group of 6 to 6. When the molding thermoplastic resin composition of the present invention is used for injection molding of a very complicated shaped article, in order to completely fill the mold with the thermoplastic resin composition as far as the size and the critical point of the filling flux are concerned. , The mold is required to have a very high temperature, generally above 260 ° C. At such temperatures, the physico-mechanical properties of the above composition are reduced to unacceptable levels. According to a further aspect of the invention, an effective amount of at least one bis (alkyl-phenyl) pentaerythritol diphosphite (D) is added to give compositions (A) and (B) of the invention. It becomes possible to widen the temperature range for molding, and further, 260 ° C. without substantially lowering the initial mechanical, physical and thermal properties of the thermoplastic resin composition for molding of the present invention.
It allows the mold to be used at higher temperatures. Bis (alkyl-phenyl) pentaerythritol diphosphite (D) is the composition (A) + (B) of the present invention.
0 to 3 parts by weight, especially 0.01
-3 parts by weight, preferably 0.05 to 1 part by weight. The composition (A) + (B) + (C) + optional component (D) according to the invention, if special mechanical properties are required, especially in the welding zone of the injection flux.
May further include a graft polymer (E) having a secondary glass transition temperature (Tg) lower than 10 ° C. and composed of an elastomer core grafted with vinyl monomer chains. 10 of the composition (A) + (B) of the present invention
For 0 parts by weight, the release agent (C) is added in an amount in the range of 0.01 to about 3 parts by weight, preferably 0.5 to 2 parts by weight. In the synergistic mixture (C), the ratio of the two esters (i) and (ii) can be varied within wide limits, but the weight ratio is from 4: 1 to 1: 4, preferably about 1:
When set to 1, a particularly excellent effect was obtained. The ester (i) of glycerol with a C ₁₆ -C ₁₈ fatty acid is a highly biodegradable product, has nonionic polarity and has the following properties. Saponification number 155-175 Iodine number 1-2 Monoester content 40-99wt% Melting point 55-65 ° C Free glycerol 1-6wt% Water content 0.1-0.5wt% These esters are HULS TROISD from Germany.
ORF AG. Trademark name SO manufactured and sold by
FTENOL, LANKRO ITALIANA.
p. A. The brand name LANKR manufactured and sold by
It is well known in the market as a product under the trade name LOXIOL manufactured and sold by OPLAST and HENKEL of Germany. The ester (i) is polystyrene, acrylonitrile-butadiene-styrene (A
BS), polyethylene, polycarbonate, polypropylene and polyvinyl chloride have been proposed as slip agents, antistatic agents, mold release agents and anti-blocking agents for many plastic materials, but according to tests carried out by the applicant, It has been found that the release properties are very limited when using the thermoplastic compositions of the present invention containing the above components A, B and C. In order to prepare the synergistic mixture (D) ester (ii) according to the invention, the following can be used. 4 OH groups and alcohols having 4 to 16, preferably 4 to 8 carbon atoms, 5 OH groups and 5 to 18 alcohols, preferably 5 to 10 carbon atoms and 6 OH groups and 6 to 18 ,
An alcohol having preferably 6 to 12 carbon atoms. As the ester (ii), those obtained by completely esterifying the OH group of 4 to 6 of alcohol with one or more C ₁₀ -C ₂₀ carboxylic acid are preferable. Alcohols containing 4 to 6 OH groups include erythritol, arabitol, adonitol, mannitol and dulcitol, especially mesoerythritol, xylitol, sorbitol and pentaerythritol. Any C ₁₀ -C
₂₀ aliphatic saturated monocarboxylic acids can be used,
It may optionally be used with a C ₁₀ -C ₂₀ polycarboxylic acid, for example capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, monodecanoic acid, eicosanoic acid. , Sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tapsinic acid and the like.
Esters (ii) used in the synergistic mixture according to the invention include pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, pentaerythritol tetramyristate,
Pentaerythritol tetralaurate, mesoerythritol tetralaurate, mesoerythritol tetrastearate, mesoerythritol tetramyristate, mesoerythritol tetraeicosanate,
Examples include xylitol pentastearate, xylitol pentapalmitate, arabitol pentastearate, arabitol pentapalmitate, sorbitol hexastearate, sorbitol hexapalmitate, dulcitol hexapalmitate, mannitol hexastearate, and mannitol hexamyristate. Preference is given to using esters of stearic acid and of palmitic acid. These esters (ii) can be prepared by known methods, for example Geor.
g Houme-We by Thieme Verlag
yl Methoden der Organisch
en Chemie ", 4th edition, Volume VIII, page 516. These esters (i
i) is well known in the market as a product under the brand name LOXIOL manufactured and sold by HENKEL of Germany. German Patent No. 2,507,748;
2,701,725 and 2,729,485 disclose the use of these esters (ii) as release agents for high molecular weight aromatic polycarbonates. However, according to a test conducted by the applicant of the present invention, in the case of the thermoplastic composition of the present invention containing the above-mentioned components (A) and (B), their release activity is very poor. The bis (alkylphenyl) pentaerythritol diphosphite (D) used in the molding thermoplastic composition of the present invention corresponds to the following general formula.

[Chemical 3] (In the formula, R ₃ and R ₄ may be the same as or different from each other, and these represent an alkyl group having 1 to 10 carbon atoms.) All the above compounds and their production methods are well known in the literature, U.S. Pat. Nos. 3,281,381; 3,310,60
9; 3,192,243; 3,205,269, the contents of which are included in the description of the present specification. Preferred bis (alkylphenyl) pentaerythritol diphosphite is represented by the following general formula.

[Chemical 4] (In the formula, R ₅ represents an alkyl group having 1 to 6 carbon atoms.) A particularly preferable compound is bis (2,4-di-tertiary) having a trade name ULTRANOX 626 manufactured and sold by General Electric Company. Butyl-phenyl) pentaerythritol. The vinyl aromatic copolymer (A) used in the molding thermoplastic composition of the present invention may be: (A.1) 2-35 wt% ethylenically unsaturated nitrile, 20 wt% or less. Impact-resistant vinyl aromatic copolymer containing diene rubber and vinyl aromatic monomer, or (A.2) 2-35 wt% ethylenically unsaturated nitrile, 5-50 wt% olefinic elastomer and 93-15 wt% Impact-resistant vinylaromatic copolymer, comprising% vinylaromatic monomer, the sum of these monomers being equal to 100. Preferably, the high impact styrene polymer (A.2) is 2-35 wt% ethylenically unsaturated nitrile, 15-30 wt% olefinic elastomer and 35-83 wt% vinyl aromatic monomer. including. The term "vinyl aromatic monomer" as used herein and in the claims
Includes an ethylenically unsaturated compound represented by the following general formula.

[Chemical 5] (In the formula, X is hydrogen or an alkyl group having 1 to 4 carbon atoms, n is 0 or an integer of 1 to 5, and Y is halogen or an alkyl group having 1 to 4 carbon atoms.) Aromatic compound having the above general formula Examples of vinyl monomers are: styrene, methylstyrene, mono-, di-, tri-, tetra- and penta-chlorostyrene and corresponding α-methylstyrenes; nuclear alkylated styrenes, and ortho-. And para
There are corresponding α-methylstyrenes such as methylstyrene, ortho- and para-ethylstyrenes, ortho- and para-methyl-α-methylstyrenes and the like. These monomers can be used alone, or mixed with one another, or mixed with other copolymerizable comonomers (eg maleic anhydride). Particularly, styrene is preferable. Copolymerized with an aromatic vinyl monomer,
The first ethylenically saturated nitrile that may be mentioned and preferred is acrylonitrile, but other ethylenically saturated nitrile monomers, such as metoacrylonitrile, acrylic acid, metoacrylic acid, and alkyl radicals having 1 to 10 carbon atoms. These alkyl esters containing 6 can also be used in an advantageous manner.
The diene rubbers used in the impact resistant copolymers (AI) include polybutadiene, polyisoprene, butadiene and / or isoprene and copolymers of styrene or other monomers. Of these, polybutadiene is preferable. The content of the diene rubber in the impact-resistant aromatic vinyl copolymer is less than 20% by weight,
.About.15% by weight is preferred. In the impact-resistant aromatic vinyl copolymer (A.2), the elastomer olefin component is in the form of an ethylenically saturated nitrile-aromatic vinyl monomer copolymer, partially grafted with the ethylenically saturated nitrile and the aromatic vinyl monomer, It is the backbone that is mechanically coupled. The elastomer olefin component is a rubber-like copolymer,
The Mooney viscosity at 100 ° C. is in the range of 10 to 150 ML-4, and there are at least two different linear α-monoolefins (eg, ethylene, propylene, butene-1, octyl-1, etc.), and at least other It has a polymerizable monomer (generally a polyene, usually a non-conjugated diene). One of the α-monoolefins is preferably ethylene for use with other long chain α-monoolefins. The weight ratio of ethylene to other α-monoolefin in the rubbery copolymer is usually from 20:80.
The range is 80:20. A particularly preferred copolymer is
Ethylene propylene non-conjugated diene terpolymers in which the non-conjugated diene is cyclic or acyclic, examples of which include 5-methylene-2-norbornene,
5-ethylidene-2-norbornene, 5-isopropylene-2-norbornene, pentadiene-1,4, hexadiene-1,4, hexadiene-1,5, heptadiene-1,5, dodecatriene-1,7,9, There are methylheptadiene 1,5, norbornadiene-2,5, cyclooctadiene-1,5, dicyclopentadiene, tetrahydroindene, 5-methyltetrahydroindene and the like. The diene content is in the range of approximately 5 to 20% by weight of diene monomer units in the rubbery terpolymer, preferably 8 to 18% by weight. Particularly preferred as the rubbery ethylene propylene non-conjugated diene is that the Mooney viscosity (ML-4) measured at 100 ° C. is 30 to 90,
The iodine value is higher than 5, and preferably 10 to 40. The high-impact aromatic vinyl copolymers (A.1) and (A.2) are prepared by known polymerization processes in suspension, bulk suspension or continuous bulk, provided that the compounds are used as starting monomers. It can be manufactured by carrying out. Impact-resistant aromatic vinyl copolymer (A.
If 1) is produced by an emulsion polymerization process, the diene rubber can also be higher than 20% by weight and up to 65% by weight, and the ethylenically saturated nitrile content is 2%.
To 35% by weight. The engineering polymer (B) used in the composition of the present invention can be a plastic material having mechanical, chemical and thermal properties suitable for use as a structural material. For more information about the term "engineering polymer," see "E
Nineered Materials Handb
look "(Vol. 2 Engineering Pl
astics-ASM Intern; 1988). Typical examples of suitable engineering polymers are: polycarbonates, polyesters, thermoplastic polyurethanes, polymethacrylates, styrene methyl methacrylate copolymers, acrylic polymers, styrene maleic anhydride copolymers, vinyl chloride polymers, etc., and fragrances. Group polycarbonates are preferred. The aromatic polycarbonate has the following formula (II)
Of bisphenol is preferred:

[Chemical 6] In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent hydrogen, or an alkyl radical having 1 to 4 carbon atoms or halogen, and A represents —O—, —C.
O -, - SO ₂ -, cycloalkyl containing alkylene radicals containing from 2 to 10 carbon atoms, alkylidene radicals containing 2 to 10 carbon atoms, a cycloalkylene radical containing 5-15 carbon atoms, 5-15 carbon atoms It is an alkylidene radical or a radical of formula (III) below:

[Chemical 7] Examples of particularly preferred bisphenols are: 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2- Bis- (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) propane and 1,1-bis- (4-hydroxyphenyl)
It is cyclohexane. Particularly preferred polycarbonates are based on one or more of the above bisphenols. Particularly preferred among these polycarbonates are 2,2-bis- (4-hydroxyphenyl) propane and 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, each alone or It is based on a mixture with the other or with one of the bisphenols indicated above. Aromatic polycarbonates have an average molecular weight of at least 10,000.
0, specifically 10,000 to 200,000
And 20,000 to 80,0 are preferable.
00. This average molecular weight is 25 ° C., CH ₂ Cl ₂
It was determined by measuring the relative viscosity at a concentration of 0.5% by weight in. Aromatic polycarbonates are well known in the art and are commercially available from several producers. For example, its products include: "LEXA
N "(registered trademark) (General Electric
Company, Pittfield, Mas
s. , USA), "SINVET" (registered trademark) (EN
IMONT-Milan), “DUROLON” (registered trademark) (Proquigel (Brazil)) and the like. In the composition of the present invention, the amount of vinyl aromatic polymer (A) and the amount of engineering polymer (B) can vary within wide limits. Generally, the vinyl aromatic polymer (A) is contained in an amount of 10 to 90% by weight, preferably 20 to 80% by weight; and, correspondingly, the engineering polymer (B) is 90 to 10% by weight, preferably 80. ~
20% by weight is contained. The compositions of the present invention also consist of an elastomeric core having a second grade glass transition temperature of less than 10 ° C and grafted onto it, especially when high mechanical properties are required at the joint of the injection flux. It is also possible to further contain a graft polymer (E) containing a vinyl monomer chain. The amount of the graft polymer (E) may be 0 to 30 parts, preferably 2 to 15 parts based on 100 parts by weight of the blend of (A) and (B). The graft polymer (E) is a "core-shell" type polymer containing an elastomer core containing vinyl monomer chains grafted onto it. Preferably, the "core shell" polymer contains from about 25% to about 95% by weight elastomeric core and correspondingly from about 75% to about 5% by weight vinyl monomer chains grafted thereon. The elastomer core has a second-grade glass transition temperature below 10 ° C., polybutadiene, a copolymer of butadiene and styrene, isoprene and / or acrylonitrile, wherein the content of butadiene is 4
It may be higher than 0 mol% or may be acrylic rubber. The vinyl monomers grafted onto the elastomeric core can be acrylic acid or methacrylic acid derivatives, vinyl aromatic compounds, vinyl cyanide compounds and polyfunctional derivatives, which may be used alone or as a mixture. .. Examples of these grafted vinyl monomers are methacrylic acid alkyl esters in which the alkyl group contains from 1 to 16 carbon atoms, preferably methyl methacrylate; for example 1,3-butylene glycol dimethacrylate and trimethylol-propane-. Esters of methacrylic acid such as trimethacrylate and polyfunctional alcohols; allyl methacrylate and / or diallyl methacrylate; styrene, vinyltoluene, α-
Vinyl aromatic compounds such as methyl styrene and halogenated styrene; vinyl naphthene or divinyl benzene;
Styrene is particularly preferred; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-halogenated acrylonitrile; acrylonitrile is particularly preferred; and maleic acid and its anhydride are included. These vinyl monomers can be used alone or in a mixture. The elastomeric core of the graft copolymer (E) used in the composition of the present invention has a second-grade transition temperature, preferably less than -10 ° C and even -50, measured by extraction.
It has a transition temperature below 0 ° C. and a degree of cross-linking above 50% by weight and up to 99% by weight (gel content). The graft copolymers used in the composition according to the invention preferably have an elastomer content of more than 35% by weight and up to 95% by weight. These copolymers are bulk polymerized,
It can be produced by any known method such as suspension polymerization, bulk-suspension polymerization, solution polymerization or emulsion polymerization.
Graft polymer (E) used in the intended composition
A typical example of is a three-step polymer, which has a rubber-like core based on butadiene, a second step polymerized from styrene and a final step polymerized from methyl methacrylate and 1,3-butylene-glycol-dimethacrylate. Or have a shell. Graft polymers (E) are known in the market, for example Rohm and Haas.
PARALOID® EXL260 from Company (Philadelphia, USA)
0, EXL2300, EXL3600 and EXL330
It is available under many trade names, or from many manufacturers, such as Kanega, the trade name KaneAce® in Belgium. Examples of preferred molded thermoplastic compositions are 2
0-60% by weight of (A.1) or (A.2) and 80
To 40 wt% aromatic polycarbonate and 0.1 to 1 part by weight of bis (alkyl-phenyl) dishoffit (D), 0.5 to 2 with respect to 100 parts by weight of this blend.
It comprises a formulation composed of parts by weight of the release synergistic mixture (C) and 0 to 15 parts by weight of the graft polymer (E). The compositions of the present invention may be manufactured by any of the known conventional mixing methods. Generally, the mixing is carried out in the molten state, for example 1-screw or 2
-In a known mixing unit such as a screw extruder, a Bambury mixer, a mixing roll, etc. first premixed at room temperature and mixed at a temperature of 180-300 ° C. The composition may be directly added to the composition, such as a plasticizer, a lubricant, a fire retardant, an antistatic agent, a dye, a pigment, glass fibers or other inorganic fillers, to impart specific properties to the material. Other additives incorporated may also be included. The composition of the present invention is easy to process,
It represents a complex of properties that make the composition suitable for use in the manufacture of articles imparted with a high degree of impact strength as well as a high degree of toughness. Therefore, the field of use of the composition is
It is generally a sector of household electrical appliances, electronics industry and industrial articles in the form of films, sheets, strips, bands, rods, boxes, breads, containers and the like. The composition may be used to make foamed articles by conventional techniques. In order to better understand and carry out the present invention, some specific but non-limiting examples are set forth below. In these examples, all parts and percentages are by weight unless otherwise specified. In these examples, the following methods were used to determine the properties of the compositions of this invention. Mechanical properties Test specimens with a thickness of 3.2 mm, standard ASTM D
256 measured notch resilience at 23 ° C. and −30 ° C., and fracture elongation in the tensile stress test according to standard ASTM D638. Thermal property VICAT B softening temperature (5 kg in oil)
306, measured by a temperature increase of 120 ° C./hour. Rheological Properties Melt Index (MFI) 260 ° C and 5
It was measured in kg according to the standard of ASTM D1238. Peel Force 220 x 110 x from a suitable mold assembled on a NEGR & BOSSI press by recording the values on an oscilloscope model HP54201D using a pressure transducer inserted in the hydraulic circuit of the ejector.
A box having a size of 70 mm and a thickness of 2 mm is
The force required to stretch at a mold temperature of 60 ° C was measured. Examples 1-4 The following ingredients were mixed at room temperature in a rotating drum mixer. -29.5 parts by weight of an impact-resistant vinyl aromatic copolymer consisting of 68.5% by weight of styrene, 9.5% by weight of polybutadiene rubber and 22% by weight of acrylonitrile; -chain of styrene-methylmethacrylate copolymer (1: 1 ratio). PARALOID® EXL consisting of a polybutadiene rubber core with 40% graft polymerization
2600 rubber 8.6 parts by weight; -ENIMONT S.
p. 70.5 parts by weight of SINVET® aromatic polycarbonate manufactured and sold by A and-a release agent of the type and amount shown in Table 1 below. The mixture thus obtained was dried at 100 ° C. for 4 hours and extruded in the degassed state at 260 ° C. in a single-screw extrusion BANDERA TR45 with a length / width ratio of 25. The strand coming out of the extruder was cut to give a granulate, which was dried for 4 hours at 100 ° C. In order to measure various properties, the above-mentioned granular material was pressed with NEGR & BOSS.
Injection molding was carried out in an IV 17-110FA at 260-270 ° C. to obtain a test piece having a size meeting the specifications. The properties measured by the test pieces thus obtained are shown in Table 1 below. * Comparative Example Example 5 The following composition was produced by the method of Example 1. AKZO Trigonox® as initiator
Bulk polymerization in the presence of 25B50 gave styrene 65
Vinyl aromatic copolymer 4 consisting of 10% by weight, 11% by weight of polybutadiene rubber and 24% by weight of acrylonitrile
0.2 parts by weight; -ENIMONT S. p. Aromatic Polycarbonate SINVET® manufactured and sold by A.
59.8 parts by weight; -rubber of example 1 PARALOID® EXL
2600, 8.6 parts by weight; 1 part by weight of a mixture composed of glycerol monostearate and pentaerythritol tetrastearate in a weight ratio of 1. The mechanical, thermal and rheological properties and peel force were measured by the method of Example 1 and the following results were obtained. IZOD: 580 J / m VICAT: 121 ° C. Melt index: 16 g / 10 ′ Peel force: 2.3 KN Examples 6 to 10 The following components were mixed at room temperature in a rotary drum mixer. -A high impact vinyl aromatic copolymer (A), the amount of which is shown in Table 2 below. It is composed of 67.5% by weight of styrene, 10.5% by weight of polybutadiene rubber, and 22% by weight of acrylonitrile. -SI for ENICEM manufacturing and sales, the amount of which is shown in Table 2 below.
NVET (registered trademark) aromatic polycarbonate (B);-Release agent (C) whose type and amount are shown in Table 2 below; -Bis- (2,4-di-ter) whose amount is shown in Table 2 below
t, butyl-phenyl) -pentaerythritol-dihofphite (ULTRANOX® 626)
(D);-PARALOID (R) E whose amount is shown in Table 2 below.
XL2600 rubber (E). The chains of styrene-methylmethacrylate copolymer (1: 1 ratio) consist of 60% by weight of polybutadiene rubber core with 40% graft-polymerized chains. The mixture thus obtained is dried for 4 hours at 100 ° C. and then degassed to 2 °
Extruded with a single screw extruder BANDERA TR45 at a temperature of 60 ° C. and a length to width ratio of 25. The strand coming out of the extruder was cut to give a granulate, which was dried for 4 hours at 100 ° C. To measure various properties, press a part of the granular material, press NEGR &
260-270 in BOSSI V 17-110 FA
Injection molding was performed at 0 ° C. to obtain a test piece having a size meeting the specifications. The other part of the granular material is the same as NEGRI &
BOSSI V 17-110FA 300 ~ in the press
Injection molded at a temperature of 310 ° C. Various properties measured by using the test pieces thus obtained are shown in Table 3 below.
Shown in.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 27/06 LEN 9166-4J 33/08 LJA 7921-4J 51/04 LKY 7142-4J 67/00 LNZ 8933-4J 69/00 LPP 9363-4J 75/04 NFX 8620-4J (72) Inventor Francesco Mori Italy 37122 Verona Piazza Simoni 31 (72) Inventor Dario Gidoni Italy 46020 Mantova Gonzaga Via Vente Simocinto Apple 1

Claims (23)

[Claims] 1. A high impact vinyl aromatic copolymer having improved release characteristics, comprising: (A) an ethylenically unsaturated nitrile, a vinyl aromatic monomer and a rubber;
(B) Engineering polymer; (C) (1) 1
An ester of a fatty acid having 6 to 18 carbon atoms with glycerin, and (2) a saturated aliphatic monocarboxylic acid having 10 to 20 carbon atoms or the above monocarboxylic acid and 10
A release agent constituted by a synergistic mixture of an ester of a mixture with a polycarboxylic acid having 20 to 20 carbon atoms and an aliphatic alcohol having 4 to 6 hydroxy groups,
Effective amount; (D) Bis (alkyl-phenyl) pentaerythritol diphosphite, component (A) + (B) 10
0-3 parts by weight with respect to 0 parts by weight; and optionally (E)
A molding thermoplastic composition comprising a graft polymer composed of an elastomer core having a secondary glass transition temperature of less than 10 ° C. and having vinyl monomer chains grafted thereon. 2. A diester (1) of a synergistic mixture (C).
Molding thermoplastic composition according to claim 1, wherein the weight ratio between (1) and (2) is from 4: 1 to 1: 4, preferably about 1: 1. 3. An ester (1) of a (C ₁₆ -C ₁₈ ) fatty acid and glycerin has the following properties: Saponification number 155-175 Iodine number 1-2 Monoester content 40-99% by weight Melting point 55-65 ° C. Free The thermoplastic composition for molding according to claim 1 or 2, which is a biodegradable product having a nonionic polar property and having 1 to 6% by weight of glycerin and 0.1 to 0.5% by weight of water. 4. A saturated aliphatic monocarboxylic acid whose ester (2) of the synergistic mixture (C) has 10 to 20 carbon atoms or a polycarboxylic acid having 10 to 20 carbon atoms with said monocarboxylic acid. An alcohol having 4 OH groups and 4 to 16 and preferably 4 to 8 carbon atoms; 5 OH groups and 5 to 18
Alcohols, preferably 5-10 carbon atoms; 6 OH groups and 6-18, preferably 6-12
The molding thermoplastic composition according to any one of claims 1 to 3, which is obtained from an alcohol having one carbon atom and an aliphatic alcohol selected from the group consisting of: 5. The ester (2) of the synergistic mixture (C) completely esterifies the 4-6 OH groups of the alcohol with one or more (C ₁₀ -C ₂₀ ) carboxylic acids. The thermoplastic composition for molding according to any one of claims 1 to 4, which is obtained by. 6. The molding thermoplastic composition according to claim 1, wherein the (C ₁₀ -C ₂₀ ) carboxylic acid is stearic acid or palmitic acid. 7. The amount of the release agent (C) is the amount of the components (A) + (B).
0.01 to 3 parts by weight per 100 parts, preferably 0.1.
The thermoplastic composition for molding according to any one of claims 1 to 6, which is contained in an amount of 5 to 2 parts by weight. 8. Bis (alkyl-phenyl) pentaerythritol diphosphite is represented by the general formula: (Wherein, R ₄ and R ₅ may be equal to or different from each other, alkyl groups are having 1 to 10 carbon atoms) with the molding according to any one of claims 1 to 7 Thermoplastic composition. 9. Bis (alkyl-phenyl) pentaerythritol diphosphite is represented by the general formula: 9. The molding thermoplastic composition according to claim 8, having the formula: wherein R ₅ is an alkyl group having 1 to 6 carbon atoms. 10. Bis (alkyl-phenyl) pentaerythritol diphosphite is bis (2,4-di-t-).
The thermoplastic composition for molding according to claim 8 or 9, which is butyl-phenyl) pentaerythritol diphosphite. 11. The amount of bis (alkyl-phenyl) pentaerythritol diphosphite is (A) + (B) 10.
The thermoplastic composition according to claim 1, which is contained in an amount of 0.01 to 3 parts by weight with respect to 0 parts by weight. 12. The amount of bis (alkyl-phenyl) pentaerythritol diphosphite is (A) + (B) 10.
The molding thermoplastic composition according to claim 11, which is contained in an amount of 0.05 to 1 part by weight based on 0 part by weight. 13. A high-impact vinyl aromatic copolymer (A) comprising component A: 2-35 wt% ethylenically unsaturated nitrile, 20 wt% or more diene rubber, preferably 2-15 wt%, and a vinyl aromatic monomer. 1);-ethylenically unsaturated nitrile 2 to 35% by weight, diene rubber 20
Impact-resistant vinyl aromatic copolymers containing from 65% by weight to 65% by weight and vinyl aromatic monomers; and-35% by weight of ethylenically unsaturated nitriles, 5-50% by weight of olefin elastomers, preferably 15-30% by weight. %,
And an impact-resistant styrene copolymer (A.2) comprising 93 to 15% by weight, preferably 83 to 35% by weight of vinylaromatic monomer; the sum of these monomers being equal to 100. The thermoplastic composition for molding according to any one of 1. 14. The molding thermoplastic composition according to any one of claims 1 to 13, wherein the ethylenically unsaturated nitrile is acrylonitol. 15. The molding thermoplastic composition according to claim 1, wherein the vinyl aromatic monomer is styrene. 16. The diene rubber is polybutadiene,
The olifine elastomer has a Mooney viscosity (ML-4) of 30 to 90 at 100 ° C. and 5 or more, preferably 10 to 4
The molding thermoplastic composition according to claim 13, which is an ethylene-propylene-non-conjugated diene rubber terpolymer having an iodine value of 0. 17. The thermoplastic composition for molding according to any one of claims 1 to 16, wherein the engineering polymer (B) is a polycarbonate. 18. The vinyl aromatic polymer (A) comprises 10 to 10.
90% by weight, preferably 20-80% by weight, correspondingly 90-10% by weight, preferably 80-20% by weight, of the engineering polymer (B).
18. The thermoplastic composition for molding according to any one of 17. 19. The amount of graft polymer (E) is 0 to 30 parts by weight with respect to 100 parts by weight of formulation (A) + (B),
The thermoplastic composition for molding according to any one of claims 1 to 18, which is preferably contained in an amount of 2 to 15 parts by weight. 20. The core-shell type wherein the graft polymer (E) comprises 25 to 95% by weight of an elastomer core and 75 to 5% by weight of a graft vinyl monomer chain.
20. The thermoplastic composition for molding according to any one of claims 1 to 19. 21. The core has a second-order transition temperature of less than 10 ° C. and is selected from polybutadiene, copolymers of butadiene and styrene, isoprene and / or acrylonitrile (butadiene content higher than 40 mol%) and acrylic rubber. The thermoplastic composition for molding according to claim 20. 22. The molding thermoplastic according to claim 20 or 21, wherein the vinyl monomer is selected from a derivative of acrylic acid, a derivative of methacrylic acid, a vinyl aromatic compound, a vinyl cyanide compound, a polyfunctional derivative and a mixture thereof. Composition. 23. A formulation composed of 20-60% by weight of vinyl aromatic copolymer (A.1) or (A.2) and 80-40% by weight of aromatic polycarbonate, and bis with respect to 100 parts by weight of said formulation. 23. 1 to 22 parts by weight of (alkyl-phenyl) diphosphite (D), 0.5 to 2 parts by weight of the releasing synergistic mixture (C) and 0 to 15 parts of graft polymer (E). The thermoplastic composition for molding according to any one of 1.