JPH01500599A - Glycidyl methacrylate grafted EPDM modifier in fiber reinforced polyester compositions - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Glycidyl methacrylate grafted EP in fiber reinforced polyester compositions DM Modifier This invention relates to impact modified reinforced thermoplastic molding compositions and more particularly Fiber-reinforced thermoplastic polyester, copolyester and polyblend molding compositions Glycidyl methacrylate or glycidyl acrylate grafted E P D Regarding k1 impact modifier.

Background of the invention High molecular weight linear polyester of glycol and terephthalic acid or isophthalic acid and Copolyesters have been used for many years. These are, among other things, U.S. Pat. No. 2,465,31 to Winrield et al. No. 9 and Pengi 1ly's specifications No. 3,047,539. It is described in. These patent specifications state that polyester is used in film and fiber forms. It is disclosed that it is particularly advantageous as a material.

By controlling molecular weight, using nucleating agents and developing a two-step molding cycle, poly( (ethylene terephthalate), or PET, is an important component of injection moldable compositions. became. Also, due to its extremely fast crystallization from the melt, poly(1,4-butylene) (ethylene terephthalate), or PBT, has become particularly useful as a component of the above compositions. ing. Processed products molded from the above polyester resin are compared to other thermoplastic resins. All exhibit a high degree of surface hardness and abrasion resistance, high gloss and low surface friction.

Furthermore, poly(1,4-butylene terephthalate) is a poly(ethylene terephthalate). It is much easier to use in injection molding than terephthalate). For example, high poly(1) to produce highly crystalline, dimensionally stable moldings in short cycle times. , 4-butylene terephthalate) at a low mold temperature of approximately 30°C to 60°C. can do. Due to the high crystallization rate even at low temperatures, molded products can be easily removed from the mold. I don't face any difficulty in getting it out. In addition, poly(1,4-butylene terephthalate) g) The dimensional stability of injection molded products is It is very good even at temperatures near or considerably higher than the transition temperature.

However, the impact resistance of unmodified polyesters is relatively low at room temperature and below. follow impact resistance at relatively high and relatively low ambient temperatures in many applications. It is desired to obtain polyester. However, the elastic modulus, yield point and breaking point Other mechanical properties such as tensile strength are not impaired or are acceptable. It should be impaired only within the range.

In many places, other polymers, including interpolymers and copolymers, are added. It is recommended to improve the impact resistance of polyester by. Toriwa Thermoplastic linear crystalline polymers containing poly(1,4-butylene terephthalate) The impact strength of the polyester is ethylene-propylene-nonconjugated diene rubbery terpolymer. It has been improved by mixing EPDM. For example, EPDM Coran et al., U.S. Patent No. 4.141.863 and 4,290°927 of Tanaka et al. Although PBT polyester compositions can be impact modified as shown in Compositions often suffer from "incompatibility" leading to stripes or delamination in molded or extruded products. be done.

European patent application m0 of Hepp () Iepp published on July 24, 1985 No. 149 No. 192 specifies that polyester, copolyester or block copolyester Epoxidized with thermoplastic resins such as esters and m-chloroperoxybenzoic acid, etc. A thermoplastic molding composition comprising EPDM is disclosed. fibrous gala Reinforcing materials such as steel can make up up to about 50% by weight of the composition, but only The examples shown in Tables 1.2 and 3 of Shiko's cited document have good impact strength and tolerance. It does not indicate possible knit-line property combinations.

Siegel, U.S. Pat. No. 3,769,260, describes the functionalization of Rubber has been shown to improve the impact strength of polyester, and dispersed A range of diameters from 0.02 to 20 microns is suggested for the rubber phase particles. glass No. 3,769,260 claims that fibers are used as fillers. However, the unnotched Izot impact strength is not particularly high.

Epstein (U.S. Pat. No. 4,172.859) discloses the use of random copolymers containing various polar monomers, and Up to % of glass fibers are claimed as fibrous reinforcement. he , and other thermoplastic polyesters including PBT and PET. Graphs with various polar monomers such as glycidyl methacrylate (GMA) It refers to the use of regulated substances. However, this patent specification is EPDM-g - Critical condition 1 for the function of G M A substance as a PBT-based impact modifier does not discuss, and therefore does not recognize, two factors. This patent specification is Non-reactive poles such as maleic anhydride or n-vinylpyrrolidone as raft monomers do not understand the advantages of reactive glycidyl (meth)acrylates over reactive monomers. .

US Patent Application Box 69 for Oliver (011ver) filed January 11, 1985 No. 0,613 and Pratt et al., filed January 16, 1987. In the disclosure of each specification of No. 004.089 of glycidyl methacrylate cGMA > grafted EPDM impact modifier taught. In specific examples, materials with high impact strength are described. ing. The best results are obtained with a GMA content of 2% by weight or more in the modifier. Ru. However, in the above disclosure, the impact-modifying composition is It is suggested or suggested that it can or even should be reinforced with reinforcement. Not yet.

Surprisingly, fibrous reinforcing materials such as glass fiber can be used as glycidyl methacrylate. Grafted EPDM (EPDM-g-GMA) thermoplastic containing impact modifier be able to mix into plastic polyester compositions, and with such compositions glass fibers; is the tensile strength, and the tensile and flexural modulus conveniently indicates an increase in the impact strength. was discovered. For example, PBT or PET is Impact strength when combined with bl A, glass fibers, and optional nucleating agent and heat resistance are both improved.

Summary of the invention According to the invention, (a) a high molecular weight thermoplastic polyester resin; (b) a rubbery polymer with an effective impact-modifying amount; rimmer and (c) an effective amount of fibrous reinforcement. 2% by weight or less based on the terpolymer as the rubbery polymer. Glycidyl methacrylate, glycidyl acrylate or mixture thereof Or, in addition, alkyl methacrylate having 1 to 18 carbon atoms. or EP D grafted with acrylates or in combination with acrylates or mixtures thereof Improved Impact Modified Reinforced Thermoplastic Compositions Using Fv1 Terpolymer is provided.

A preferred embodiment of the present invention is a composition comprising 100 parts by weight of a combination of (a), (b) and (c). Poly(1,4- butylene terephthalate), and component (b) is about 1.5 to about 351ij1 and component (c) comprises glass fibers in an amount of about 5 to about 45 parts by weight. A composition as defined above.

It is also preferred that component (a) consists of poly(ethylene terephthalate). , component (b) is grafted with glycidyl methacrylate and EPDM. The ratio of the former to the latter is from 1:1 to about 10:1 Component (C) consists of glass fibers, and furthermore ( d) A composition as defined above comprising an effective amount of a nucleating agent.

Details of the invention The high molecular weight linear polyester used as component (a) in carrying out the above description is , polymeric glycol esters of terephthalic acid and isophthalic acid. this are commercially available or prepared by glycol phthalates, for example. method by alcoholysis followed by polymerization, glycol and free acid or its by known methods such as by heating with halide derivatives and similar methods. It can be manufactured by These are U.S. Pat. Nos. 2,465,319 and 3,047. ．． No. 539, each specification, and others.

The glycol portion of the polyester may contain from 2 to 10 carbon atoms, but is preferred. or contains 2 to 4 carbon atoms in the form of methylene chains.

Suitable polyesters have the general formula: (In the formula, n is an integer from 2 to 4) High molecular weight polymeric glycol terephthalate or isophthalate having repeating units of tallate, and terephthalate containing up to about 30 mole percent isophthalic acid units. consisting of mixtures of the aforementioned esters, including copolyesters of isophthalic acid and isophthalic acid. belong to a group.

Particularly suitable polyesters are poly(ethylene terephthalate) and poly(1 , 4-butylene terephthalate).

For example, high molecular weight polyester is 60:40 phenol-tetrachloroethane. at least about 0.7 dl/g measured at 30°C, and preferably At least 0°Btu! /g. at least about 1.0dj2/ At an intrinsic viscosity of g, the toughness of the composition of the present invention is further increased.

The copolyester used in the present invention is preferably terephthalic acid and/or isophthalic acid. linear or branched aliphatic or cyclic glycan acids and/or their reactive derivatives. and one or more glycols, which may be cols.

For example, glycols include ethylene glycol, 2-methyl-1,3-propanedio alcohol, 1,4-butanediol, 1゜5-bentanediol, 1,6-hexane Diol, 1゜9-nonanediol, 1.10-decanediol, neopentyl Glycol, 1,4-cyclohexanediol, 1゜4-cyclohexane dimeta tools, mixtures of any of the above glycols, etc. Mixed aromatic/aliphatic state Examples of suitable aliphatic dicarboxylic acids are speric acid, sebacic acid, azelaic acid. and adipic acid.

The copolyester may be produced by transesterification according to standard methods. Ru. The copolyester preferably contains at least 50% butylene terephthalate. derived from the unit.

The block copolyesters useful in the compositions of this invention preferably have low molecular weight terminal polymers. reactive poly(1,4-butylene terephthalate) and terminal reactive copolyester or with aliphatic polyesters or both, e.g. zinc acetate, manganese acetate. , produced by reaction in the presence of a transesterification catalyst such as a titanium ester. It will be done. Terminal groups can be hydroxyl (including their reactive derivatives), carboxyl, It can consist of carbalkoxy, etc. After starting the mixing, the curve of the chain segment distribution is In order to produce a block copolymer with minimal randomization, the polymerization is carried out at e.g. Performed under standard conditions at 280°C and under high vacuum, e.g. 0.1 to 2ausHg. be exposed. Of course, the result of the reaction of the two terminal reactive groups is an ester bond. these The copolyester described in West German Patent Application Section P2756167.7 It is listed.

The copolyester component of these block copolyesters is the copolyester component described above. may be the terminal reactive segment of the molecule. These copolyesters are optimally The molar concentration of aliphatic glycol and aromatic acid to aliphatic acid is from 1:9 to about 9: 1. Aromatic and aliphatic dibases with a particularly preferred range of about 3=7 to about 723 Derived from a mixture of acids.

The terminally reactive aliphatic polyester component of these block copolyesters is essentially Contains stoichiometric amounts of aliphatic diols and aliphatic dicarboxylic acids.

In addition to its ease of production by well-known methods, the aromatic/aliphatic copolymers Both ester and aliphatic polyesters are commercially available. one of the above substances Source: Hicksville, NY, USA Ruc Chemical Company Ruco Division (Ruc.

Divlslon / Hooker Chea+1cal Company ), designated as Rucoflex.

The block copolyester used in the present invention is preferably a block copolyester from about 95 to about 50 parts by weight of poly(1,4-butylene terephthalate) based on segment). Poly(1,4-butylene terephthalate) block is , preferably phenol, before being incorporated into the block copolyester. - at least 60:40 of tetrachloroethane, measured at 30°C. about 0.1 dI/g, and preferably about 0.1 to about 0. 5cU/g range It has an intrinsic viscosity within the range. The remaining 50 to 5 parts by weight of the copolyester is Consisting of blocks of aromatic/aliphatic copolyesters and/or aliphatic polyesters .

As will be understood by those skilled in the art, poly(1,4-butylene terephthalate) g) The blocks may be linear or based on e.g. terephthalate units. from about 0.05 to about 1 mole percent of at least three ester-forming groups as It may be branched by using a branched component or the like. The branching component is e.g. Polyols such as erythritol, trimethylolpropane, or trimesic acid It can be a polybasic acid compound such as methyl.

In addition, the above homopolymers, copolymers and/or block copolymers or Blends of these derivatives are also useful in the present invention.

Glycidyl ether used in the rubbery polymeric impact modifier (b) in the present invention The stell-grafted terpolymer additive is the well-known E P D M terpolymer additive. It can be produced from any of the mer gums. Preparation of the grafted material used in the present invention EP D useful for construction! lb! Terpolymers are, for example, copolymers φcope ( EpsynO 55 is a registered trademark of Copolymer Corp. are commercially available or can be produced using Ziegler type catalysts. Noriyoshi Typical methods for making EPDM terpolymers have been described, for example, by Gresha et al. U.S. Patent No. 2.933.480 to Tarne et al. y) No. 3,000,866, Guglielmino et al. 3,407.15111 of Gladdln et al. g) described in the specifications of No. 3,093.621 and No. 3.379.701 of ing. These terpolymers are characterized by the absence of unsaturation in the chain or backbone and the Makuuchi unsaturation suspended from polymer chains or within the outer cyclic structure of the main polymer chain Characterized by the presence of a sum site.

For the production of glycidyl ester grafted terpolymers used in the present invention Useful EPDM terpolymers are ethylene, preferably propylene From linear or branched α-olefins having 3 to 16 carbon atoms and non-conjugated diolefins Become. A satisfactory non-containing monomer which can be used as said third monomer in the terpolymer Conjugated dienes include linear dienes such as 1,4-hexane diene, cyclooctadiene, etc. and bridged cyclic dienes such as ethylidene norbornene.

Suitable EP D kl terpolymers have a molecular weight of about 10 to 95, preferably 45 to 95. 70 mole percent ethylene, about 5 to 90, preferably 30 to 55 mole percent -cent polypropylene, and preferably polyunsaturated cross-linked cyclic hydrocarbons or a small amount of a halogenated derivative of, most preferably 5-ethylidene-2-norbornene. Consists of diene monomers. These EPDM terpolymers are approximately 79 g/10 min. Melt Index, Mooney Viscosity of about 78 and Durham Molecular Weight of about 21.600 exists.

The backbone rubber is then grafted with epoxy-functional acrylate or methacrylate. Graft modified by monomer.

Grafting can occur virtually anywhere on the backbone rubber by a variety of reaction mechanisms. However, grafting usually occurs at unreacted unsaturations on the polyene. Therefore, carbon source ethylene, containing at least 2 unsaturated carbon-carbon bonds per 1000 children; It is preferable to use mono-olefin, polyene backbone rubbers and unsaturated skeleton rubber containing more than 20 carbon-carbon double bonds per 1000 Its use provides little additional benefit. In a preferred implementation of the invention is an unsaturated compound containing 4 to 10 carbon-carbon double bonds per 1000 carbon atoms. rubber is used.

The ethylenic unsaturation on the epoxy-functional graft monomer is the unsaturation of the polyene. or graft chains or It needs to be sufficiently reactive to react with the combination of this and the polyene unsaturation. be. The above-mentioned degree of reactivity is suitable for example for epoxy resins of acrylic acid or alkyl acrylic acids. Requires an α-β configuration of ethylenic unsaturation as seen in xy-functional esters Ru.

Free radical initiators, such as dialkyl peroxides, may be used to accelerate the grafting reaction. used for The above initiator is usually 1 to 5 parts per 100 parts by weight of unsaturated rubber. used in amounts ranging from 1 part to 2 parts by weight, and preferably from 1 to 2 weight percent. It will be done.

In the present invention, glycidyl methacrylate ( G　M　A　”).

The grafted chains formed during the grafting process onto the backbone rubber are homopolymers. It is not necessary, nor does it need to be entirely epoxy functional graft monomer. example For example, a combination of two of the above epoxy-functional graft monomers, and any one of them. one or both (1 to 18 carbon atoms are methyl, ethyl, isopropyl, 2- (Can be straight chain or branched chain such as ethylhexyl, decyl, n-octadecyl, etc.) and others. The combination of alkyl having 1 to 18 carbon atoms with acrylate or methacrylate is Available for use. A particularly useful comonomer graft monomer is glycidyl Acrylate and/or glycidyl methacrylate and methyl methacrylate It is a raft monomer.

In the present invention, the gel content of the elastomeric material is greater than about 10% by weight and 80% by weight. It is preferably adjusted during polymerization or during subsequent processing to take a value of less than % by weight. Delicious. If the gel content is too low, the impact strength will be high but the knit-line strength will be low. Become. If the gel content is too high, the impact modifier will be difficult to disperse.

In a particularly convenient analysis according to ASTM D-3616, the gel content is Weight percentage of elastomeric material remaining after extraction in hexane or toluene It is measured by Gel content is an indicator of the degree of crosslinking in elastomeric materials. be. Of course, those skilled in the art are familiar with various methods of adjusting the degree of crosslinking. Therefore, gel content can also be determined by a number of other methods. cross-linked anti- For example, direct bonding between rubber skeletons, epoxy functional groups of epoxy functional groups or Bonding to a rubber backbone or graft chain to a second graft chain or rubber backbone can be a free radical addition of In addition, since crosslinking effectively achieves any of the above reactions, This can also be achieved by the addition of a crosslinking agent. Therefore, how many for gel content adjustment? Any of the manufacturing processes can be adopted. Heat aging can increase gel content. epoxy functionality Increasing the amount of grafting monomer will increase the gel content.

Increasing the amount of polyene monomer in the rubber backbone will increase the gel content. rack Addition of a crosslinking agent will increase the gel content. Grafting monomers with a high tendency to crosslink The use of glycidyl acrylate will increase the gel content, e.g. Remer graft is a homopolymer graft of glycidyl methacrylate or glycidyl methacrylate. Easier to crosslink than copolymer grafts of dilacrylate and methyl methacrylate .

As mentioned above, the gel content of the elastomeric material used in the present invention is approximately 80%. should be in the range of . As already mentioned, cross-linking goes well beyond this level. can also be used, but a high degree of crosslinking reduces the dispersibility of the elastomeric material and may result in non-uniform bring about a mixture. Additionally, such highly localized crosslinks can occur within elastomeric materials. This creates brittle areas in the parts and impairs the properties of the rubber. Crosslinking occurs in elastomeric materials It is clear that it should be uniformly distributed.

In the present invention, the elastomeric material has at least 2 carbon atoms per 1000 carbon atoms. ．． 5 epoxy functional groups, and preferably about 5.0 to 1000 carbon atoms. It is preferred to have an epoxy functionality with an epoxy functionality ranging from to 13.

The epoxy functionality probably reacts in a cross-linking reaction and is exposed after such functionality disappears. Refers to the epoxy moieties remaining in the impact modifier resin. epoxy functional graft single When using GM A or GA as the polymer, the minimum epoxy as shown above is about 1% by weight or more, preferably about 1.5% by weight or more, and Grafting levels of about 2% by weight or greater are optimally used. The upper limit is especially a critical condition. It is possible to use up to 10 to 15% by weight, but even if these amounts are exceeded, No particular advantage is seen.

The grafting reaction involves an unsaturated rubber skeleton present at a concentration of 10 to 30 percent by weight. In a solvent solution containing , for a period of time ranging from 1/2 to 2 hours. Reaction conditions are determined by those skilled in the art. This will vary somewhat depending on the type and amount of catalyst and temperature conditions, as is well known to those skilled in the art. can be done. When bonding a large amount of graft monomer to the backbone rubber, the grafting reaction It has been found to be advantageous to carry out the grafting in the molten state of the skeleton rubber, i.e. in an extruder. I was taken out. This method involves adding backbone rubber, excess graft monomer and Supplying a suitable catalyst, mixing, and reacting the supplied components at high temperatures. This is done more easily.

Fibrous reinforcing materials useful as component (C) in the practice of this invention include glass, graphite, Metals such as wollastonite, carbon, aluminum, iron, nickel, stainless steel, etc. , titanates such as titanate whiskers, quartz, mixtures thereof, etc. , including but not limited to a range of substances.

The only requirement is that at least an amount of reinforcement be present, but generally polyester Stell component (a) is about 30 to about 80, preferably about 40 to about 7 of the total composition. 0 parts by weight and rubbery polymer (b) comprises about 1.5 to about 35, preferably about 5 to about 25 weight percent, and reinforcement (c) comprises about 1 to about 80 weight percent. It constitutes a quantity part.

Particularly suitable reinforcing fillers are those made of glass and are relatively soda-containing. Fibrous glass filaments made of free lime-aluminum borosilicate glass It is preferable to use This is known as "E" glass. but , when electrical properties are not very important, e.g. known as rCJ glass. Other glasses may also be used, such as low soda glass. G-as a filament Particular mention is made of the known glass filaments. The filament is e.g. Manufactured by standard methods such as steam or air blowing, flame blowing and mechanical stretching. P Filaments suitable for plastic reinforcement are produced by mechanical drawing. filamen The diameter is within the range of approximately 0.00012 to 0.00075 inches, but This is not a critical condition for the invention.

the length of the glass filaments and whether they are bundled into fibers; whether the fibers are bound into yarn, rope or roving, or woven into mats; Whether or not this is the case is not a critical condition for the present invention. However, the present invention When preparing the composition, the length is about 1/8 inch to about 1 inch, preferably 1/8 inch long. It is advantageous to use filamentary glass in the form of chopped strands of 4 or less. Ru.

On the other hand, in articles molded from said compositions, considerable fragmentation occurs during compounding. Therefore, shorter lengths also occur. However, the filament length is about 0.00000 Thermoplastic injection molded products ranging from 5 inches to 0.125 (1/8) inches This is desirable because it provides the best properties.

Generally, the best properties are achieved when dimensioned filamentary glass reinforcement from about 1 to about 80% by weight based on the combined weight of the polyester and the polyester, and preferably or about 5 to about 50% by weight. Particularly preferably, The glass constitutes about 5 to about 40% by weight based on the combined weight of the glass and the resin. do. Generally, up to about 60% glass by weight can cause flow problems for direct molding applications. can exist without However, it can also be used in significantly larger amounts, e.g. up to 70-80% by weight. It is also useful to prepare compositions containing glasses of These concentrates are then Non-glass-reinforced resin blocks to give the desired glass content at lower values. Blended to order with Lend.

The elastomeric material is in the continuous phase of a thermoplastic matrix resin or blend. in a thermoplastic polymer melt to form discrete particles of rubbery polymer. be physically dispersed. At least an impact strength improving amount of the elastomeric material is Dispersed in Trix resin. Generally, this means that the elastomeric material Based on the total thermoplastic content including elastomeric material of the shaped composition, at least 1.5 weight percent, preferably 3.5 to 80 weight percent, optimally 1.5 to 80 weight percent. It is necessary to make up 0 to 55 weight percent. The composition range is enhanced Ideal for manufacturing rigid plastic articles, but acceptable molding materials are It is clear that mixtures with rubber contents considerably higher than this range can also be produced. That's it. Molding compounds of the thermoplastic elastomer type have an elastomer content of 5 Mixtures made with more than 5 weight percent and with a phase inversion composition or more material, i.e. the thermoplastic resin phase is semicontinuous or discontinuous within the rubbery polymer matrix. Mixtures that are interdispersed with each other can produce flexible molded articles with excellent properties. can be used to 80 weight percent elastomer is a typical upper limit. be. The formulation of rubber, thermoplastic and reinforcing material can be achieved, for example, by simple melt blending or by dry mixing and pressing at a temperature appropriate for the given thermoplastic matrix. This is done using standard methods. The resulting mixture is then molded into a thermoplastic of specific dimensions. Formed into plastic resin products or further extruded into film or sheet products It will be done.

Extrusion of the resin melt is important for the final properties of molded parts containing elastomeric materials. It is important that there is sufficient mixing. Here, inside the extruder Several reactions have been taught or suggested to occur and, of course, these reactions This is achieved through in-flight mixing and residence time.

Therefore, sufficient mixing of the polymer melt is suggested and, depending on the equipment used, may require two consecutive extrusions of the melt.

As previously described, in preferred compositions the glycidyl ester is grafted with The particle size of the rubber particles is at least 60% by weight of the particles, preferably 70% by weight of the particles. - cent or more is selected on the condition that the diameter exceeds 1 micron. This kind of composition The product combines optimal notched izot impact strength and knit line strength, and For example, only about 50 weight percent of the particles are larger than 1 micron in diameter. The impact strength and knit-line strength are far superior to those obtained with the composition. Ru. Particle size is measured by any method known in the art, but especially An advantageous method is to use a computer to measure photomicrographs of scanning electron microscopy (SEM) images. using a grain size analyzer.

Compounding can be performed using conventional equipment. For example, thermoplastic polyester After pre-drying the fat, for example at 125°C for 4 hours, the screw used will ensure melting. Polyester, complementary Strength and additive components are provided. On the other hand, for example, the 28-year Union Freida A twin-screw extruder, such as a Werner Pf'1eidere machine, has a feed port. Resins and additives can be supplied from. In either case, the generally preferred machine temperature is The degree is approximately 450 to 520 degrees.

The formulated composition is extruded and formulated by standard methods, e.g. It is cut into molded components such as lettuce.

The compositions of the present invention can be prepared using any equipment conventionally used for thermoplastic compositions. It can also be molded. For example, poly(1,4-butylene terephthalate) , for example, in an injection molding machine such as a Newbury type. At a conventional cylinder temperature, such as about 480 to 500 degrees below, and for example 150"F. Good results are obtained at conventional mold temperatures such as . On the other hand, poly(ethylene terephthalate) (G)), due to the lack of uniformity of crystallization from the inside to the outside of thick products, Less conventional but well known methods may be used. for example, LIOH, sodium stearate, graphite or ZnO included in component (d) Actually, M! Nucleating agents such as metal oxides such as 10 and standards below about 150 to 230 A mold temperature is used.

The composition includes a nucleating agent, a mold release agent, a glidant, a coloring agent, a coupling agent and a stabilizer. Other additives known in the art, including but not limited to fixing agents, etc. It should be understood that agents may be included. Elastomer-containing molding composition of the present invention The product can be used as a molded pellet and contains pigments, dyes, stabilizers, plasticizers, etc. obtain. It is easy to determine which one is needed and which one is suitable for a particular application. You can

Description of preferred embodiments The following examples illustrate the preferred invention. In any sense, the claims The scope should not be construed as limited by these.

Example 1 An impact-modified glass-reinforced PBT composition is prepared and suitable workpieces are constructed for testing. shaped. grafted with 4.5% glycidyl methacrylate and 21% Gel content of EPD 1 (EPDM-g-GMA) was used as an impact modifier. It was. This modifier is described in U.S. Patent Application No. 337-1997 (8CT-4294). It can be produced by the method of Example 9(a) of the specification, for example. Typically, 100 Parts by weight of skeleton rubber, registered trademark Nibsyn 55 resin, EPDM rubber [23R5V, charcoal 9 carbon-carbon double bonds per 1000 atoms, polyene; 5-ethylidene -2-Norbornene 8% by weight, ethylene/propylene ratio -2.1, Mooney viscosity & -50, Copolymer Chemical and Rubber Corporation (Copo lymer Chemical and Rubber Corporation n)], 0. 1 part by weight of hindered phenol antioxidant; I1m quotient tl il tf) -/') s (IRGANOX O) 1076 [Raba Ga Ciba-Gelgy Corp.

ration)], 7. 4 parts by weight of glycidyl methacrylate and 0.5 parts by weight 6 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy); The Sun initiator was passed through a Unilunar Friderer WP57 twin screw extruder.

A zone temperature of 200° C. and a screw speed of 150 revolutions/min were used. appear The water-cooled strands of elastomeric material were chopped into pellets. with PBT The blend was rotary mixed and a Brodex (P rodex) was extruded once through a 2+ inch extruder. This substance is then dried and molded on a 75 ton Cincinnati injection molding machine. Molded. The composition and results are shown in Table 1.

Table 1 Glass reinforced thermal τ type composition PBT/EPDM-EPDM-g-GMA 15 Glass fiber, 178 inch shredded strands, 30 properties Izot with notch 4.1 (feet bond/inch) Song: Bumodulus (p s i) 750,000 tensile strength p s i) 14.200 Tensile modulus (psi) 809,000 The above result is , EP　D　Nl　-g　-G　NI　A modified PBT composition is Demonstrates excellent mechanical properties such as tensile strength, tensile modulus, and impact strength. It is shown that.

The molded article prepared in Example 1 was examined with a scanning electron microscope (SEPwl). . In the EP D kl-g-G M A impact modified glass reinforced composition, The fibers show no separation from the matrix and the exposed fibers have an extremely rough surface. , indicating a high degree of adhesion of the matrix to the glass.

Examples 2 to 5 A glass reinforced impact modified PET composition was prepared according to the present invention. impact modifier and Then, the play between 2596PET and 75%EPDM-g-GMA The blended combination was added. The composition and results are shown in Table 2.

Table 2 Note) a X5202A, Rohm & Haas Company (Rohc & l 1ass Company), b 75% E P D M -g -G NI A/25% PET.

C1/8 inch shredded strand, d Sodium stearate.

The above results indicate that high impact strength articles were obtained from 30% glass-reinforced nucleator-added PET compositions. It is shown that it can be produced by adding EP　D　M　-g　-G　MA　to are doing.

Examples 6 to 15 In Examples 6 to 15 below, EP D M - g - GM A and G The lath content has been changed. Except for the use of a Buss kneader for extrusion, A PBT composition was blended according to the method of Example 1.゛Products suitable for testing are completed. shaped.

The composition and results are shown in Table 3.

Table 3 Note) a Registered trademark Valox [F] 315, General Electric Kanbanii, b 25PBT-75EPDM-g-GMA added as concentrate, C1/8 inch shredded strand, 1 Registered trademark Barox 295, General Electric Company The above results demonstrate that compositions with high impact strength and good heat resistance are produced according to the present invention. It shows that you can get.

Examples 16 to 18 The impact modified glass reinforced compositions of PBT and PBT/PET are as shown in Example 1. Blended according to law. Workpieces suitable for testing were prepared. Composition used and the data obtained are shown in Table 4.

Table 4 Note) 1 Registered trademark Barox 315, General Electric Company, 2 Registered trademark Barox 295, General Electric Company, a See footnote to Table 3, b 1/8 inch shredded strands.

The above results demonstrate that reinforced impact modified polyester compositions can be made according to the present invention. It shows.

Many variations will occur to those skilled in the art in light of the foregoing detailed description. cormorant. For example, as component (a) poly(1,4-butylene terephthalate) or Instead of using ethylene terephthalate, e.g. and/or aromatic dicarboxylic acids and one or more linear or branched aliphatic or includes random or block copolyesters derived from cycloaliphatic glycols. Other polyester resins may be used, such as copolyesters containing. injection molding cost Alternatively, blow molding, including injection blow molding, may be used. glycidyl methacrylate Instead of a mixture of glycidyl methacrylate and methyl methacrylate, Mixture of lycidyl acrylate and methyl methacrylate, glycidyl methacrylate mixture of ester and octadecyl methacrylate, or glycidyl acrylate alone Germany may be used. In addition, nucleating agents, mold release agents, glidants, colorants, flame retardants, and carbon including but not limited to coupling agents and stabilizing agents. Other additives known to those skilled in the art may be added to the impact modifying compositions of the present invention in conventional amounts. Ru.

All such obvious variations are within the full intended scope of the claims. Ru.

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Claims (23)

[Claims] (1) (a) high molecular weight thermoplastic polyester resin; (b) effective impact-modifying amount of rubber; (c) an effective amount of a fibrous reinforcement; 2% by weight or less based on the terpolymer as the rubbery polymer. Glycidyl methacrylate, glycidyl acrylate or mixture thereof Improved impact modification using EPDM terpolymer grafted with Stringed thermoplastic composition. (2) The fibrous reinforcement (c) is glass, metal, ceramic, silicate, quartz and charcoal. The composition of claim 1, wherein the composition is selected from the group consisting of: (3) The composition according to claim 1, wherein the fibrous reinforcing material (c) is glass. (4) The grafted EPDM terpolymer contains about 45 to 70 mole percent ethyl about 30 to 55 mole percent propylene and a small amount of 5-ethylidene- A composition according to claim 1, which is derived from 2-norbornene. (5) EPDM-glycidyl ester grafted terpolymer bases the entire composition. The composition of claim 1, wherein the composition is present in an amount of about 1.5 to 35 weight percent. . (6) The grafted EPDM terpolymer is present in the entire composition, i.e. (a), (b) and of claim 1, present in an amount of about 5 to 25 weight percent based on (c). Composition. (7) High molecular weight thermoplastic polyester resin (a) is poly(ethylene terephthalate) g), poly(1,4-butylene terephthalate), copolyester or these A composition according to claim 1 selected from the group consisting of all combinations. (8) Thermoplastic polyester resin (a) is poly(1,4-butylene terephthalate) 8. The composition according to claim 7, which is (9) Thermoplastic polyester resin (a) is poly(ethylene terephthalate). 8. The composition according to claim 7. (10) Thermoplastic polyester resin (a) contains one or more aliphatic and/or is an aromatic dicarboxylic acid and one or more linear or branched aliphatic or cycloaliphatic groups. 8. The composition of claim 7, which is a copolyester derived from Recall. (11) The composition according to claim 10, wherein the copolyester is a random copolyester. thing. (12) The composition according to claim 10, wherein the copolyester is a block copolyester. thing. (13) Thermoplastic polyester resin (a) is poly(ethylene terephthalate) Claim 7 which is a polyblend with poly(1,4-butylene terephthalate). Composition of. (14) Based on the entire composition of 100 parts by weight of the combination of (a), (b) and (c). Component (a) is present in an amount of about 30 to about 80 parts by weight of poly(1,4-butylene tereph). component (b) constitutes about 1.5 to about 35 parts by weight, and The set of claim 1, wherein component (c) comprises glass fiber in an amount of about 5 to about 45 parts by weight. A product. (15) Component (a) consists of poly(ethylene terephthalate) and component (b) EPDM and poly(ethylene terephthalate) grafted with glycidyl methacrylate or a pre-blend in which the ratio of the former to the latter (rate) is from 1:1 to about 10:1. Component (c) consists of glass fiber, and other components effective as (d) A composition according to claim 1, comprising an amount of a nucleating agent. (16) Based on the total weight of 100 parts of the combination of (a), (b), (c) and (d). Component (a) constitutes about 30 to about 80 parts by weight and component (b) constitutes about 1.5 parts by weight. component (c) constitutes an amount of from about 5 to about 45 parts by weight; and component (d) constitutes an amount of about 0.5 to about 5 parts by weight. Composition of. (17) (a) high molecular weight thermoplastic polyester resin; (b) effective impact modification amount; a rubbery polymer and (c) an effective amount of a fibrous reinforcement. In a method for producing a reinforced impact-modified thermoplastic molding composition comprising blending , The rubbery polymer contains 2% by weight or more of rubber based on the terpolymer. Only lycidyl methacrylate, glycidyl acrylate or a mixture thereof, Or in addition, methacrylate or acrylate of alkyl having 1 to 18 carbon atoms. EPDM terpolymers grafted in combination with rylates or mixtures thereof and the impact modifier has a gel content in the range of about 10 to about 80% by weight. The above manufacturing method. (18) The fibrous reinforcement (c) is glass, metal, ceramic, silicate, quartz and 18. The method according to claim 17, wherein the carbon is selected from the group consisting of carbon. (19) High molecular weight thermoplastic polyester resin (a) is poly(ethylene terephthalate) ), poly(1,4-butylene terephthalate), copolyester or these 18. The method according to claim 17, wherein the method is selected from the group consisting of all combinations of. (20) High molecular weight thermoplastic polyester is poly(1,4-butylene terephthalate) 20. The manufacturing method according to claim 19, which is g). (21) The high molecular weight thermoplastic polyester is poly(ethylene terephthalate). The manufacturing method according to claim 19. (22) The manufacturing method according to claim 17, wherein the reinforcing material is made of glass fiber. (23) A manufactured article thermoformed from the impact-modified thermoplastic composition of claim 1.