CA1130945A - Reinforced polybutylene therephthalate molding composition - Google Patents
Reinforced polybutylene therephthalate molding compositionInfo
- Publication number
- CA1130945A CA1130945A CA332,375A CA332375A CA1130945A CA 1130945 A CA1130945 A CA 1130945A CA 332375 A CA332375 A CA 332375A CA 1130945 A CA1130945 A CA 1130945A
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- Prior art keywords
- molding composition
- monomer
- molded article
- injection molded
- composition according
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/40—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
Abstract
ABSTRACT OF THE DISICLOSURE
Polybutylene terephthalate molding composition containing thermally stable reinforcing fibers such as glass fibers, mica and a multiphase composite polymer. The multiphase polymer has a first elastomeric phase polymerized from a monomer system including C1 - C6 alkyl acrylate as well as crosslinking and graftlinking monomers and has a final rigid thermoplastic phase polymerized in the presence of the elastomeric phase.
Polybutylene terephthalate molding composition containing thermally stable reinforcing fibers such as glass fibers, mica and a multiphase composite polymer. The multiphase polymer has a first elastomeric phase polymerized from a monomer system including C1 - C6 alkyl acrylate as well as crosslinking and graftlinking monomers and has a final rigid thermoplastic phase polymerized in the presence of the elastomeric phase.
Description
1~3~9~`~S
BACKGROUND OF THE INVENTION
. ~
Polybutylene terephthalate (PBT) reinforced with thermally stable reinforcing fibers such as glass fibers is well known as a molding resin and is described in numerous patents and publications including for instance United States 3,814,725, United States 3,814,786 and United States 3,624,024.
Fiber reinforcement generally improves ~he tensile strength, flexural strength, flexural modulus and heat distortion temperature of the molding composition. However, moldings, especially injection moldings of large fiber glass reinforced articles of PBT, nylon and other semicrystalline thermo-plastics tend to display distortion or warping whi]e glass fiber reinforced amorphous thermoplastic compounds do not present such problems. It is believed that strains resulting from the different degrees of volumetric contraction parallel to and transverse to the direction of plastic melt flow into the mold during the cooling of molded articles are responsible for such warping. Orientation of the glass fibers parallel to the direction of melt flow during molding produces this directional difference in volumetric contraction. The warping is thus believed due to the presence of the very reinforcing fibers which contribute to the enhanced physical characteristics of the finished product. It is known that addition of mica to fiberglass reinforced PBT reduces warping.
Unfortunately, the mica also greatly reduces impact strength.
, ., e~
Various impact modifiers are also known which improve ~he impact strength of molded PBT compositions. Some of these are described for instance in United States patents 4,096,202 and 4,034,013. It is generally believed and unfortunately true, that some modifiers which improve impact characteristics of PBT molding compositions, especially fiber reinforced compositions, also tend to increase the warping characteTistics of the compo-sitions.
Therefore, this invention seeks to provide an improved fiber glass reinforced PBT molding composition and method for producing same as well as molded articles of such composition. As compared with known prior art compositions, the molded compositions of the invention have an especially desirable combination of properties including reduced warpage and improvecl impact strength.
Improved polyester tnolding compositions of the invention consist essentially of at least about 40 wt% PBT having an intrinsic viscosity between about 0.5 and about 2.0 deciliters per gram ~dl/g). Such molding compositions also include:
(a) between about 3 and about 50 wt% based on total molding composition of thermally stable reinforcing fibers having diameters between about 5 and about 20 microns and aspect ratios of at least about 5;
~, ~
(b) between about 1 and about 40 wt% based on total molding composition of phlogophite mica flake having an average particle size between about 40 and about 325 mesh ~nd with at least about 90% of such mica having particle si es between about 40 and about 200 mesh; and (c) between abou~ 5 and about 30 wt% based on total molding composition of a multiphase composite polymer comprising;
(1) about 25 to about 95 wt% of a first elastomeric phase polymerized from a monomer system comprising about 75 to 99.8% by weight Cl to C6 alkyl acrylate, 0.1 to 5%
by weight crosslinking monomer, and 0.1 ko 5% by weight graftlinking monomer, said crosslinking monomer heing a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactive groups all of which polymerize at substantially the same rate of reaction, and said graftli~king monomer being a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactive groups, at least one of which polymerizes at a substantially 2d different rate of polymerization from at least one other of said reactive groups; and
BACKGROUND OF THE INVENTION
. ~
Polybutylene terephthalate (PBT) reinforced with thermally stable reinforcing fibers such as glass fibers is well known as a molding resin and is described in numerous patents and publications including for instance United States 3,814,725, United States 3,814,786 and United States 3,624,024.
Fiber reinforcement generally improves ~he tensile strength, flexural strength, flexural modulus and heat distortion temperature of the molding composition. However, moldings, especially injection moldings of large fiber glass reinforced articles of PBT, nylon and other semicrystalline thermo-plastics tend to display distortion or warping whi]e glass fiber reinforced amorphous thermoplastic compounds do not present such problems. It is believed that strains resulting from the different degrees of volumetric contraction parallel to and transverse to the direction of plastic melt flow into the mold during the cooling of molded articles are responsible for such warping. Orientation of the glass fibers parallel to the direction of melt flow during molding produces this directional difference in volumetric contraction. The warping is thus believed due to the presence of the very reinforcing fibers which contribute to the enhanced physical characteristics of the finished product. It is known that addition of mica to fiberglass reinforced PBT reduces warping.
Unfortunately, the mica also greatly reduces impact strength.
, ., e~
Various impact modifiers are also known which improve ~he impact strength of molded PBT compositions. Some of these are described for instance in United States patents 4,096,202 and 4,034,013. It is generally believed and unfortunately true, that some modifiers which improve impact characteristics of PBT molding compositions, especially fiber reinforced compositions, also tend to increase the warping characteTistics of the compo-sitions.
Therefore, this invention seeks to provide an improved fiber glass reinforced PBT molding composition and method for producing same as well as molded articles of such composition. As compared with known prior art compositions, the molded compositions of the invention have an especially desirable combination of properties including reduced warpage and improvecl impact strength.
Improved polyester tnolding compositions of the invention consist essentially of at least about 40 wt% PBT having an intrinsic viscosity between about 0.5 and about 2.0 deciliters per gram ~dl/g). Such molding compositions also include:
(a) between about 3 and about 50 wt% based on total molding composition of thermally stable reinforcing fibers having diameters between about 5 and about 20 microns and aspect ratios of at least about 5;
~, ~
(b) between about 1 and about 40 wt% based on total molding composition of phlogophite mica flake having an average particle size between about 40 and about 325 mesh ~nd with at least about 90% of such mica having particle si es between about 40 and about 200 mesh; and (c) between abou~ 5 and about 30 wt% based on total molding composition of a multiphase composite polymer comprising;
(1) about 25 to about 95 wt% of a first elastomeric phase polymerized from a monomer system comprising about 75 to 99.8% by weight Cl to C6 alkyl acrylate, 0.1 to 5%
by weight crosslinking monomer, and 0.1 ko 5% by weight graftlinking monomer, said crosslinking monomer heing a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactive groups all of which polymerize at substantially the same rate of reaction, and said graftli~king monomer being a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactive groups, at least one of which polymerizes at a substantially 2d different rate of polymerization from at least one other of said reactive groups; and
(2) about 75 to S wt~ of a final, rigid thermoplastic phase polymerized in the presence of said elastomeric phase.
Preferred compositions of the invention i~clude use of glass fibers as the thermally stable reinforcing fibers and the use of the preferred multiphase polymers described below.
1~3~
As mentioned above, the invention includes a novel molding composition, molded articles o such composition and method for producing such composition. The molding composition broadly comprises at least a~out 40 wt% of PBT
having an intrinsic viscosity between about 0.5 and about 2.g dl/g and containing thermally stable reinforcing fibers, mica and multiphase composite polymer as described herein.
Polybutylene terephthalate (PBT) used in the invention may be produced in any suitable manner such as by reacting terephthalic acid or a dialkyl ester of terephthalic acid, e.g., dimethyl terephthalate, with diols having our carbon atoms, e.g., tetramethylene glycol. PBT for use in the invention has an intrinsic viscosity (I.V.) between about 0.5 and about 2.0 dl/g measured in orthochlorophenol at 25C., with material having an I V. between about 0.5 and about 1.1 dl/g being preferred. Manufacture of PBT is well known to those skilled in the ar~ as are the techniques for obtaining PBT of desired intrinsic viscosity. Such conventional production techniques for P~T are disc~ssed in greater detail, for instance, in U.S. Patent 3,465,319.
Thermally stable reinforcin~ fibers used in the invention may be any such fibers which are thermally stable at the conditions normally used in the production of products from PBT molding compositions and include, for instance, fibers of materials such as glass, aramid, calcium sulfate, ~ 3~
aluminum metal, boron, asbestos, carbon, ibrous potassium titanate, iron whiskers, etc9 Such fibers should normally have diameters between about 5 and about 20 microns and aspect ratios (ratio of length of fiber to diameter of fiber) of at least about 5. Glass fibers .are pref~rred for use in the invention. Glass fibers, where used, preferably have diameters between about 10 and about 15 microns and aspect ratios of at least about 20.
Reinforcing fibers used in the invention are normally used in amounts between about 3 and about 50 wt%
based on total weight of PBT molding composition, more preferably in amounts between about 3 and about 20 wt% on the same basis. As is commonly recognized, the use of such ibers improves substantially such ph~sicaL properties as tensile strength, Elexural strength, flexural modulus and heat distortion temperature of the PBT. GIass or other fibers for use in the invention may be manufactured and incorporated into the P~T in any suitable manner, such as by separate extrusion blending with the PBT, extrusion blending with other ingredients of the compositions of the invention or incorporating into the PBT or PBT containing composition during injection molding of products from the PBT.
As mentioned above, products molded from fiber reinforced PBT, while having substantially improved physical properties in certain respects, suffer from excessive warpage believed to be due to the preferential orientation of the fibers parallel to the direction of melt flow within the mold.
It is thus nPcessary in accordance with the present invention to incorporate in the compositions and the produc~s of the ~ 3~
invention additional filler material for the purpose of reducing the adverse effec~ of the reinforcing fibers on warpage. More specifically, ~he present invention re~uires the use o between about 1 and about: 40 wt% based on total molding compositlon of phlogophite mica having an average particle size be~ween about 40 and about 325 mesh with at least about 90% of such mica having particle sizes between about 40 and about 200 mesh (i.e. passing through a 40 mesh screen but retained on a 200 mesh screen). ~o alleviate the la adverse effect of mica on impact strength, the invention also requires the presence of between about 5 and about 30 wt%
based on total molding composition of a multiphase composite polymer comprising:
~1) about 25 to about 95 wt% of a first elastomeric phase polymerized from a monomer system comprising about 75 to 99.8% by weight Cl to C6 alkyl acrylate, 0.1 to 5% by weight crosslinking monomer, and 0.1 to 5~ by weight graftlinking monomer, said crosslinking monomer being a polyethylenically unsaturated monomer having a plurality of addition 2Q polymerizable reactive groups all of which polymerize at substantially the same rate of reaction, and said graftlinking monomer being a polyethylenically unsaturated monomer having a plurality of addition polymerizable reaction groups, at least one of which polymerizes at a substantially different rate of polymerization from at leas~ one other of said reactive groups; and (2~ about 75 ts 5 wt~ of a ~inal, rigid thermoplastic phase polymerized in the presence of said elastomeric phase.
9~5 The multiphase composite poly~er used in compositions of the invention comprises from about 25 to about 95 wt~ of a first elastomeric phase and about 75 to 5 wt% of a final rigid thermoplastic phase. One or more intermediate s phases are optional, for example, a rniddle s~age polymerized from about 75 to 100 percent by weight s~yreneO The first stage is polymerized from about 75 to 99.8 wt% Cl to C6 acrylate resulting in an acrylic rubber core having a glass transition temperature bel~w about 10C and crosslinked with 0.1 to 5 percent crosslinking monomer and further containing 0.1 to 5 percent by weight graftlinking monomer. The preferred alkyl acrylate is butyl acrylate. The crosslinking monomer is a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactve groups all o which polymerize at ~ubstantially the same rate of reaction.
Suitable crosslinking monomers include poly acrylic and poly methacrylic esters of polyols such as butylene diacrylate and dimethacrylate, trimethylol propane trimethacrylate, and the like; di- and trivinyl benzene, vinyl acrylate and methacrylate, and the like. The preferred crosslinking monomer i-s butylene diacrylate. The graftlinking monomer is a polyethylenically unsaturated monomer having a plurality of adition polymerizable reactive groups, at least one of which polymerizing at a substantially different rate of pol~merization from at least one other of said reactive groups. The function of the graftlinking monomer is to provide a residual level of unsaturation in the elastomeric phase, particularly in the latter stages of polymerization and, consequently, at or near the surface of the elastomer particles.
~ 3~ 5 When the rigid thermoplastic phase is subsequently polymerized at ~he surface of the elastomer, the residual unsa~urated addition polymerizable r~active group contributed by the graftlinking monomer participates in the subse~uent reaction sa that at least a portion of the rigid phase is chemically attached to surface of the elastomer. Among the effective graftlinking monomers are allyl group-containing monomers o~ allyl esters of ethylenically unsaturated acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumaratet diallyl itaconate, allyl acid maleate, allyl acid fumarate, and allyl acid itaconate. Somewhat less preferred are the diallyl esters of polycarboxylic acids which do not generally have a favorable polymerization rate. The preferred gra~tlinking monomers are allyl methacrylate and diallyl maleate. A most pref~rred interpolymer has only two stages, the first s~age comprising about 60 to 95 percent by weight of the interpolymer and being polymerized from a monomer system comprising 95 to 99.8 percent by weight butyl acrylate, 0.1 to 2.5 percent by weight butylene diacrylate as crosslinking agent/ 0.1 to 2.5 percent by weight -allyl methacrylate or diallyl maleate as a graftlinking agent, with a final stage polymerized from about 60 to 100 percent by weight methyl methacrylate.
The final stage monomer system can be comprised of Cl to C16 methacrylate, styrene, acrylonitrile, alkyl acrylates, allyl methacrylate, diallyl methacrylate, and the like, as long as the overall glass transition temperature is at least about 20C. Preferably the final stage monomer system is at least about 50 wt~ Cl to C4 alkyl methacrylate.
In a pre~erred embodiment the final stage monomer system may also contain epoxy functionality. By "epaxy functionality" is 9'~5 meant epoxy units which are pendant from the final stage polymer. The preferred way of incorporating epoxy functionality-into the final stage polymer is by use of epoxy containing ~onomer such as glycidyl acrylate or glycidyl methacrylate in the final stage monomer mixture. Alternate epoxy containing monomers are butadiene monoepoxide, allyl glycidyl ether, 4,5-epoxy pentyl methacrylate or acrylate, l0, ll-epoxy undecyl methacrylate, or other expoxy-containing ethyleneically unsaturated monomers. Other ways of introducing epoxy functionality into the final stage of the multiple stage polymer are possible, such as post expoxidation. It is further preferred that the final stage polymer be free oE units which tend to degrade poly (alkylene terephthalates), for example, acid, hydroxyl, amino, and amide groups.
For further descriptions and examples of various multiphase polymers suitable for use in the present invention~
reference may be had to the aforementioned U.S. Patent 4,096,202 the disclosure of which is incorporated herein by reference. Additional examples of multiphase ~olymers suitable for use in the invention may be found in U.S. Patent 4,034,013 the disclosure of which is also incorporated herein by reference.
In addition to the ingredients mentioned above, compositions and products of the invention may contain suitable flame retardant additives in amounts up to about 2Q
wt% based on total molding composition and may contain relatively minor amounts of other materials which do not unduly affect the desired characteristics oE the finished ~3~3`9'~
product. Such additional materials, may, depending upon the par~icular compositions employed and products desired, include for instance, colorants and lubricants. Where present, such additional materials normally comprise no more than about 5 wt% of the total composition or finished product.
In preparing molded compositions of the invention, the reinforcing fibers may be intimately blended into the PBT
by any suitable means suc~ as by dry blending followed by melt blending, blending in extruders, heated rolls or other types I~ of mixers, etc. Conventional master batching techniques may also be used. The same considerations apply to addition of the other essential or op~ional ingredients of the composition o ~he invention. Suitable blending and molding techniques are well known in the art and need not be described in detail 15, herein~ In a preferred embodiment o~ the invention, the composition o the invention is compounded by dry blending ollowed by melt mixing in an extruder with barrel temperatures between about 240 and about 270C. Likewise, in molding products of the invention from molding compositions of ~a the invention, injection molding is preferred. When injection molding is used, barrel temperatures between about 250C and 265C are preferred. In a preferred embodiment, the molding composition of the invention is formed by extrusion and pelletized. Products of the invention are then produced by injection molding the pelletized extrudate.
As mentioned above, one of the major advantages of the compositions and products of the invention is that the addition of mica and the above described multiphase polymers to glass fiber reinforced PBT substantially reduces shrinkage s and warpage normally associated with the use of reinforcing fibers without substantial harm to the desira~le improvements in physical proper~ies associated with the use of such fibers.
While warpage is freqent:Ly determined by visual S inspection, a quantitative de~inition can be expressed in terms of percent warp equals (dm-t)tl where '~dm" equals maximum distance from a flat surface to a point on a warped side of the article being evaluated, and "t" equals the thickness of the warped side of the article. This equation defines warp in terms of wall thickness without regard to length of the part. Since some absolute deviation from a straight line gives the same percent warp, a correction for part length must also be included to more accurately define warpage of a part in terms o~ the visual efect of the warp.
Part warp (PW) may therefore be defined as PW =
wherein PW e~uals part warp, "L" equals total length of the warp member and the other values are as stated immediately .above. In evaluating warpage of samples and products, an average warpage value for a five sided plain box is frequently calculated based upon measurements of warpage of the right, left, front and back sides of the box.
In addition to required and optional ingredients mentioned above, compositions of the invention may also include between about l and about 35 wt% based on total composition of polyethylene terephthalate (PET). Where PET is used in compositions of the invention a nucleating agent such as talc etc. is also preferably employed in amounts between about .01 and about 10 wt% based on total composition. The PET
function is to reduce warpage problems and reduce cost. PET
having an intrinsic viscosity between about 0.4: and about 1.2 dl/g as measured in or~hochlorophenol at 25C is ~referred.
The following examples are intended to illustrate the applicat~on and useulness oE the invention without limiting the scope thereof~ In the example, all quantities are given in terms of wt% based on ~otal composition unless otherwise specified~ Physical properties, including warpage, were measured by the following criteria and reported as an average for samples of each composition tested:
PropertY Test Procedures Tensile Yield Strength ASTM D-638 Flexural Yield Strength AS~M D-790 Flexural Modulus ASTM D-790 Notched Izod Impact Strength ASTM D-256 Cantilever Beam Reversed Notch Izod Impact Strength ASTM D-256 Percent warp As defined above Example I
PBT (O.8 I.Y.~ was compounded on a Midland Ross 1.5 inch extruder with various amounts of phlogophite mica and other ingredients as specified below to form various molding compositions as speci~ied in Table I below. The mica used was . Marietta Resources International Su~orite HAR 60-S mica flake having the ~ollowing size distribution.
trace -20 + 40 mesh (U.S. sieve) 76~ -40 + 100 mesh 19% -100 + 200 mesh
Preferred compositions of the invention i~clude use of glass fibers as the thermally stable reinforcing fibers and the use of the preferred multiphase polymers described below.
1~3~
As mentioned above, the invention includes a novel molding composition, molded articles o such composition and method for producing such composition. The molding composition broadly comprises at least a~out 40 wt% of PBT
having an intrinsic viscosity between about 0.5 and about 2.g dl/g and containing thermally stable reinforcing fibers, mica and multiphase composite polymer as described herein.
Polybutylene terephthalate (PBT) used in the invention may be produced in any suitable manner such as by reacting terephthalic acid or a dialkyl ester of terephthalic acid, e.g., dimethyl terephthalate, with diols having our carbon atoms, e.g., tetramethylene glycol. PBT for use in the invention has an intrinsic viscosity (I.V.) between about 0.5 and about 2.0 dl/g measured in orthochlorophenol at 25C., with material having an I V. between about 0.5 and about 1.1 dl/g being preferred. Manufacture of PBT is well known to those skilled in the ar~ as are the techniques for obtaining PBT of desired intrinsic viscosity. Such conventional production techniques for P~T are disc~ssed in greater detail, for instance, in U.S. Patent 3,465,319.
Thermally stable reinforcin~ fibers used in the invention may be any such fibers which are thermally stable at the conditions normally used in the production of products from PBT molding compositions and include, for instance, fibers of materials such as glass, aramid, calcium sulfate, ~ 3~
aluminum metal, boron, asbestos, carbon, ibrous potassium titanate, iron whiskers, etc9 Such fibers should normally have diameters between about 5 and about 20 microns and aspect ratios (ratio of length of fiber to diameter of fiber) of at least about 5. Glass fibers .are pref~rred for use in the invention. Glass fibers, where used, preferably have diameters between about 10 and about 15 microns and aspect ratios of at least about 20.
Reinforcing fibers used in the invention are normally used in amounts between about 3 and about 50 wt%
based on total weight of PBT molding composition, more preferably in amounts between about 3 and about 20 wt% on the same basis. As is commonly recognized, the use of such ibers improves substantially such ph~sicaL properties as tensile strength, Elexural strength, flexural modulus and heat distortion temperature of the PBT. GIass or other fibers for use in the invention may be manufactured and incorporated into the P~T in any suitable manner, such as by separate extrusion blending with the PBT, extrusion blending with other ingredients of the compositions of the invention or incorporating into the PBT or PBT containing composition during injection molding of products from the PBT.
As mentioned above, products molded from fiber reinforced PBT, while having substantially improved physical properties in certain respects, suffer from excessive warpage believed to be due to the preferential orientation of the fibers parallel to the direction of melt flow within the mold.
It is thus nPcessary in accordance with the present invention to incorporate in the compositions and the produc~s of the ~ 3~
invention additional filler material for the purpose of reducing the adverse effec~ of the reinforcing fibers on warpage. More specifically, ~he present invention re~uires the use o between about 1 and about: 40 wt% based on total molding compositlon of phlogophite mica having an average particle size be~ween about 40 and about 325 mesh with at least about 90% of such mica having particle sizes between about 40 and about 200 mesh (i.e. passing through a 40 mesh screen but retained on a 200 mesh screen). ~o alleviate the la adverse effect of mica on impact strength, the invention also requires the presence of between about 5 and about 30 wt%
based on total molding composition of a multiphase composite polymer comprising:
~1) about 25 to about 95 wt% of a first elastomeric phase polymerized from a monomer system comprising about 75 to 99.8% by weight Cl to C6 alkyl acrylate, 0.1 to 5% by weight crosslinking monomer, and 0.1 to 5~ by weight graftlinking monomer, said crosslinking monomer being a polyethylenically unsaturated monomer having a plurality of addition 2Q polymerizable reactive groups all of which polymerize at substantially the same rate of reaction, and said graftlinking monomer being a polyethylenically unsaturated monomer having a plurality of addition polymerizable reaction groups, at least one of which polymerizes at a substantially different rate of polymerization from at leas~ one other of said reactive groups; and (2~ about 75 ts 5 wt~ of a ~inal, rigid thermoplastic phase polymerized in the presence of said elastomeric phase.
9~5 The multiphase composite poly~er used in compositions of the invention comprises from about 25 to about 95 wt~ of a first elastomeric phase and about 75 to 5 wt% of a final rigid thermoplastic phase. One or more intermediate s phases are optional, for example, a rniddle s~age polymerized from about 75 to 100 percent by weight s~yreneO The first stage is polymerized from about 75 to 99.8 wt% Cl to C6 acrylate resulting in an acrylic rubber core having a glass transition temperature bel~w about 10C and crosslinked with 0.1 to 5 percent crosslinking monomer and further containing 0.1 to 5 percent by weight graftlinking monomer. The preferred alkyl acrylate is butyl acrylate. The crosslinking monomer is a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactve groups all o which polymerize at ~ubstantially the same rate of reaction.
Suitable crosslinking monomers include poly acrylic and poly methacrylic esters of polyols such as butylene diacrylate and dimethacrylate, trimethylol propane trimethacrylate, and the like; di- and trivinyl benzene, vinyl acrylate and methacrylate, and the like. The preferred crosslinking monomer i-s butylene diacrylate. The graftlinking monomer is a polyethylenically unsaturated monomer having a plurality of adition polymerizable reactive groups, at least one of which polymerizing at a substantially different rate of pol~merization from at least one other of said reactive groups. The function of the graftlinking monomer is to provide a residual level of unsaturation in the elastomeric phase, particularly in the latter stages of polymerization and, consequently, at or near the surface of the elastomer particles.
~ 3~ 5 When the rigid thermoplastic phase is subsequently polymerized at ~he surface of the elastomer, the residual unsa~urated addition polymerizable r~active group contributed by the graftlinking monomer participates in the subse~uent reaction sa that at least a portion of the rigid phase is chemically attached to surface of the elastomer. Among the effective graftlinking monomers are allyl group-containing monomers o~ allyl esters of ethylenically unsaturated acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumaratet diallyl itaconate, allyl acid maleate, allyl acid fumarate, and allyl acid itaconate. Somewhat less preferred are the diallyl esters of polycarboxylic acids which do not generally have a favorable polymerization rate. The preferred gra~tlinking monomers are allyl methacrylate and diallyl maleate. A most pref~rred interpolymer has only two stages, the first s~age comprising about 60 to 95 percent by weight of the interpolymer and being polymerized from a monomer system comprising 95 to 99.8 percent by weight butyl acrylate, 0.1 to 2.5 percent by weight butylene diacrylate as crosslinking agent/ 0.1 to 2.5 percent by weight -allyl methacrylate or diallyl maleate as a graftlinking agent, with a final stage polymerized from about 60 to 100 percent by weight methyl methacrylate.
The final stage monomer system can be comprised of Cl to C16 methacrylate, styrene, acrylonitrile, alkyl acrylates, allyl methacrylate, diallyl methacrylate, and the like, as long as the overall glass transition temperature is at least about 20C. Preferably the final stage monomer system is at least about 50 wt~ Cl to C4 alkyl methacrylate.
In a pre~erred embodiment the final stage monomer system may also contain epoxy functionality. By "epaxy functionality" is 9'~5 meant epoxy units which are pendant from the final stage polymer. The preferred way of incorporating epoxy functionality-into the final stage polymer is by use of epoxy containing ~onomer such as glycidyl acrylate or glycidyl methacrylate in the final stage monomer mixture. Alternate epoxy containing monomers are butadiene monoepoxide, allyl glycidyl ether, 4,5-epoxy pentyl methacrylate or acrylate, l0, ll-epoxy undecyl methacrylate, or other expoxy-containing ethyleneically unsaturated monomers. Other ways of introducing epoxy functionality into the final stage of the multiple stage polymer are possible, such as post expoxidation. It is further preferred that the final stage polymer be free oE units which tend to degrade poly (alkylene terephthalates), for example, acid, hydroxyl, amino, and amide groups.
For further descriptions and examples of various multiphase polymers suitable for use in the present invention~
reference may be had to the aforementioned U.S. Patent 4,096,202 the disclosure of which is incorporated herein by reference. Additional examples of multiphase ~olymers suitable for use in the invention may be found in U.S. Patent 4,034,013 the disclosure of which is also incorporated herein by reference.
In addition to the ingredients mentioned above, compositions and products of the invention may contain suitable flame retardant additives in amounts up to about 2Q
wt% based on total molding composition and may contain relatively minor amounts of other materials which do not unduly affect the desired characteristics oE the finished ~3~3`9'~
product. Such additional materials, may, depending upon the par~icular compositions employed and products desired, include for instance, colorants and lubricants. Where present, such additional materials normally comprise no more than about 5 wt% of the total composition or finished product.
In preparing molded compositions of the invention, the reinforcing fibers may be intimately blended into the PBT
by any suitable means suc~ as by dry blending followed by melt blending, blending in extruders, heated rolls or other types I~ of mixers, etc. Conventional master batching techniques may also be used. The same considerations apply to addition of the other essential or op~ional ingredients of the composition o ~he invention. Suitable blending and molding techniques are well known in the art and need not be described in detail 15, herein~ In a preferred embodiment o~ the invention, the composition o the invention is compounded by dry blending ollowed by melt mixing in an extruder with barrel temperatures between about 240 and about 270C. Likewise, in molding products of the invention from molding compositions of ~a the invention, injection molding is preferred. When injection molding is used, barrel temperatures between about 250C and 265C are preferred. In a preferred embodiment, the molding composition of the invention is formed by extrusion and pelletized. Products of the invention are then produced by injection molding the pelletized extrudate.
As mentioned above, one of the major advantages of the compositions and products of the invention is that the addition of mica and the above described multiphase polymers to glass fiber reinforced PBT substantially reduces shrinkage s and warpage normally associated with the use of reinforcing fibers without substantial harm to the desira~le improvements in physical proper~ies associated with the use of such fibers.
While warpage is freqent:Ly determined by visual S inspection, a quantitative de~inition can be expressed in terms of percent warp equals (dm-t)tl where '~dm" equals maximum distance from a flat surface to a point on a warped side of the article being evaluated, and "t" equals the thickness of the warped side of the article. This equation defines warp in terms of wall thickness without regard to length of the part. Since some absolute deviation from a straight line gives the same percent warp, a correction for part length must also be included to more accurately define warpage of a part in terms o~ the visual efect of the warp.
Part warp (PW) may therefore be defined as PW =
wherein PW e~uals part warp, "L" equals total length of the warp member and the other values are as stated immediately .above. In evaluating warpage of samples and products, an average warpage value for a five sided plain box is frequently calculated based upon measurements of warpage of the right, left, front and back sides of the box.
In addition to required and optional ingredients mentioned above, compositions of the invention may also include between about l and about 35 wt% based on total composition of polyethylene terephthalate (PET). Where PET is used in compositions of the invention a nucleating agent such as talc etc. is also preferably employed in amounts between about .01 and about 10 wt% based on total composition. The PET
function is to reduce warpage problems and reduce cost. PET
having an intrinsic viscosity between about 0.4: and about 1.2 dl/g as measured in or~hochlorophenol at 25C is ~referred.
The following examples are intended to illustrate the applicat~on and useulness oE the invention without limiting the scope thereof~ In the example, all quantities are given in terms of wt% based on ~otal composition unless otherwise specified~ Physical properties, including warpage, were measured by the following criteria and reported as an average for samples of each composition tested:
PropertY Test Procedures Tensile Yield Strength ASTM D-638 Flexural Yield Strength AS~M D-790 Flexural Modulus ASTM D-790 Notched Izod Impact Strength ASTM D-256 Cantilever Beam Reversed Notch Izod Impact Strength ASTM D-256 Percent warp As defined above Example I
PBT (O.8 I.Y.~ was compounded on a Midland Ross 1.5 inch extruder with various amounts of phlogophite mica and other ingredients as specified below to form various molding compositions as speci~ied in Table I below. The mica used was . Marietta Resources International Su~orite HAR 60-S mica flake having the ~ollowing size distribution.
trace -20 + 40 mesh (U.S. sieve) 76~ -40 + 100 mesh 19% -100 + 200 mesh
3% -200 + 325 mesh 2~ -325 mesh 9~S
Marietta Resources ~nternational Suzorite ~AR 200~S
mica flake was also used. T~is ma~erial had the ollowing size distribution:
trace -20 ~ 4a mesh (U.S. sieve) 1% -40 + 100 mesh 55% -100 + 200 mesh 20% -200 + 325 mesh 24~ -325 mesh The following conditions were employed:
I~Extruder Zone Temperatures Back Pressure 0-200 1 270C Amperage 12 25 2 265C Screw rpm 90 3 260C.
Marietta Resources ~nternational Suzorite ~AR 200~S
mica flake was also used. T~is ma~erial had the ollowing size distribution:
trace -20 ~ 4a mesh (U.S. sieve) 1% -40 + 100 mesh 55% -100 + 200 mesh 20% -200 + 325 mesh 24~ -325 mesh The following conditions were employed:
I~Extruder Zone Temperatures Back Pressure 0-200 1 270C Amperage 12 25 2 265C Screw rpm 90 3 260C.
4 255~C. Melt temperature 243-251C.
250C.
Each o~ the experimental molding compositions specified in Table I and produced as described above was then molded on a 50 ton 3 ounce reciprocating .screw injection molding machine to provide ASTM test specimens. Parts suitable for measuring warpaye (camera slide storage box with four large flat sides) were molded on a 250 ton 36 ounce Impco screw ram machine.
~olding conditions were:
~13V~S
Barrel temperature --- front 480F
rear 480F.
nozzle 480F~
Injection pressure 1100 psi 9crew rpm 75 Injection time 10 sec.
Mold time 20 sec.
Total cycle time 30 Oec.
Mold temperature 100 F.
36 oz., 350 ton moldlng machine Barr~l temperature --- front 480F.
center 480 F.
rear 480F.
nozzle 490F.
Measured melt temperature 420F.
Screw rpm Total cycle time 94 Oec.
Mold temperature 175 F.
Mold time 40 sec.
Ihjection pressure 1100 psi Physical properties were as shown in Table 2 below.
TABLE I
EXPERIMENTAL MOLDING COMPOUNDS
Wt %
In~redient 1 2 3 -PBT (0.8 I.V.) 25 25 30 PET (0.8 I.V.) 20 20 20 60-S Mica Flake 20 200-S Mica Flake 20 15 Glass Fibers (OC~ 419 AA
3/16 inch) 20 20 20 RM 330 Acrylic Impact Modif er 14.3 14.3 14.3 Acrowax C Lubricant 0.2 0.2 0.2 Epon 815 Diepoxy Modifier0.5 0.5 0O5 TABLE II
Wt %
Warp Annealed 100 120 % Warp Unannealed 81 97 Notched Izod Impact Strength (Foot Pounds per Inch)1.8 1.7 1.4 Cantilever Beam Reversed Notch I~ Izod Impact Strength (Foot Pounds per Inch)7.8 8.2 7.5 Flexural Strength (psi)18,00019,10016t300 Flexural Modulus (psi)1.23 1.27 .gO
. Tensile Strength (psi)11,43012,308 10,000 While the invention has been descr:ibed above with respect to certain preferred embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made without depar~ing from the spirit or scope of the invention.
250C.
Each o~ the experimental molding compositions specified in Table I and produced as described above was then molded on a 50 ton 3 ounce reciprocating .screw injection molding machine to provide ASTM test specimens. Parts suitable for measuring warpaye (camera slide storage box with four large flat sides) were molded on a 250 ton 36 ounce Impco screw ram machine.
~olding conditions were:
~13V~S
Barrel temperature --- front 480F
rear 480F.
nozzle 480F~
Injection pressure 1100 psi 9crew rpm 75 Injection time 10 sec.
Mold time 20 sec.
Total cycle time 30 Oec.
Mold temperature 100 F.
36 oz., 350 ton moldlng machine Barr~l temperature --- front 480F.
center 480 F.
rear 480F.
nozzle 490F.
Measured melt temperature 420F.
Screw rpm Total cycle time 94 Oec.
Mold temperature 175 F.
Mold time 40 sec.
Ihjection pressure 1100 psi Physical properties were as shown in Table 2 below.
TABLE I
EXPERIMENTAL MOLDING COMPOUNDS
Wt %
In~redient 1 2 3 -PBT (0.8 I.V.) 25 25 30 PET (0.8 I.V.) 20 20 20 60-S Mica Flake 20 200-S Mica Flake 20 15 Glass Fibers (OC~ 419 AA
3/16 inch) 20 20 20 RM 330 Acrylic Impact Modif er 14.3 14.3 14.3 Acrowax C Lubricant 0.2 0.2 0.2 Epon 815 Diepoxy Modifier0.5 0.5 0O5 TABLE II
Wt %
Warp Annealed 100 120 % Warp Unannealed 81 97 Notched Izod Impact Strength (Foot Pounds per Inch)1.8 1.7 1.4 Cantilever Beam Reversed Notch I~ Izod Impact Strength (Foot Pounds per Inch)7.8 8.2 7.5 Flexural Strength (psi)18,00019,10016t300 Flexural Modulus (psi)1.23 1.27 .gO
. Tensile Strength (psi)11,43012,308 10,000 While the invention has been descr:ibed above with respect to certain preferred embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made without depar~ing from the spirit or scope of the invention.
Claims (24)
1. Polyester molding composition consisting essentially of at least about 40 wt% polybutylene terephthalate having an intrinsic viscosity between about 0.5 and about 2.0 dl/g, such composition containing:
(a) between about 3 and about 50 wt% based on total molding composition of thermally stable reinforcing fibers having diameters between about 5 and about 20 microns and aspect ratios of at least about 5;
(b) between about 1 and about 40 wt% based on total molding composition of phlogophite mica flake having an average particle size between about 40 and about 325 mesh and with at least about 90% of such mica having particle sizes between about 40 and about 200 mesh; and (c) between about 5 and about 30 wt% based on total molding composition of a multiphase composite polymer comprising;
(1) about 25 to about 95 wt% of a first elastomeric phase polymerized from a monomer system comprising about 75 to 99.8%
by weight C1 to C6 alkyl acrylate, 0.1 to 5% by weight crosslinking monomer, and 0.1 to 5% by weight graftlinking monomer, said crosslinking monomer being a polyethylenically unsaturated monomer having a plurality of addition polymerizable. reactive groups all of which polymerize at substantially the same rate of reaction, and said graftlinking monomer being a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactive groups, at least one of which polymerizes at a substantially different rate of polymerization from at least one other of said reactive groups; and (2) about 75 to 5 wt% of a final, rigid thermoplastic phase polymerized in the presence of said elastomeric phase.
(a) between about 3 and about 50 wt% based on total molding composition of thermally stable reinforcing fibers having diameters between about 5 and about 20 microns and aspect ratios of at least about 5;
(b) between about 1 and about 40 wt% based on total molding composition of phlogophite mica flake having an average particle size between about 40 and about 325 mesh and with at least about 90% of such mica having particle sizes between about 40 and about 200 mesh; and (c) between about 5 and about 30 wt% based on total molding composition of a multiphase composite polymer comprising;
(1) about 25 to about 95 wt% of a first elastomeric phase polymerized from a monomer system comprising about 75 to 99.8%
by weight C1 to C6 alkyl acrylate, 0.1 to 5% by weight crosslinking monomer, and 0.1 to 5% by weight graftlinking monomer, said crosslinking monomer being a polyethylenically unsaturated monomer having a plurality of addition polymerizable. reactive groups all of which polymerize at substantially the same rate of reaction, and said graftlinking monomer being a polyethylenically unsaturated monomer having a plurality of addition polymerizable reactive groups, at least one of which polymerizes at a substantially different rate of polymerization from at least one other of said reactive groups; and (2) about 75 to 5 wt% of a final, rigid thermoplastic phase polymerized in the presence of said elastomeric phase.
2. Molding composition according to Claim 1 which also contains between about 1% and about 40% wt% based on total molding composition of polyethylene terephthalate.
3. Molding composition according to Claim 2 which also contains between about .01 and about 10% wt% based on total molding composition of a nucleating agent.
4. Molding composition according to Claim 1 wherein the reinforcing fibers are glass fibers.
5. Molding composition according to Claim 4 wherein the glass fibers have diameters between about 10 and about 15 microns and aspect ratios of at least about 20.
6. Composition according to Claim 1 wherein the final rigid thermoplastic phase of the multiphase polymer contains epoxy groups.
7. Composition according to Claim 4 wherein the epoxy groups are derived from glycidyl acrylate or glycidyl methacrylate.
8. Composition according to Claim 1 wherein said graftlinking monomer is allyl methacrylate or diallyl maleate.
9. Composition according to Claim 2 wherein the crosslinking monomer is butylene diacrylate.
10. Composition according to Claim 1 wherein the final rigid thermoplastic phase of the multiphase polymer is polymerized from a monomer system comprising from about 50 to 100 wt%
of a C1 to C4 alkyl methacrylate.
of a C1 to C4 alkyl methacrylate.
11. Composition according to Claim 1 wherein the final phase monomer system is free of acid, hydkoxyl, amino and amide groups and wherein the glass transition temperature of the final thermoplastic phase is at least about 20°C.
12. Composition according to Claim 1 wherein the reinforcing fibers are glass fibers, said first phase of the multiphase polymer comprises between about 60 and about 95 wt% of said multiphase polymer, said first phase is polymerized from a monomer system comprising between 95 and about 99.8 percent by weight butyl acrylate, between about 0.1 and about 2.5 wt% butylene diacylate as a crosslinking agent, and between about 0.1 and about 2.5 wt% allyl methacrylate or diallyl maleate as a graftlinking agent and said final phase of said multiphase polymer is polymerized from about 60 to 100 wt% methyl methacrylate.
13. An injection molded article molded from molding composition of Claim 1.
14. An injection molded article molded from molding composition of Claim 2.
15. An injection molded article molded from molding composition of Claim 3.
16. An injection molded article molded from molding composition of Claim 4.
170 An injection molded article molded from molding composition of Claim S.
18. An injection molded article molded from molding composition of Claim 6.
19. An injection molded article molded from molding composition of Claim 7.
20. An injection molded article molded from molding composition of Claim 8.
21. An injection molded article molded from molding composition of Claim 9.
22. An injection molded article molded from molding composition of Claim 10.
23. An injection molded article molded from molding composition of Claim 11.
24. An injection molded article molded from molding composition of Claim 12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US459679A | 1979-01-18 | 1979-01-18 | |
| US004,596 | 1979-01-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1130945A true CA1130945A (en) | 1982-08-31 |
Family
ID=21711554
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA332,375A Expired CA1130945A (en) | 1979-01-18 | 1979-06-23 | Reinforced polybutylene therephthalate molding composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5599949A (en) |
| CA (1) | CA1130945A (en) |
| DE (1) | DE2931430A1 (en) |
| FR (1) | FR2446848A1 (en) |
| GB (1) | GB2040958B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5693751A (en) * | 1979-12-26 | 1981-07-29 | Gen Aniline & Film Corp | Reinforced polyester molding composition |
| JPS57170952A (en) * | 1981-04-15 | 1982-10-21 | Teijin Ltd | Polyester resin composition |
| DE3117052A1 (en) * | 1981-04-29 | 1982-11-18 | Bayer Ag, 5090 Leverkusen | "AGING-RESISTANT, PROCESS-STABLE MIXTURES OF HIGH TOUGHNESS BASED ON THERMOPLASTIC POLYESTER" |
| US4390657A (en) | 1981-10-19 | 1983-06-28 | General Electric Company | Composition of polycarbonate, an ABS resin and an acrylate-methacrylate interpolymer |
| US4393153A (en) * | 1981-10-30 | 1983-07-12 | General Electric Company | Impact modified glass/mineral reinforced polyester blends |
| JPS614758A (en) * | 1984-06-20 | 1986-01-10 | Dainippon Ink & Chem Inc | Reinforced polybutylene terephthalate resin composition |
| DE3601422A1 (en) * | 1986-01-20 | 1987-07-23 | Basf Ag | THERMOPLASTIC MOLDS BASED ON POLYCARBONATES AND POLYESTERS |
| DE3733838A1 (en) * | 1987-10-07 | 1989-04-20 | Basf Ag | GLASS FIBER AMPLIFIED THERMOPLASTIC MOLDINGS BASED ON POYESTERS AND POLYMERPROPYLENE |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2207162A1 (en) * | 1972-11-20 | 1974-06-14 | Eastman Kodak Co | Polyester moulding materials with increased toughness - from 1,4-butane diol and terephthalic acid, with alkyl (meth) acrylate (co) polymers |
| DE2346056A1 (en) * | 1973-09-13 | 1975-04-24 | Basf Ag | FLAME RESISTANT AND SELF-EXTINGUISHING MOLDING COMPOUNDS |
| JPS5128141A (en) * | 1974-09-03 | 1976-03-09 | Asahi Chemical Ind | MUKIJUTENZAIGANJUSENJOHORIESUTERUJUSHISOSEIBUTSU NO SEIZOHO |
| US4034013A (en) * | 1975-11-13 | 1977-07-05 | Rohm And Haas Company | Impact and melt strength improvement of poly(alkylene terephthalate) |
| US4096202A (en) * | 1976-06-09 | 1978-06-20 | Rohm And Haas Company | Impact modified poly(alkylene terephthalates) |
| US4140670A (en) * | 1977-07-11 | 1979-02-20 | Gaf Corporation | PBT Injection molding composition |
| US4195011A (en) * | 1977-07-11 | 1980-03-25 | Gaf Corporation | Injection molding compositions |
| US4200567A (en) * | 1977-08-22 | 1980-04-29 | Rohm And Haas Company | Synergistic impact modifier system for poly (alkylene terephthalates) |
-
1979
- 1979-06-23 CA CA332,375A patent/CA1130945A/en not_active Expired
- 1979-08-02 DE DE19792931430 patent/DE2931430A1/en not_active Ceased
- 1979-09-06 FR FR7922339A patent/FR2446848A1/en active Granted
-
1980
- 1980-01-17 GB GB8001600A patent/GB2040958B/en not_active Expired
- 1980-01-17 JP JP316180A patent/JPS5599949A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2446848B1 (en) | 1983-07-08 |
| GB2040958A (en) | 1980-09-03 |
| GB2040958B (en) | 1983-07-27 |
| FR2446848A1 (en) | 1980-08-14 |
| DE2931430A1 (en) | 1980-07-31 |
| JPS5599949A (en) | 1980-07-30 |
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