JP2002526330A - Vehicle equipment based on thermoplastic polyketone - Google Patents

Abstract

  (57) [Summary] The present invention relates to vehicle equipment based on thermoplastic polyketones or blends of such polyketones with other polymers and the use of the thermoplastic polyketones for manufacturing vehicle equipment.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD [0001] The present invention relates to vehicle equipment based on thermoplastic polyketones or blends thereof with other polymers, and the use of the thermoplastic polyketone for manufacturing vehicle equipment.

BACKGROUND OF THE INVENTION Today, due to design and cost considerations, the use of plastics as a raw material for the production of external parts of vehicles is ever increasing. Vehicle-painted plastic lacquer-applied bracelets have always been an important factor. Plastic vehicle equipment provides greater design flexibility than metal ones. The use of plastic brace, especially as a body brace with a large surface area, offers significant cost advantages, the greater the lower the production output of the vehicle production line.

[0003] Lacquering of plastic vehicle equipment is an off-line performed on a large scale in a plastic lacquering unit in the manufacturer's building or vehicle manufacturing plant. Off-line lacquered equipment will be mounted on a fully lacquered bodywork at the end of the original lacquering line. Off-line lacquering has the advantage that special lacquering units are available with properties tailored to be particularly suited to the plastic material and the end use. There is virtually no limit on the choice of plastics from the thermoplastics field. However, offline lacquering has disadvantages such as changes in color and gloss, expensive lacquer materials and investment, high operating costs, high repair costs and costly material management.

[0004] As a measure to eliminate such difficulties of off-line lacquering,
It is conceivable to include a plastic device in the lacquering process of the vehicle and to partially or completely paint the device during the lacquering process of the vehicle body. The term on-line or in-line lacquering is used when the plastic equipment in the lacquering process of a car body is to be treated continuously by this type of coating method.

[0005] In the case of in-line lacquering, the plastic garment is introduced into the original lacquering line after the priming (for example, using a cathodic lacquer) and before or after the application of the filler. Is done. In the case of an in-line process, the plastic appliance may have to be lacquered, if desired, by electrostatic coating. This painting can be done using conductive plastic, or
For example, this is done using a conductive primer that has been lacquered off-line. When heating the filler layer and the subsequent lacquer layer (generally formed by applying a clear lacquer after priming), the plastic material, which is the base of the plastic appliance, has a temperature of up to 160 ° C. Must be heat-resistant so as not to be damaged under the conditions of processing for a predetermined time (for example, 30 minutes). A disadvantage of the in-line process is that the plastic appliances require a separate cleaning process. In addition, there is a risk of fouling if the plastic appliance is introduced into the lacquering line after priming.

[0006] In the case of online lacquering, there is the problem that when mounting the plastic equipment on the car body before priming, the car body and the plastic equipment go through the original complete lacquering process. Thus, in the case of on-line lacquering, the plastic garment is passed exactly through the lacquering line.
For the use of online lacquering, the whole body with the brace or the whole body with the brace on the assembly holder must first be degreased and phosphatized, for example, before being placed in an immersion bath. (Generally performed by a cathodic dip coating method), and then baking the undercoat layer at a temperature of up to 230 ° C. Further, lacquer coating is performed in the same manner as in the case of the in-line method.

In the case of the on-line method, there is no danger of fouling of the plastic equipment since the plastic equipment is not guided between the two lacquering stations. Direct assembly has significant cost advantages over off-line and in-line methods. For on-line lacquering, temperatures up to 230 ° C. (typically 160-2
(10 ° C.) for a predetermined time (for example, 30 minutes). Although suitable for the on-line process, the use of a non-conductive plastic requires pre-coating with a conductive primer if desired.

[0008] The advantages of treating the bodywork equipment in the lacquering process of the car body by in-line or on-line lacquering methods include the reduction of the lacquering cost, the simplification of the lacquering process, the color and pattern on the car body. Better harmony and simplified material management.

In the in-line and on-line processes, high heat resistance as well as high low-temperature strength are required, which hinders the application of almost all cost-effective thermoplastics to the lacquering process of car bodies. The addition of reinforcing materials (for example, glass fiber, talcum, kaolin, and wollastonite) to thermoplastics can increase heat resistance and lower the thermal coefficient.
This results in a reduction in cold strength. Although the low-temperature strength can be improved by adding an impact modifier (for example, ABS-rubber and EPDM-rubber) to the thermoplastic, the heat resistance becomes insufficient.

The only commercially important thermoplastics are polyphenylene oxide / polyamide (PPO / PA) blends that have the required heat resistance. PP
O / PA blends are currently mainly used as wing material to be lacquered by in-line or on-line methods. However, PPO / PA blends suffer from low low-temperature strength and high water absorption. Water absorption not only changes the dimensions, but also affects the properties of the applied lacquer. Another disadvantage of PPO / PA blends is that they are difficult to mix well because the blend consists of an amorphous thermoplastic and a partially crystalline thermoplastic.

To obtain sufficient phase gating with reproducible phase morphology and to avoid demixing phenomena, a compatible additive (compatibility agent) is required. is there. In addition to increasing costs, the chemical and physical complexity of the PPO / PA blend under the manufacturing conditions poses a problem when trying to ensure reproducible quality products.

DISCLOSURE OF THE INVENTION The present inventors have determined that thermoplastic polyketones or blends thereof with other thermoplastics combine properties that are ideal for vehicle equipment that can be lacquered in-line or on-line. did. Polyketones are partially crystalline thermoplastics that exhibit sufficient rigidity, heat resistance and dimensional stability at the high temperatures used in in-line or on-line lacquering processes. Polyketones or blends of these with other thermoplastics are characterized by outstanding impact resistance at low temperatures and absorb little moisture from the environment.

[0013] Polyketones and the like exhibit resistance to hydrolysis, exhibit very good resistance to fuel, and serve as an effective barrier to fuel. Polyketones and the like exhibit very good recovery properties. Polyketones can be made flameproof without the use of halogens or phosphorus. In addition, polyketones are produced from inexpensive raw materials such as carbon monoxide, ethylene and propylene.

In particular, polyketones or blends of these with other thermoplastics have both remarkable high temperature resistance and low temperature impact resistance. Furthermore, polyketones and the like can be processed by conventional plastic processing techniques such as injection molding, extrusion, thermoforming, deep drawing, compression, welding, contact pressure molding, and any combination thereof.

The present invention provides a vehicle brace and a vehicle body brace based on a thermoplastic polyketone.

[0016] Vehicle equipment based on thermoplastic polyketones or blends thereof with other thermoplastics as desired is suitable for in-line and on-line lacquering. In particular, such vehicle equipment can be used for online lacquering.

[0017] The thermoplastic polyketone may be mixed with other thermoplastics, thermoplastic elastomers or any mixture thereof as a blending component. Thermoplastic molding compositions containing thermoplastic polyketones and other blending components are particularly suitable for vehicle equipment.

The present invention also relates to the use of thermoplastic polyketones or blends thereof with other thermoplastics, thermoplastic elastomers or any mixtures thereof for making vehicular and vehicle body orthoses.

Thermoplastic polyketones have a linear alternating structure and contain substantially one molecule of carbon monoxide per unsaturated hydrocarbon molecule. Ethylenically unsaturated hydrocarbons suitable as monomers for the production of polyketone polymers are those having up to 20 and preferably up to 10 carbon atoms and include aliphatic hydrocarbons such as ethylene and other olefins such as propylene, -Butene, 1-isobutylene, 1-hexene, 1-octene and 1-dodecene) or araliphatic hydrocarbons having an aryl substituent on one carbon atom in the straight chain. Examples of the araliphatic monomer include styrene, α-methylstyrene, p-ethylstyrene, and m-isopropylstyrene.

Preferred polyketones are copolymers of carbon monoxide and ethylene or terpolymers of carbon monoxide, ethylene and a second ethylenically unsaturated hydrocarbon having at least 3 carbon atoms, especially α-olefins such as propylene. It is.

Terpolymers, one of which is ethylene and the other of which is a second hydrocarbon, having at least two monomer units are particularly preferred. It is preferred to use a second hydrocarbon having about 10 to 100 monomer units.

Preferred polymer chains of the polyketone are represented by the following formula (I): [CO (CH ₂ CH ₂ )] _x [CO (G)] _y (I) wherein G is an ethylenic double bond Having at least 3 carbon atoms polymerized through
Preferably 3 to 10 ethylenically unsaturated hydrocarbon-based monomer units,
The ratio of y: x is not greater than about 0.5, and y = 0 for copolymers of carbon monoxide and ethylene. When y is not 0, a terpolymer is used and -C
The O- (CH2CH2)-and -CO- (G)-units are randomly distributed along the polymer chain. The preferred y: x ratio is from 0.01 to 0.1.

Preferred polyketones are those having a number average molecular weight of from 1000 to 200,000, especially from 20,000 to 90,000 as determined by gel permeation chromatography. See U.S. Patent U.S. Pat.
See S-A5166252. The polyketone may be used alone or as a mixture of two or more.

Examples of blending components include: polyalkylene terephthalates, thermoplastic vinyl (co) polymers, graft polymers (eg, ABS-rubber, acrylate rubber, etc.), polyolefins, thermoplastic elastomers, such as Thermoplastic polyurethane, EP (D) M-rubber, polypropylene (PP) / EPDM-
Rubber, polyphenylene ether and any mixtures thereof.

The polyalkylene terephthalate used in the present invention is a reaction product of an aromatic dicarboxylic acid or a reactive derivative thereof (eg, dimethyl ester, acid anhydride, etc.) with an aliphatic, alicyclic or aromatic-aliphatic diol. And any mixture of the reaction products.

A preferred polyalkylene terephthalate can be prepared by reacting terephthalic acid or a reactive derivative thereof with an aliphatic or alicyclic diol having 2 to 10 carbon atoms by a known method (“Kunstsch”). Toff-
Hand Buch, Vol. 8, p. 695 et seq .; Carl-Hansel, Munich, 1973).

Preferred polyalkylene terephthalates contain at least 80 mol%, preferably 90 mol%, of terephthalic acid groups with respect to the dicarboxylic acid and at least 80 mol%, preferably at least 90 mol% of ethylene with respect to the diol component. Glycol group and / or 1,3-propanediol group and / or 1
, 4-butanediol groups.

Preferred polyalkylene terephthalates are, in addition to terephthalic acid groups, other dicarboxylic acid groups having 8 to 14 carbon atoms or aliphatic dicarboxylic acid groups having 4 to 12 carbon atoms, for example, phthalic acid groups, Contains up to 20 mol% of isophthalic acid group, naphthalene-2,6-dicarboxylic acid group, 4,4'-diphenyldicarboxylic acid group, succinic acid group, adipic acid group, sebacic acid group, azelaic acid group or cyclohexane diacetate group It may be.

Preferred polyalkylene terephthalates are ethylene glycol groups or 1
In addition to 1,3-propanediol or 1,4-butanediol, other aliphatic diols having 3 to 12 carbon atoms or alicyclic diol groups having 6 to 12 carbon atoms, for example, 1,3 -Propanediol group, 2-ethyl-1,3-propanediol group,
Neopentyl glycol group, 1,5-pentanediol group, 16-hexanediol group, cyclohexane-1,4-dimethanol group, 3-methyl-2,4-pentanediol group, 2-methyl-2,4-pentane Diol group, 2,2,4-trimethyl-1,3
-Pentanediol group, 2,2,4-trimethyl-1,5-pentanediol group, 2-ethyl-1,3-hexanediol group, 2,2-diethyl-1,3-propanediol group,
2,5-hexanediol group, 1,4-di- (β-hydroxyethoxy) -benzene group, 2,2-bis- (4-hydroxycyclohexyl) -propane group, 2,4-dihydroxy-1,1,1,2 Contains up to 20 mol% of 3,3-tetramethylcyclobutane group, 2,2-bis- (3-β-hydroxyethoxyphenyl) -propane group or 2,2-bis- (4-hydroxypropoxyphenyl) -propane group (DE-OS 2407 774, DE 240 77 776 and 271 593)
No. 2).

The polyalkylene terephthalate can be separated, for example, by blending a relatively small amount of a trihydric or tetrahydric alcohol or a tribasic or tetrabasic carboxylic acid as described in DE-OS 1920070 and US Pat. No. 3,692,744. It may be branched. Preferred branching agents include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, pentaerythritol and the like. It is desirable to use no more than 1 mole% of the branching agent, based on the acid component.

[0031] Terephthalic acid and its reactive derivatives (eg, its dialkyl esters) and polyalkylene terephthalates (polyethylene and polybutadiene) prepared exclusively from ethylene glycol and / or 1,3-propanediol and / or 1,4-butanediol Butylene terephthalate) and mixtures of these polyalkylene terephthalates are particularly preferred.

Preferred polyalkylene terephthalates are copolyesters prepared from at least two of said acid components and / or at least two of said alcohol components. A particularly preferred copolyester is poly (ethylene glycol / 1,4-butanediol) terephthalate.

The polyalkylene terephthalate generally has a value of about 0.4 to 1.5 when measured at 25 ° C. in a 1: 1 (weight ratio) mixed solvent of phenol / o-dichlorobenzene.
, Preferably having an intrinsic viscosity of 0.5 to 1.3.

The thermoplastic thermoplastic polyurethane used in the present invention is produced from a linear polyol (generally, a polyester polyol or a polyether polyol), an organic diisocyanate, and a short-chain diol (a chain extender). Additional catalysts may be used to facilitate the production reaction. The molar ratios of the reactants can be varied over a wide range, which can adjust the properties of the product. A molar ratio of polyol to chain extender of 1: 1 to 1:12 has proven useful. By adopting such a molar ratio, a product in the range of 70 Shore A to 75 Shore D is obtained.

The thermoplastic polyurethane elastomer may be prepared by a method of reacting the reaction components stepwise (prepolymer method) or a method of simultaneously reacting all the reaction components in one step (one-shot method). In the prepolymer method, an isocyanate-containing prepolymer is prepared from a polyol and a diisocyanate, and the prepolymer is reacted with a chain extender in a second step. The TPU may be prepared in a continuous or batch process. The best known preparation methods are the belt method or the extrusion method.

Thermoplastic polyurethanes can be obtained by reacting the following polyurethane-forming components (A), (B) and (C): (A) organic diisocyanates, (B) hydroxyl-terminated. Linear polyol (molecular weight: 500 to 500)
0), (C) a diol or diamine chain extender (molecular weight: 60 to 500). In this case, the molar ratio between the NCO groups in (A) and the groups in (B) and (C) that can react with the isocyanate is 0.9 to 1.2.

Suitable organic diisocyanates are, for example, aliphatic, cycloaliphatic, araliphatic as described in “Justus Liebigs Analen del Chemie”, vol. 562, pages 75-136. (Araliphatic), heterocyclic and aromatic diisocyanates.

Specifically, the following compounds are exemplified: aliphatic diisocyanates, for example, hexamethylene diisocyanate; alicyclic diisocyanates, for example, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4. -
Cyclohexane diisocyanate and 1-methyl-2,6-cyclohexane diisocyanate and the corresponding isomer mixture, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexyl methane diisocyanate and 2,2'-dicyclohexyl methane diisocyanate and the corresponding A mixture of isomers; aromatic diisocyanates such as 2,4-toluylene diisocyanate, a mixture of 2,4-toluylene diisocyanate and 2,6-toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4 ′ -Diphenylmethane diisocyanate and 2,2'-diphenylmethane diisocyanate, a mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, liquid 4,4'-diphenyl meta modified with urethane Diisocyanate and 2,4'-diphenylmethane diisocyanate, 4,4'-diisocyanatodiphenylethane (1,2) and 1,5-naphthylene diisocyanate.

Preferred diisocyanates are 1,6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and an isomer mixture of diphenylmethane diisocyanate (content of 4,4′-diphenylmethane diisocyanate:> 96% by weight), particularly preferred. 4,4'-diphenylmethane diisocyanate and 1,5-naphthylene diisocyanate.

The above diisocyanates may be used alone or as an arbitrary mixture. These diisocyanates may be used in combination with up to 15% by weight, based on their total weight, of a polyisocyanate, for example triphenylmethane 4,4 ′, 4 ″ -triisocyanate or polyphenyl-polymethylene polyisocyanate.

A linear polyol having a hydroxyl group as a terminal group (molecular weight: 500 to 5000)
Is used as component (B). Depending on the preparation, these polyols often contain small amounts of non-linear polyols. For this reason, these polyols are often also referred to as "substantially linear polyols". Polyester diols, polyether diols, polycarbonate diols or mixtures thereof are preferred.

Suitable polyether diols are prepared by reacting one or more alkylene oxides having an alkylene group of 2 to 4 carbon atoms with an inducing molecule having two active hydrogen atoms. Can be. Examples of the alkylene oxide include ethylene oxide, 1,2-propylene oxide, epichlorohydrin,
Examples thereof include 1,2-butylene oxide and 2,3-butylene oxide. Preference is given to ethylene oxide, propylene oxide and mixtures of 1,2-oxo-pyrene oxide and ethylene oxide. The alkylene oxide may be used alone or as an arbitrary mixture.

Inducing molecules include water, amino alcohols (eg, N-alkyldiethanolamines such as N-methyldiethanolamine, etc.) and diols (eg,
Ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol and the like). If desired, the inducing molecules may be used as a mixture.

Suitable polyether diols may be the polymerization products of hydroxyl-terminated tetrahydrofuran. From 0 to 30% by weight of the trifunctional polyether with respect to the difunctional polyether may be used, but the amount used should be at most such that a thermoplastic product is obtained. The molecular weight of the substantially linear polyether diol is from 500 to 5,000, and the polyether polyol may be used alone or as an arbitrary mixture.

Suitable polyester diols may be prepared, for example, from dicarboxylic acids having 2 to 12, preferably 4 to 6, carbon atoms and polyhydric alcohols. Suitable dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, and the like. Is exemplified. The dicarboxylic acids may be used alone or in any mixture, for example as a mixture with succinic acid, glutaric acid and adipic acid. In preparing the polyester diol, a corresponding dicarboxylic acid derivative, for example, a diester of a carboxylic acid having 1 to 4 carbon atoms in an alcohol group, a carboxylic anhydride or a carboxylic acid chloride may be used instead of the dicarboxylic acid, if desired. May be used.

Examples of the polyhydric alcohol include those having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms.
And specifically, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2- Dimethyl-1,3-propanediol,
Examples thereof include 1,3-propanediol and dipropylene glycol. Depending on the properties desired, the polyhydric alcohols may be used alone or in any mixture.

Esters of the above-mentioned diols, especially diols having 4 to 6 carbon atoms (for example, 1,4-butanediol or 1,6-hexanediol) with carbonic acid, hydroxycarboxylic acids (for example, caproic acid) Also suitable are polymerization products of condensation products and lactones (eg, optionally substituted caprolactone). Preferred polyester diols include ethanediol-polyadipate, 1,4-butanediol-polyadipate, ethanediol-1,4-butanediol-polyadipate, 1,6-hexanediol-neopentyl glycol-polyadipate,
, 6-hexanediol-1,4-butanediol-polyadipate and polycaprolactone. The molecular weight of the polyester diol is from 500 to 5,000, and these may be used alone or as an arbitrary mixture.

A diol or diamine having a molecular weight of 60 to 500 is used as a chain extender (C). Preferred chain extenders are diols having 2 to 14 carbon atoms, such as ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and especially 1,4-butanediol. However, diesters of terephthalic acid and glycols having 2 to 4 carbon atoms (eg, terephthalic acid
-Bis-ethylene glycol or terephthalic acid-bis-1,4-butanediol),
Hydroxyalkylene ethers of hydroquinone (eg, 1,4-di- (hydroxyethyl) -hydroquinone), ethoxylated bisphenols, (cyclo) aliphatic diamines (eg, isophorone diamine, ethylene diamine, 1,2-propylene diamine, 1.3) -Proprendiamine, N-methylpropylene-1,3-diamine,
N, N′-dimethylethylenediamine) and aromatic diamines (eg, 2,4-
Toluylenediamine, 2,6-toluylenediamine, 3,5-diethyl-2,4-toluylenediamine, 3,5-diethyl-2,6-toluylenediamine and primary mono-,
Di-, tri- or tetra-substituted 4,4'-diaminodiphenylmethane) are also suitable chain extenders. The above chain extenders may be used as any mixture. In addition, relatively small amounts of triols may be used.

In addition, small amounts of conventional monofunctional compounds may be used, for example, as chain terminators or release agents. Examples of such compounds include alcohols such as octanol and stearyl alcohol, and amines such as butylamine and stearylamine.

To prepare thermoplastic polyurethanes, the structural components of the polymer are reacted in the presence of optional catalysts, auxiliaries and additives. In this case, the reaction amount of the structural components is such that the ratio of the equivalent of NCO groups to the total equivalent of NCO-reactive groups, especially low molecular weight diols / triols and the total equivalent of OH groups in the polyol is 0.9: 1.0-1. 2 to 1.0,
In particular, the ratio is set to 0.95: 1.0 to 1.10: 1.0.

Suitable catalysts are known in the art and are customary tertiary amines such as triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N′-dimethylpiperazine, 2- (dimethylaminoethoxy) -ethanol , Diazabicyclo- (
2.2.2) -Octane and the like, and especially metal compounds such as titanates, iron compounds, tin compounds such as tin diacetate, tin dioctoate, tin dilaurate or tin dialkyl salts of aliphatic carboxylic acids, for example Examples thereof include dibutyltin diacetate and dibutyltin dilaurate. Preferred catalysts are organometallic compounds, especially titanates, iron compounds or tin compounds.

The thermoplastic polyurethane may be used alone or as a mixture of two or more. The TPU may be continuously prepared by a so-called extrusion method, for example, using a multi-screw extruder. The addition of the components (A), (B) and (C) of the TPU may be performed simultaneously by a one-shot method or may be performed sequentially by a prepolymer method. The prepolymer may be introduced in a batch mode or may be prepared continuously in one section of the extruder or in a separate upstream prepolymer unit.

Polyolefins are, for example, polyethylene, polypropylene, poly-1-butene and pomethylpentene, which may contain small amounts of copolymerized non-conjugated dienes. These polymers are known and are described, for example, in "Lemps Chemie-Lexicon", 8th edition (1987), Vol. 5, p. 3307 and the references cited therein.

Suitable thermoplastic vinyl (co) polymers include vinyl aromatics, vinyl cyanides (unsaturated nitriles), (C ₁ -C ₈ ) -alkyl (meth) acrylates, unsaturated carboxylic acids and unsaturated carboxylic acids. A polymer prepared from at least one monomer selected from the group consisting of derivatives of acids (eg, acid anhydrides and imides). (Co) polymers obtained from the following components (D.1) and (D.2) are preferred: (D.1) Vinyl aromatic compounds and / or ring-substituted vinyl aromatic compounds (
For example, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (C ₁ -C ₄ ) -alkyl methacrylate (eg, methyl methacrylate, ethyl methacrylate) 50 to 99 parts by weight, preferably 60 ~
80 parts by weight (D.2) vinyl cyanide (unsaturated nitrile) (e.g., aquo Lilo nitrile, methacrylonitrile) and / or _(C 1 -C ₈₎ - alkyl (meth) acrylates (e.g., methyl methacrylate, n -Butyl acrylate, t-butyl acrylate) and / or unsaturated carboxylic acids (eg, maleic acid) and / or derivatives of unsaturated carboxylic acids (eg, acid anhydrides and imides) (eg, maleic anhydride and N- Phenylmaleimide) 1 to 50 parts by weight, preferably 20 to 40 parts by weight

The (co) polymer is resinous, thermoplastic and contains no rubber. (D.
A copolymer in which the component (1) is styrene and the component (D.2) is acrylonitrile is particularly preferred. Further, polystyrene or α-methyl polystyrene optionally substituted with an alkyl group and / or a halogen atom is also preferable.

These (co) polymers are known and can be prepared in particular by radical polymerization by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization. (Co) polymer preferably has (measured by light scattering or sedimentation) _{M W} weight average molecular weight of 15,000 to 200,000.

Suitable graft polymers are one or more graft polymers obtained from the following components (E.1) and (E.2): (E.1) at least one vinyl monomer 5 95% by weight, preferably 30
(E.2) 95 to 5% by weight, preferably 70 to 20% by weight of one or more graft backbones having a glass transition temperature of <10 ° C, preferably <0 ° C, especially <-20 ° C. %

[0058] grafting base (E.2) is generally have an average particle size of 0.05 to 5 [mu] m _{(d 50} value). The monomer (E.1) is composed of the following components (E.1.1) and (E.1.
(E.1.1) vinyl aromatic compounds and / or ring-substituted vinyl aromatic compounds (eg styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) ) and / or _(C 2 -C ₄₎ - alkyl methacrylate (e.g., methyl methacrylate, ethyl methacrylate) from 55 to 99 parts by weight (E.1.2) vinyl cyanide (acrylonitrile or methacrylonitrile unsaturated nitrile such as nitrile ) and / or _(C 1 -C ₄₎ - alkyl (meth) acrylates (e.g., methyl methacrylate, methyl acrylate, n- butyl acrylate, t- butyl acrylate) and / or derivatives of unsaturated carboxylic acids (e.g., acid anhydride And imides) (eg, maleic anhydride and N-Fe Nilmaleimide) 1 to 50 parts by weight

Preferred monomer components (E.1.1) are at least one monomer selected from styrene, α-methylstyrene and methyl methacrylate;
Preferred monomer components (E.1.2) are acrylonitrile, maleic anhydride,
It is at least one monomer selected from methyl acrylate and methyl methacrylate. Particularly preferably, the component (E.1.1) is styrene and the component (E.1.2) is acrylonitrile.

Suitable graft backbones (E.2) for graft polymerization include, for example, diene rubbers, EP (D) M-rubbers (ie rubbers based on ethylene / propylene and optional diene), acrylate rubbers, polyurethane rubbers, Examples include silicone rubber, chloroprene rubber and ethylene / vinyl acetate rubber. Preferred graft bases (E.2) are diene rubbers (for example, rubbers based on butadiene, isoprene, etc.), mixtures of diene rubbers or copolymers of diene rubbers, or other copolymerizable monomers thereof (for example, components (E.1. 1) and (E.1)
. 2), wherein the glass transition temperature of component (E.2) is <10 ° C., preferably <0 ° C., in particular <−10 ° C.).

[0061] Pure polybutadiene rubber is particularly preferred. Particularly preferred polymers are, for example, ABS polymers (ABS polymers by emulsion polymerization, bulk polymerization and suspension polymerization), such polymers being described, for example, in DE-OS 2035390 (DE-OS 2035390).
U.S. Pat. No. 3,644,674), DE-OS 2248242 (corresponding to GB-PS 1409275) or Ullmann, eds., Encyclopedia / Tehnischen Chemie, Vol. 19 (1980), pages 280 et seq. Has been described. The graft polymer is prepared, for example, by radical polymerization by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization (preferably emulsion polymerization).

A suitable acrylate rubber according to component (E.2) is preferably an alkyl acrylate polymer, which optionally comprises other polymerizable ethylenically unsaturated monomers relative to component (E.2). It may contain up to 40% by weight. Preferred polymerizable acrylates include C ₁ -C ₈ -alkyl esters, for example, halogenated alkyl esters such as methyl ester, ethyl ester, butyl ester, n-octyl ester and 2-ethylhexyl ester, preferably halogenated C ₁ -alkyl esters. Examples are C ₈ -alkyl esters such as chloroethyl acrylate and the like, and mixtures of these monomers.

For crosslinking, a monomer having one or more polymerizable double bonds is copolymerized. Preferred examples of the crosslinking monomer include an unsaturated monocarboxylic acid having 3 to 8 carbon atoms and an unsaturated monohydric alcohol having 3 to 12 carbon atoms or a saturated polyol having 2 to 4 carbon atoms and having 2 to 4 carbon atoms. And the ester with is exemplified. Such esters include ethylene glycol dimethacrylate, allyl methacrylate,
Polyunsaturated heterocyclic compounds, for example, trivinyl cyanurate, triallyl cyanurate, polyfunctional vinyl compounds, for example, divinyl benzene, trivinyl benzene and the like, and triallyl phosphate and diallyl phthalate are also preferable. It is.

Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are cyclic monomers such as triallyl cyanurate, triallyl isocyanurate, triacryloyl hexahydro-s-triazine and triallyl benzene. The amount of the crosslinking monomer to be used is preferably 0.02 to 5% by weight, particularly 0.05 to 2% by weight, based on the graft base component (E.2). It is advantageous to use a cyclic crosslinking monomer having at least three ethylenically unsaturated groups, because the amount of the graft base component (E.2) can be less than 1% by weight.

Other polymerizable ethylenically unsaturated monomers which may optionally be used in addition to acrylate to prepare the graft base component (E.2) include acrylonitrile, styrene, α-methylstyrene, acrylamide, vinyl -C 1 _-C 6 _- alkyl ethers, methyl methacrylate and butadiene and the like. Preferred acrylate rubbers used as graft base component (E.2) are emulsion polymers having a gel content of at least 60% by weight.

Another suitable graft base component (E.2) is a silicone rubber having a graft-active site, such a silicone rubber being described in DE-OS 37
04657, DE-OS704655, DE-OS3631540 and DE-O
What is described in S3631539 is illustrated. Graft backbone component (E.
The gel content of 2) is measured at 25 ° C. in a suitable solvent (M. Hoffman,
H. Klemmer and R.A. See Kuhn, "Polymer Analytics I and II" (Georg Cime, Stuttgart, 1977).

The average particle size d ₅₀ value is such that a particle size of 50% by weight of the particles is present before and after said value. This value can be determined by ultracentrifugation measurements (W. Scholtan and H. Lange, "Colloid. Z. and Z. Polymere," No. 250.
Vol. (1972), pages 782 to 1796).

The polyphenylene ether used in the present invention is described, for example, in European Patent E
It is described in P-A164767.

[0069] Fillers and reinforcing agents, especially mineral fillers, may be mixed into the polyketones and polyketone blends. Fillers and reinforcing agents that may be used include kaolin, talcum,
Wollastonite, glass fiber (including long glass fiber, continuous glass strand, glass fabric and glass mat), glass beads, calcium carbonate, carbon fiber,
Examples thereof include aramid fiber, mica, natural fiber, and any mixture thereof.
The amount of filler used is usually up to 50% by weight, preferably from 5 to 30%, based on the total mixture.
% By weight.

The molding compounds of the polyketones or polyketone blends may contain customary additives, such as, for example, lubricants, release agents, nucleating agents, antistatic agents, coloring agents and pigments. To obtain a conductive molding compound, the conductivity of the compound may be increased by adding conductive carbon black, carbon fibrils, graphite, conductive polymers, metal fibers and other conventional additives. Good.

The external parts of the vehicle brace or body according to the invention are produced by processing polyketones or polyketone blends by conventional processing techniques for plastics. Such processing techniques include injection molding, extrusion molding, thermoforming, deep drawing,
Examples include compression molding, welding molding, contact pressure molding, sintering molding, blow molding, gas injection technology, and any combination thereof.

To this end, the polyketone is mixed with the optional blending ingredients and the optional conventional fillers, reinforcing agents and / or additives by known methods, and the mixture is processed by conventional plastics processing techniques into semi-finished products ( For example, they can be used to produce plates, films, profiles or molded parts according to the invention, or they can be mixed at high temperatures in conventional equipment (eg extruders, internal compounders, twin-screw). After forming a thermoplastic compound for compounding by melt-blending at (preferably 200 to 350 ° C.), the compound is subjected to, for example, a granulation treatment. The semi-finished product (e.g., is obtained by further processing the particulate material comprising a polyketone or polyketone blend using conventional plastic processing techniques as described above.
Plate, film, profile) or molded part according to the invention (vehicle equipment)
Is obtained. Further processing of the semi-finished product using conventional techniques, such as thermoforming, results in a vehicle orthosis according to the invention.

The vehicle equipment made of polyketone or polyketone blend according to the present invention may comprise other materials,
For example, it may be used in combination with a metal or a plastic. After subjecting the vehicle equipment to the lacquering process, the lacquer layer may be present directly on the molding compound and / or the combination material of the polyketone or polyketone blend.

Mixtures of polyketones, blending components, fillers, reinforcing agents and / or additives, molding compounds of the polyketones or polyketone blends according to the invention, or polyketones or semi-finished products made of polyketones, alone or else Vehicle orthoses may be manufactured using conventional techniques in combination with materials.
Such conventional techniques are techniques for connecting or joining a plurality of members or parts, such as coextrusion, back spraying of a film, sandwich injection molding, back compression, back contact pressure molding, injection molding of insert parts. Encapsulation, injection molding of multiple parts, welding, compression, bonding, fusion, screwing and clamping
) And the like.

Preferred vehicle equipment includes the following: wings, bumpers, rear doors, boot lids, side door cladding, engine covers, bodywork roofs, radiator grills and exterior mirrors.

[0076] In Example Example The following components were used. (A) Polyketone: a linear alternating terpolymer made from carbon monoxide, ethylene and propylene ("Carilon DP P1000": Shell International International)
(B) Polyketone / ABS: 95% by weight of "Karilon DP P1000" and 5% by weight of ABS Polyketone: "Karilon DP P1000": Commercial product of Shell International ABS graft rubber: rubber mixture (average particle size _{d 50} is at 280 nm, 50 wt% polybutadiene rubber latex form a gel content of 53 wt% and an average particle diameter _{d 50} of 420
latex polybutadiene rubber 50 having a gel content of 85% by weight in nm
A graft rubber prepared by emulsion polymerization (initiator: potassium persulphate) using 50% by weight of rubber and a grafted shell (27 parts by weight of acrylonitrile and 73 parts by weight of styrene) A graft rubber having a content of 50% by weight of a shell formed by graft polymerization of a mixture consisting of
The polyketone and rubber were mixed at 220-240 ° C using a ZSK32 extruder.

(C) Polyketone / TPU: 95% by weight of “Carillon DP P1000” and 5% by weight of TPU Polyketone: “Carillon DP P1000” (see (A) above) Thermoplastic polyurethane (TPU): “Desmopan 385” A commercial product of Bayer AG (Revelksen, Germany) (a polymer containing polybutanediol-1,4-adipate, butanediol-1,4 and methylenediphenyldiisocyanate as raw materials). Polyketone and TPU are ZKS 32/1. It mixed at 220-240 degreeC using the mold extruder. (D) PBT: "Pocan 1300"; Bayer AG (Revelxen, Germany) (E) PPO / PA (polyphenylene ether / polyamide blend): "Noryl GTX964"; General Electric Plastics (Pittsfield: USA) Commercial product (F) Blend with improved impact resistance: “Pokan KU2-7912”; Commercial product of Bayer AG (Revelxen, Germany)

The molded body for the test was an injection molding machine (320-210-500 manufactured by Arburg).
(Molding machine) using the raw materials and molding temperatures recommended by the thermoplastic manufacturer.

The dynamic mechanical measurement of the complex shear modulus of a test rod (80 × 10 × 4 mm 3) was performed at a measurement frequency (1 Hz) in a torsional vibration test using an RDS II measuring machine (manufactured by Rheometrics). As a function of temperature. The shear modulus G 'provides information about stiffness and was used as a measure of heat resistance and dimensional stability. The value of the shear modulus G 'at an appropriate baking temperature of the lacquer is about 80 to
A pressure of 100 MPa means that the vehicle equipment can be considered sufficient to be subjected to the lacquering process without deformation.

The behavior of a disc having a diameter of 60 mm and a thickness of 3 mm when an impact stress was applied was measured according to ISO 6
According to 603-2, it was examined in a biaxial penetration test. The elastic modulus was measured on a dumbbell-shaped specimen in a tensile test according to ISO 527.2. Lacquer coatability was determined by standard methods known to those skilled in the art. The surface condition of the molded article was visually evaluated.

[0081]

[Table 1]

Polyketone and PBT are partially crystalline thermoplastics. The polyketone has a glass transition temperature of about 12 ° C., ie, below room temperature, but the stiffness (shear modulus) at high temperatures is substantially higher than PBT or other comparable partially crystalline thermoplastics. . Thus, polyketones, unlike other typical partially crystalline thermoplastics, have sufficient heat resistance for vehicle equipment subjected to in-line and on-line lacquering. Compared to PBT and PPO / PA blends, polyketones exhibit better impact resistance at low temperatures and transition from ductile to brittle at about -30 ° C. PC / PBT blends with improved impact resistance are typical blend systems for vehicle equipment subjected to off-line lacquering. This blend system shows good low temperature toughness, but shows very poor heat resistance for in-line and on-line lacquering. The examples for polyketone / ABS and polyketone / TPU show that the beneficial properties of polyketones associated with in-vehicle and on-line lacquering vehicle equipment are also retained in polyketone blend systems.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID , IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (71) Application Person D-51368 Leverkusen, Germany F-term (reference)

Claims (6)

[Claims] 1. A vehicle orthosis based on a thermoplastic polyketone. 2. A thermoplastic polyketone or at least one thermoplastic selected from the group consisting of polyalkylenes, terephthalates, thermoplastic vinyl (co) polymers, graft polymers, polyolefins and / or thermoplastic elastomers. Vehicle equipment based on a blend with polyketone. 3. The vehicle equipment according to claim 1, which can be lacquered in-line. 4. The vehicle equipment according to claim 1, which can be lacquered online. 5. A thermoplastic polyketone or blend thereof comprising fillers and / or reinforcing agents, and lubricants, release agents, nucleating agents, antistatic agents, stabilizers, colorants, pigments and additives for increasing conductivity. A vehicle orthosis according to any of the preceding claims, comprising at least one optional additive selected from the group consisting of agents. 6. Use of a thermoplastic polyketone, optionally mixed with other thermoplastics and additives for making vehicle equipment.