CN1105376A

CN1105376A - Coating compositions

Info

Publication number: CN1105376A
Application number: CN93117683.2A
Authority: CN
Inventors: K·H·多德; P·J·斯蒂芬森; N·J·韦尔顿
Original assignee: Laporte PLC
Current assignee: Evonik UK Holdings Ltd
Priority date: 1992-09-24
Filing date: 1993-09-23
Publication date: 1995-07-19
Also published as: CN1085575A

Abstract

A coating combination is suitable for mould inner coating method. Wherein, the used thermoplastic coating materials and the thermoplastic basis material mould and produce the basis body with coating in one mould, such as the components and parts of motor vehicles with high quality color lacquer coating. The polymers materials of the coating combination contain reversible crosslinked materials and thermoplastic alloy. Polypropylene basis coating combination can be utilized to produce the color lacquer layer on the components and parts of the polypropylene motor vehicles.

Description

Coating compositions

The present invention relates to coating composition, be applicable to, more particularly the preparation of the goods of forming by the polymeric matrix that coating (for example facing coating and/or supercoat) is arranged thereon by cated matrix.The present invention is relevant especially to the coating composition that is suitable for preparing the cated plastic components that is used for automotive industry, but is not special-purpose purposes.

By convention, the cated manufacturing that especially is coated with the polymeric matrix of coloured enamel layer almost only relates to preformed matrix coating solvent-based coating.Many methods can be used to applying coatings solution, for example spraying of matrix or dip-coating, and solvent-based coating can use for the number of different types matrix.

In the occasion that a kind of solvent-based coating is coated to a kind of based article such as molded plastic parts, often coat operations as an independent operation after the goods molding one for this reason the exclusive district of design carry out.It is possible that the content of coating quality and for example dust and solvent is well controlled.Consider recently with the discharging of organic solvent and handle relevant environmental legislation, last-mentioned that be particularly important.And the independent working procedure of coating of coating region use in special use can obviously increase productive expense, comprising reducing productivity.

Advise in addition, coating is coated to sheet or powdery makes cated polymer product on the preformed matrix, and, powder coating method in the mould having been produced interest recently, this method can form coating and matrix in same mould.In this mould in the powder coating method, the coated material that is pulverulence normally was used for topped mold inside before the matrix moulding.The coating of mould is finished by electrostatic spraying usually.

Advise in addition, coated material and body material are expelled in the same mould or by co-extrusion come out to form a kind of cated goods.

Jian Yi coating and coating method were suitable in some cases in the past, but were not all to be suitable in all cases.For example, in many industry, desirable is to come article of manufacture by the durable thermoplastic material such as polypropylene.For instance, if it is can method simple, paint to reasonable price to polypropylene, polypropylene can be of great use to goods and other trolley part of producing such as bumper so, and the occasion of many other situations arranged, desirable meeting provides a kind of belt surface coating thermoplastic material, and this coating all is different from the body of material at outward appearance and/or aspect of performance.But in the past the production method of the cated matrix that contains the thermoplastic material such as polypropylene of suggestion did not produce really with what reasonable price can access and had high quality, goods of durable surface facing.Be suitable on thermoplastic matrix, providing the coating composition of high quality coating must show the obvious improvement effect.

The invention provides a kind of coating composition in the coating process in the mould that is applicable to, comprise first kind thermoplastic, polymeric materials, thermoplastic, polymeric materials that second class can reversible crosslink and at least a material that is selected from broken pearly-lustre material, ultraviolet screener and antioxidant of coloring material, fine powder broken metallics, fine powder.In a preferred embodiment of the present invention, first kind thermoplastic, polymeric materials comprises alfon or multipolymer.

The present invention also provides a kind of coating composition in the coating process in the mould that is applicable to, comprises a kind of thermoplastic alloy, and at least a coloured material that is selected from, the material of pearlescent material, ultraviolet screener and antioxidant that broken metallic substance, the fine powder of fine powder is broken.

The present invention further provides a kind of thermoplasticity color paint composition, comprised alfon or multipolymer, coloured material and at least a material that is selected from broken pearlescent material, ultraviolet screener and antioxidant of the broken metallic substance of fine powder, fine powder.Said composition is applicable in the interior coating process of mould, is used to produce the goods that are made of the polypropylene matrix that scribbles the formed coating of said composition on it.

The present invention also provides a kind of thermoplasticity color paint composition, comprise alfon or multipolymer, ultraviolet screener and at least a coloured material that is selected from, the metallic substance that fine powder is broken, the pearlescent material that fine powder is broken and the material of antioxidant, said composition is applicable to coating process in the mould, the goods that production is made of polypropylene matrix and the coating that formed by said composition on it, ultraviolet screener and the usage ratio of described material in composition should make through the QUV test of this paper definition after 200 hours, reduces no more than former glossy 50% and coating does not chap by the coating gloss of ASTM D523-67 test, chalking or do not have crazing not.

The present invention and then a kind of thermoplasticity color paint composition is provided, comprise alfon or multipolymer, and at least a material that is selected from coloured material, fine powder cutting metal material, the broken pearlescent material of fine powder, ultraviolet screener and antioxidant, said composition is applicable in the interior coating process of mould, the goods that production is made of polypropylene matrix and the coating that formed by said composition on it, this coating has resistance to abrasion, can circulate and finish test 250 times by the Taber test of ASTM D1044.

The present invention also provides a kind of alfon or multipolymer and at least a thermoplasticity color paint composition that is selected from the material of coloured material, fine powder broken metallic substance, fine powder broken pearlescent material, ultraviolet screener and antioxidant of comprising, said composition is applicable in the interior coating process of mould, produce the goods that a kind of coating that is formed by polypropylene matrix and said composition constitutes thereon, the shock resistance of these goods is pressed BS 3900,1973, the PartE3 standard test is at least 2J, is lower than polypropylene matrix impact strength test value and is no more than 10%.

Coloured material such as pigment will hereinafter be done more detailed discussion at this specification sheets.

The present invention and then provide the present composition in mould, to be used to produce the application of the goods that constitute by thermoplastic matrix basically and the coating that forms by said composition on it in the coating process.

The composition that the present invention also provides the ionomer by the alfon of larger proportion or multipolymer and less ratio to constitute is used to produce a kind of application of the goods that are made of polymeric matrix and the coating that formed by said composition on it.This polymeric matrix preferably contains alfon or multipolymer.

If desired, can suitably use thermospray, apply composition of the present invention as the mode of flame plating.In addition, or in addition, can suitably said composition be used in injection-moulding device.Said composition also can suitably be used in coextrusion equipment.Said composition can be powder or particulate state, but also can other be suitable for using any form of the coating method of said composition to use.

The present composition is applicable to that wherein coated material and body material are made goods in same die for molding in the interior coating process of mould.Composition of the present invention also can prepare in the method that applies matrix at other certainly and uses, for example coetrusion.Said composition is particularly suitable for using with the matrix that is made of thermoplastic, polymeric materials.

The goods that present composition manufactured coating constitutes can have any shape of wanting.For example, such goods can be trolley parts.Another kind of possibility be these goods with co-extrusion techniques precedent such as a kind of frameworks, as the shape of window frame, make a kind of shape of the cable of forming by two layers of thermoplastic material at least, perhaps make the shape of fiber.

Composition of the present invention preferably suitably is used for a kind of by forming coating on the goods that thermoplastic matrix and its at least one lip-deep thermoplastic coating constitute basically, in this method this coating composition and for the macromolecular material of doing matrix be added in the mould and in this die for molding to produce this goods, heating if desired, can make softening, be preferably fluid, or the coating composition of molten state contacts with die surface or with body material.

Said composition of the present invention can be used for, for example make only 1mm of thickness maximum, for example maximum only coating of 500 μ m.

Said composition can be used for producing a kind of goods that comprise callable trolley part, these goods comprise a kind of thermoplastic basically matrix that salvage material is arranged, the thermoplastic basically coating that has one deck to form on this matrix, for example thermoplasticity colored paint coating by the present composition.In one embodiment of the invention, coated material and body material both are made up of a kind of alfon or multipolymer.

The present composition has special purposes in trolley part production, recoverable automobile parts for example, and also have many other purposes.The goods that can make with the present composition and the example that can use the method for said composition see with the application simultaneously by Laporte plc ﹠amp; The related content (application number GB 92.2020706) of the common pending application that is entitled as " cated matrix " that Rover Group Limited submits to.

Some compositions of the present invention is suitable for producing a kind of transparent or semitransparent layer, and this layer preferably contains a kind of ultraviolet screener, and this agent is used to protect lower floor's matrix and/or improves outward appearance and/or the performance of this top layer for its a part of goods.For example said composition can suitably be made colourless or painted Clear paint layer.But in an embodiment preferred of the present invention, said composition is suitable for making opaque coating and contains a kind of macromolecular material and fine powder is broken than refractory material, a kind of as a rule pigment.Thin material crushed can give this coating performance of wanting and/or the outward appearance of wanting.When this coating is opaque, if needed, can apply another layer in the above as the Clear paint layer.

In a particularly preferred embodiment of the present invention, said composition comprises one or more and is selected from pigment, the metallic substance that fine powder is broken, and the pearlescent material that fine powder is broken, the material of ultraviolet screener and antioxidant, and can on matrix, form thermoplasticity colored paint layer.The advantage that this colored paint layer has especially is to use the solvent of colored paint in its coating method.Especially, suitably make for the present composition of the solvent-free colored paint of solid under available a kind of room temperature and have the outward appearance of wanting, for example attrition resistant the and weatherable coating of metal and/or pearlescent appearance.And if needed, can obtain the high gloss facing.Thereby this based composition can reach degree like this, so that for example, can use it for to be formed in does not need outside their forming mould the colored paint finish coat of coating is done surface processing, though also can be such as restock another coating, especially Clear coating on these goods.

In another embodiment preferred of the present invention, said composition includes conductive particle, and this particle gives the coating made with said composition capability of electromagnetic shielding.Use another kind of method, promptly also have in addition by using a kind of conducting polymer composite, for example a kind of composition of polyaniline is to give capability of electromagnetic shielding.

Do more detailed discussion in this manual after a while for the preferred material that the present composition uses.

Will appreciate that this coating made from the present composition and is not the coating that is coated on the preformed matrix as a rule not necessarily.Therefore, the goods that contain the coating that useful said composition makes can be made by a kind of method, being added to time in the mould for doing the thermal softening of matrix or melting material in the method, is before adding softening or melt coating composition, afterwards or basically simultaneously.With regard to coetrusion, use one or more heads rather than mould, coating and matrix form basically simultaneously.This coating can be on one or more surfaces of matrix.

Concerning the purposes of this specification sheets, this coating is the outermost layer on the matrix.Therefore, if between coating and matrix main body one extra play is arranged, this extra play is regarded as the part of matrix concerning this specification sheets purposes.This extra play can be, for example a kind of polymer colored paint layer with metal appearance is coated layer at polymer colored paint layer and formed a Clear coating, and this extra play also can be the polymer prime coat of colored paint coating.Above-mentioned extra play can be made with following method easily, for example with a kind of many cylindrical shells injection molding machine or with coextrusion succeeded by blowing.But, in some cases preferably this dope layer directly contact with the body body material, between does not inject extra play.

In the occasion of making goods with moulding method, the thermoplastic coating material preferably is fusion or flowable soft state when it is coated on mould or the matrix surface, that is to say, preferably make this coating by fusion or remollescent thermoplastic material flow on mould or matrix surface, this thermoplastic material can be particulate state.This coating preferably is not, or do not form the part of ready-made tablet, and this tablet then contacts with matrix or body material.

Applicant unexpectedly finds, the present composition can be used for producing as a rule without further processing and just is suitable for the coating used.For example, the curing process after the molding is optional, and the outward appearance of coating and performance reach such degree so that there is no need to apply another layer, for example colored paint layer or other protective layer again before goods use.For example, as mentioned above, this coating can form a kind of " colored paint " layer with the performance wanted and outward appearance.In this occasion, the preferred thickness of this coating is only 500 μ m of maximum, better be only 200 μ m of maximum, coat-thickness is to be advisable less than 100 μ m in some cases, there is the coating of this thickness also can be favourable to other purposes, for example, when coating provides a kind of electromagnetic interference (EMI) screen layer.Preferably, the thickness of the coating of preparation of compositions of the present invention is at least 5 μ m.(when a certain coating is said to be when having a specific maximum ga(u)ge, the regional area of this coating thickness in some cases can be greater than this maximum value, but whole in other cases coating in fact can not surpass the maximum value of this regulation.) composition of the present invention can be used for making thickness and stipulate aforesaid coating.Usually, thin colored paint layer will need more additive such as pigment so that the opacifying power of wanting to be provided in proportion.

By for example selected suitable pigment and/or other fine powder broken than refractory material metallic substance for example, pearlescent material and filler, select the appropriate level of these materials, and/or come a performance of wanting to give the coating of making by said composition in the said composition by following one or more additives are doped to.These additives are ultraviolet screener for example, thermo-stabilizer, and flow aids, pigment, dispersion agent, the shock-resistance modifying agent, intermiscibility dose (Compatibilizers), muddy control agent, stress cracking weaken agent and antioxidant.(as discussed in detail after a while in this specification sheets, also can come the performance of improved coating) by selected suitable thermoplastic macromolecule material.

What so-called fine powder was broken refers to the broken material of infusible basically fine powder under the temperature of said composition coating and use than refractory material, therefore the broken material of this fine powder still is being graininess as in the macromolecular material of said composition, and phenomenon such as for example liquefaction does not take place in this material.What this fine powder was broken as a rule is inorganic than refractory material, but also can be organically, especially with regard to pigment.The broken material of this fine powder preferably contains one or more and is selected from pigment, the material of metallic substance and pearlescent material.Can use the broken mixture of one or more different fine powders than refractory material.If suitable, can also give this coating other performance of wanting as the material of pigment.If needed, the broken infusible basically material of this fine powder can be an electroconductibility, and as following discussed in detail, said composition is suitable for producing conductive coating, this is desirable in some cases.For purposes of the invention, a kind of material does not hinder each manufacturing procedure when being used for making the goods that comprise the coating of being produced by said composition, and it is broken just to be considered to fine powder.The people of the industry can be familiar with being included in the color paint composition the not appropriate granularity of melt material.

The suitable pigment that is entrained in the present composition comprises, titanium oxide for example, and titanium dioxide, zinc oxide, quinacridone, phthalocyanine be the copper phthalocyanine complex compound for example, anthraquinone type compound, thioindigo color, and carbon black.Calculate according to said composition weight, the consumption of pigment preferably accounts for 0.5-35%(weight).The consumption of pigment will depend on the color of pigment under specific circumstances, and this available routine test is measured.

In some cases the color of wanting being given can be a kind of pigment that is dissolved in the dyestuff of this thermoplastic, polymeric materials rather than still keeps graininess in thermoplastic material by the thermoplasticity colored paint layer of present composition production.For example can use this dyestuff, though for example the occasion that opacity is given the coating of producing with said composition at the broken infusible basically filler of fine powder also can be used dyestuff in the occasion of a kind of painted transparent layer of needs.

The broken metallic substance of fine powder that is used for being entrained in the present composition comprises the metal that fine powder is broken, the metal derivative that fine powder is broken, and be coated with the metallic particle material.Metallic substance can make the goods that contain by the coating of present composition production have metal shape facing.Metallic substance can be any proper state, for example is particulate state, flakey, and strip, or fibrous.If needed, available a kind of organic substance metallizing material is helped them and is disperseed in thermoplastic material.The example that is applicable to the metal of coating composition is nickel, aluminium, stainless steel and silver, and the alloy that contains one or more above-mentioned metallic substance.The example than the metal derivative of refractory material broken as fine powder is oxide compound, carboxide or salt.Wherein there is the material of the particulate material of metallic coating to comprise, for example is coated with the graphite of nickel and is coated with silver-colored graphite.The consumption of the metallic substance that calculates according to composition weight, if you are using, 5-25%(weight preferably), 10-20%(weight preferably).

Fine powder broken be the occasion of conductive material than refractory material, if needed, this material should use with such ratio and/or such mode, so that have static resistance by the coating of present composition production, semiconductive, or conductivity.For the electro-conductive material of using like this can be, but not necessarily metallic.For example, carbon black is made a kind of antistatic coating, and the broken silver of available fine powder is made a kind of coated semiconductor.Obtain the occasion that the electric component electromagnetic interference (EMI) shields in hope, conductive coating can be particularly preferred.Aspect a kind of coating that EMI shielding can be provided of supply, Stainless Steel Fibre (for example below the diameter 300 μ m, length 3mm is following) is particularly preferred, though other metal for example also can use by nickel or aluminium.The high molecular products that its floating coat forms a kind of EMI screen layer can be used as, and for example needs a kind of cheapness of the electric installation that shields, portable bell housing.

Available a kind of coating composition of the present invention that comprises fine powder cutting metal material is for example forming metal shape facing on the car body part, and does not need to paint again.This metal shape facing not only can improve artistic charm but also can improve wearing quality.Also can accomplish by on transparent material such as sun glasses or the windscreen with the dispersion of a kind of metallic particles in colourless or painted clear coating composition, form metal shape facing.

Pearly pigment comprises, for example micaceous titanium dioxide or superfine titanium dioxide, pearl white; Scribble the pearl white or the mica of titanium dioxide; Titanium oxide; Oxide compound or oxyhydroxide with chromium.The pearlescent material that can make coating contain them to have pearl effect if needed, can make with fine powder cutting metal material and be used for improving the decorative effect that is provided by this metal.Some pearlescent material for example scribbles the mica of titanium dioxide, and a kind of " flicker " outward appearance also is provided.Pearlescent material preferred content in use press composition weight calculate be 5-25%(weight), 10-20%(weight preferably).

Ultraviolet screener comprises, for example hindered phenol.

Following coating performance is particularly preferred during as trolley part with the goods of present composition production, and these performances also can be preferred in other cases.

Said composition preferably contains ultraviolet screener, preferably also contain a kind of pigment, its glossy reduction afterwards is no more than 50% of original size to its content so that coating exposes 200 hours in the QUV test in such ratio, and cracking, efflorescence or be full of cracks do not appear in this coating.Glossy is measured and is carried out according to ASTM D523-67, and the QUV test is as described below.

In QUV test, the good goods of coating or its smooth are exposed under the QUV artificial accelerated aging weather resistance test machine that 8 QUV313nm-B mercury lamps are housed 200 hours, adopt following circulation:

Made light irradiation 4 hours with 60 ℃ of black panel temperature.

With 50 ℃ of black panel temperature lamp was turned off 4 hours.

On goods, form condensation product between exposure period.During whole test, regularly measure gloss and carry out visual inspection according to ASTM D523-67.

Preferably such so that its Taber by ASTM D1044 regulation tests with the coating abrasion performance that said composition is produced, circulation is carried out 250 times.If needed, can be by selected different filler, macromolecular material and/or pigment, and/or the above-mentioned materials of different ratios changes its wear resistance.

The shock strength that the matrix that applies at needs has goods that the occasion of shock strength applies is preferably less than this body material shock strength and is no more than 10%, and can be to be at least 2J(according to BS3900,1973, Pt.E3 illustrates the value of measuring), and the good matrix of this coating preferably shows ductility rather than brittle fracture.By using a kind of thermoplasticity (melt processable) elastomer material, for example the described after a while a kind of material of this specification sheets can improve shock-resistance.

The coating of producing with said composition preferably has to be comparable to the solvent primary colours coats with lacquer the A level automobile facing that can reach.The sign that should not have orange-peel.Good facing can be obtained according to the present invention,, when coated material is the molten state coating, good especially effect can be obtained because in the manufacture method of goods the coated material of softening or molten state is coated on the press polished die surface of energy.

Preferably at least 155 ℃ of softening temperatures through record the composition of a coating on the polypropylene with Vicat tenderizer (ISO306, method A).Beginning remollescent thermal plastic high polymer coated material can obtain preferred coating under comparatively high temps by using.

Applicant has found that the present invention can produce, through Rover industry standard specifications RES.30.EE.102(1990 for example June) goods that are up to the standards.

In general, the present invention can obtain high-quality facing, the facing that uses solvent-free coated material to make before for example high-quality colored paint facing, this facing are better than.In some cases, press polished die surface is desirable to make press polished surface, and it also is desirable heating this die surface.Can use the exasperate die surface when needing the outward appearance of black light, and this die surface is remained under the lower temperature.

The thermoplastic basically coating of available composition production of the present invention.This coating is that the thermoplastic meaning is external phase or the masterbatch that it has one or more thermoplastic materials basically.The coating that is formed by the present composition comprises one or more additives in the external phase inside that thermoplastic macromolecule material forms usually.For example the thermoplasticity external phase of coating can contain the broken material of one or more even or inhomogeneous dispersion fine powders wherein.It is melt-processable that preferred said composition can make the goods by its production, thereby for example makes it and might reclaim.In the case, any additive that is included in the goods for example resembles strongthener or middle layer, all should make them not hinder the melt-processed operation.At the needs goods are callable occasions, and these goods preferably do not contain any middle layer, bonding coat for example, and this layer is infusible under the temperature of carrying out melt-processed.It is peculiar advantage of the present invention that these goods can make its entirely recyclable this fact.

As mentioned above, to make by its coating that forms be that the thermoplastic basically meaning is meant that they have the external phase or the masterbatch of one or more thermoplastic materials to said composition.Wherein this external phase is that a kind of coating of thermosetting polymer does not just have all advantages that can obtain according to the present invention.For example, the goods that contain this coating can not be melt processable thereby be difficult to reclaim easily.On the other hand, the cross-link bond that is the ionic linkage state between the polymer chain of ionomer material is ruptured by this material of heating, but material forms cross-link bond again when cooling off again.Above-mentioned this ionomer is that ionomer just can melt-processed, thereby is included in noun " thermoplastic material " scope that is used for this specification sheets.Also having thermoplastic elastomer also is like this, and wherein cross-link bond can reversibly rupture when heating.

Said composition with ionomer or thermoplastic elastic material or in general, the use possibility of the material that cross-link bond can reversibly rupture when heating is a peculiar advantage of the present invention, make it can make the coating that performance is better than thermoplastic coating, thermoplasticity colored paint layer for example is not because thermoplastic material at room temperature contains cross-link bond between the macromolecular chain.Also the reversible crosslink material to be discussed after a while in this manual.

As mentioned above, coating composition of the present invention can be used for producing the goods that are made of the thermoplastic coating on the thermoplastic matrix.In the case, said composition preferably comprises a kind of thermoplastic macromolecule material, and this material is miscible with the thermoplastic matrix of being produced by the present composition under the temperature of die for molding at goods at least.The compatibility of coating and body material has strengthened the bounding force of coating to matrix, and when coating did not have complete enclosing substrate, this catered to the need especially.

The compatibility polymkeric substance that is used to prepare the goods that are made of the thermoplastic coating on the thermoplastic matrix should at least at least in part can be miscible under the temperature of die for molding at goods.But with regard to some coating/matrix combination, especially when for example adopting the hot spray process article of manufacture, on the interface that two kinds of materials of controlled refrigerative are arranged, produce quite closely and mix, thereby this can be trapped in the polymer network that the body material the inside forms a kind of interpenetration to coated material.(this tight mixing can not take place usually when applying coated material with electrostatic spraying).For purposes of the invention, the blended material also is considered to compatibility by this way.

Adopt hot spray process, especially flame spraying to apply coated material and also may accomplish to use originally immiscible coated material, this coated material makes it become more miscible and formation adherent coating by the heat of spray equipment.

Just can promote bounding force (that is to say, can improve compatibility) by in immiscible coating composition originally, adding the compatibility dose.Suitable compatibility dose comprises that those have the polymkeric substance that partly polymkeric substance of each blend is had avidity in molecule, and those make the crosslinked additives of formation low degree between the polymkeric substance under the situation of not damaging polymeric thermoplastic.

In order to obtain good bounding force, preferably in the coating composition in contained its most of repeating unit of polymkeric substance and the body material contained most of repeating unit identical, but this is not always to be absolutely necessary.

Preferably selected like this coating and body material, and working condition, so that goods can pass through cross network cross cut test (BS3900E6/ISO2409), this experimental measurement coating is to the bounding force of matrix.

If body material is surrounded and sealed to coating fully, between not necessarily always will have good bounding force so.Can use immiscible material in this case without any modification.Available a kind of unmixing coating of sealing matrix is come the protecting group surface, this on matrix bonding not firm coating, can easily remove and expose clean surface.

In some cases, the selected thermoplastic macromolecule material of this coating composition that is used for is just for obtaining the maximum adhesion to matrix.But under other situation, the contribution that thermoplastic macromolecule material is made the coating physicals also is important.What can influence coating performance is, the molecular weight of polymeric coating material for example, polymeric coating material particular type selected, and/or the use of polymeric coating material mixture.

A kind of during when wanting to make than the more tough and tensile more durable coating of matrix surface, preferably use a kind of polymkeric substance higher than the molecular weight of matrix.An advantage of the invention is, can be higher than the molecular weight of the coated material that the coating of common solvent primary colours lacquer and/or coating electrostatic coating be suitable for for the molecular weight of thermoplastic polymer of doing coated material.For example, when with the electrostatic method applying powder coating, the molecular weight of macromolecular material and melting index are subjected to making the restriction of the required flowing property of a kind of coating that qualified outward appearance arranged.The present composition can suitably be used for coated material wherein and be the production method that plastic state exists when contacting with die surface, therefore can allow higher molecular weight.With compare to the coating of die surface electrostatic coating, use the polymkeric substance of higher molecular weight can obtain fabulous scuff resistance, hardness and mechanical property.

In an embodiment preferred of the present invention, coating composition comprises a kind of reversible crosslink plastic macromolecule material hot in nature, for example, and ionomer or thermoplastic elastomer, wherein cross-link bond reversibly fracture by heating.Comprise the occasion of ionomer or thermoplastic elastomer at coated material, wherein preferably also comprise another kind of thermoplastic macromolecule material, preferably exist with vast scale, then the reversible crosslink material is to exist than small proportion.

Ionomer is a kind of by adding metal-salt at the crosslinked thermoplastic material of solid-state generation low degree, and this metal-salt forms ionic linkage between this polymer chain.The ionic linkage that forms is hot reversible, therefore can adopt the melt-processed method that is suitable for the typical heat plastic material to make goods from ionomer.If needed, ionomer can with the polymer blending of other type, the thermoplastic polymer of for example mentioning in this manual.Using ionomeric occasion, its consumption advantageously accounts for the 5-80%(weight of coating composition weight), better be 5-15%(weight), preferably about 10%(weight).

Ionic cross-linked bond in the ionomer makes by the toughness/rigidity that contains the coating that ionomeric coating composition thing makes, and hardness and heat deflection temperature (HDT) are improved.In addition, do not form free radical (this base can carry out deleterious reaction) during owing to the ionic linkage fracture, the shock strength of coating also is improved.Ionomer can also make the pigment in the coating composition and the compatibility of macromolecular material be improved, and the illuminated (paintability) of final coating is improved.The improved performance of final coating is to realize by the crosslinking degree in ionomer ratio in thermoplastic polymer/ionomeric concurrent mixture in the suitably selected coated material and/or the suitably selected ionomer.Crosslinking degree depends on the ratio of used metal-salt in the ionomer manufacturing processed usually.In the occasion of the black light facing of end article needs, preferably use the ionomer of larger proportion; Preferably use ionomer with need be the time than small proportion than the glossy facing.

For making coating have desirable shock strength, preferably doping is a kind of in said composition can reversible crosslinked melt processable elastomer material.This elastomer material, if exist, its consumption is the 1-70% of coating composition weight preferably, preferably 10%(weight) below.An example of this thermoplastic elastic material is a kind of styrene-ethylene/butylene-styrene multipolymer, and this multipolymer is at room temperature crosslinked.This cross-link bond is ruptured by heating, thereby makes this material can melt-processed.

In a preferred embodiment of the present invention, this coating composition comprises a kind of thermoplastic polymer alloy.Thermoplastic polymer alloy can make by two or more thermoplastic polymers melt blending under the situation that the compatibility dose is arranged, the chemistry of gained alloy and/or physicals are better than any one independent part polymkeric substance, and are better than the simple mixtures of each polymkeric substance.If needed, the compatibility dose can add after the melt blending operation.An example that is applicable to thermoplastic polymer alloy of the present invention is polymeric amide/polypropylene alloy.

Composition of the present invention can comprise more than a kind of thermoplastic macromolecule material so that make the coating of being produced by said composition have desirable character.For example, said composition can comprise a kind of thermoplastic macromolecule material and the another kind of blend that improve the thermoplastic macromolecule material of coating physicals good with the body material compatibility that proposes.(the above-mentioned another kind of material and the compatibility of body material can be got well also can be bad).Mention some kinds of preferred blends in this manual.

In an embodiment preferred of the present invention, this coating composition comprises the host polymer component of body material, in suitable occasion, add one or more be selected from fine powder broken than refractory material and above mentionedly be suitable for making this coating to have the annexation of the performance of catering to the need.For example the polypropylene colored paint produces good coating on polypropylene matrix.The macromolecular material of coating, for example polyacrylic molecular-weight average can be identical with the molecular-weight average of matrix, if needed, and also can be different, for example can be higher than the molecular-weight average of matrix.

The used polyacrylic preferred type of coating composition of the present invention be number-average molecular weight greater than 150, the 000(gel permeation chromatography) linear polypropylene.Particularly preferred coating composition comprises a kind of thermoplastic material and polypropylene of energy reversible crosslink.

In a preferred embodiment of the present invention, this coating composition comprises a kind of blend, it consists of in the miscible polymkeric substance of at least a and body material and/or at least a its molecule the identical polymkeric substance of most of repeating unit in the most of repeating unit and matrix material molecules, with at least a macromolecular material, for example, a kind of material (this material can make this coating have to be different from the various performances of matrix) that can reversible crosslink.By component and the ratio that changes this blend, can make blend be fit to the coating performance that provides required.For example, a kind of preferred blends of using for polypropylene matrix be a kind of polyethylene that comprises small proportion (if needed, the material that can comprise a kind of energy reversible crosslink, polyacrylic blend with vast scale, and a kind of preferred blends of using for polyamide substrate is a kind of polyamide/polypropylene blends, for example polymeric amide/polypropylene alloy of the trade(brand)name Orgalloy of AtoChem company R60ES.

The example that can be used for the thermoplastic material of the present composition comprises the homopolymer and the multipolymer of propylene and contains alfon and/or the thermoplastic alloy of multipolymer (for example, polypropylene/polyamide alloy), the homopolymer of ethene and multipolymer, polymeric amide, abs polymer, polystyrene, poly-(methyl) acrylate, polycarbonate, thermoplastic polyimide, polyester, urethane, polyvinylidene difluoride (PVDF), and polyvinyl chloride.Certainly use the blend and the alloy of two or more above-mentioned materials.

Thermoplastic macromolecule material is for degree that the muddiness in the final coating is minimized in the selected better said composition.

Enable goods japanning subsequently though the present composition can be used for producing the colored paint layer and become unnecessary, this situation also can be arranged, wherein apply another layer, for example Clear coating can be desirable.In addition, desirable is that this coating composition is such colored paint form, can repair when the colored paint coating is in use impaired.In this occasion, desirable is to comprise a kind of polymkeric substance (for example functionalised polyolefin) that contains low ratio polar group (for example carboxyl) in coating, or comprises the additive that another kind makes the bounding force raising that is coated to colored paint on the coating subsequently.But often importantly the ratio of polar group should be too not high, in order to avoid coating composition adheres on the metal easily: the coating composition that adheres to easily on the metal is not suitable for coating process in the mould usually.Can measure suitable polar group content easily with routine test.

Coated material of the present invention can prepare with suitable method.In a preferable methods; with thermal plastic high polymer parent or solid support material for example at rotary drum; in fountain or other mixing tank with desired additive pigment for example; filler; metallic particles or UV absorption agent are puddled together in advance; make this mixture melting mixing then, cooling, and be transformed into particulate state.Impel additive abundant dispersive melting mixing in fertile material to realize with for example forcing machine or two-roller mill.Molten mixture then can for example chilling be to make extrusion by head and at the head face or in water-bath, and this extrusion is used the cutting blade granulation subsequently.In one case, find that when adopting the two-way injector to form goods the colored paint particle of length 3mm diameter 2mm is preferred, though can use the particle of any size that is suitable for the injection molding machine feeding unit.

In another possibility, some additives for example metallic particles and/or pearlescent particles are not to add but add in later phases puddling operation in advance, and this is in order to prevent that processing from causing the damage particle.A kind of method that reaches this purpose is at first to make the particle that contains whole components in coating compositions (except that metal or pearlescent material) softening in the fluidized bed dryer of a heating, add metal or pearlescent particles then, this particle adhesion is at the outside surface of softening particle.Use another kind of method, can add metal or pearlescent particles in remaining coated material to towards extruder barrel tail end direction by the enriched material in the intermiscibility carrier.

When being the used coating composition of some manufacturing process (for example flame spraying) preparation of goods, preferably the coating cryogenic freezing is ground to form coating powder.Generally be when coated material comprises more than a kind of component, blend is extruded in these component elder generation blend; granulation or pelleting, cryogenic freezing is ground then, and the temperature in the grinding machine is-50 ℃ or lower; generally be lower than one 80 ℃, also available other the preparation method of thermoplastic powder.

If needed, can be added to pigment in the coating and other material with than the thermoplastic macromolecule material blend of small proportion forming a kind of masterbatch, this masterbatch is in the need time spent, can with remaining for the thermoplastic material blend that do coating.The preparation of masterbatch can help to disperse and avoid using pigment powder in extensive the manufacturing.This is to preventing the local environment pollution and/or preventing potential explosive dust mixture particularly advantageous.

In principle, any thermoplastic material all can be used to make the matrix in the goods that comprise the coating of being made by composition of the present invention, but owing to for example physicals and/or material price, specific material can have advantage in some applications.Owing to can make high-quality coating with composition of the present invention, can not consider that the surface property and/or the outward appearance of goods select body material, this can accomplish to use at a low price and/or salvage material under many circumstances, for example, the material of pbz polymer material blends and/or contain pigment and/or from the material of other graininess material that reclaims the thermoplastic article melt-processed.Even, can contain relatively large admixture in the salvage material as long as they do not hinder and are used for producing the working method of goods or the performance of goods.Body material can contain the material that makes this material have the character of catering to the need, and for example filler if needed, can contain whipping agent so that obtain the matrix of foaming.

The example of suitable body material is the homopolymer and the multipolymer of propylene, the homopolymer of ethene and multipolymer, polymeric amide, abs polymer, polystyrene, poly-(methyl) acrylate, polycarbonate, thermoplastic polyimide, polyester, urethane and polyvinyl chloride, and the blend of these polymkeric substance and/or alloy.

As mentioned above, the goods that comprise the coating of being made by composition of the present invention can be made with any suitable method.Preferred product molding method comprises makes coating and matrix in same die for molding, and moulding Front-coating mirror material and body material drop in mould in proper order or simultaneously.But can use coetrusion in suitable occasion.

The example that drops into the method for coated material in mould comprises hot spray process, and flame spraying especially is a coated material in the condition of spray-on coating material on the die surface wherein softens or molten state with should being before the surface contacts; For example Powdered coated material is coated on the die surface, makes powder melts form coating then with electrostatic spraying.Preferably with before die surface contacts, this coated material is softening or molten state (mixture that comprises softening and melting material).

In some cases, preferably be coated in coated material on the body material rather than be coated on the die surface.For example, the available heat spraying method is sprayed on coated material on the body material, subsequently body material is placed in the mould.

Body material can drop in the mould in any suitable manner.For example, body material can be the cohesiveness bulk, and this block is placed in the mould like this, submits to the compacting molding process to handle then.In the case, be preferably in body material and put into before the mould, be coated in coated material on the substrate material surface and apply on die surface.

In another preferable methods, the body material that is molten state is injected in the mould.If needed, can or send out in the body material input mould of spumescence foam materials.

Make according to the present invention in the another kind of method of goods, coated material and body material are extruded by an extruder head simultaneously in the coextrusion operation.

Can comprise thermoplastic coating material and thermoplastic matrix material owing to contain the goods of the coating that is formed by composition of the present invention, after molded, coating or matrix do not need to solidify.Ready-made product can effortlessly just take out from mould.Necessary words are in product cooling back or its cooling back is taken out.The words that need can make product cooling beyond mould.

Provide the data of more relevant preferred product manufacture method below.

As shown above, a kind of preferred method of making coating is, makes coated material be sprayed on the surface under following condition, promptly allows this material be in fusion and/or remollescent state before with the surface contact.This material is coalescent from the teeth outwards then and form continuous coating basically.This method is well suited for makes injection molding product and compression molded article, and the words that need also can be used for making the goods with other method moulding.

The surface that coated material was coated with can be the surface of mould or the surface of body material.Preferably all basically coated materials all were in softening or molten state (or mixture of softener material and melting material) before surface in contact, though there is the small portion material still can be in solid, nonplastic state, as long as its is with the fusion of when contact surface with flow, or fusion and mobile when contact with lip-deep softening or molten coated material.Under this preferable case, be coating with the occasion that has been melted before the surface contacts, this material not heat of abutment surface melts it, but also can be by one of mould and body material or both, and the words that need also can provide additional heat by carrier.Therefore, keep mould more than room temperature but the melt temperature that is lower than body material can be reasonably, thereby obtain satisfied cycling time and form matrix and coating.

This coated material can be coated on the surface of the internal surface of a surface such as open mould or closed molds.

Heat can impose on coated material by any suitable extra power before the coated material surface in contact.Therefore, for example, can add warm air with hot air gun, the powder coating material heats by Hot air quilt when to surface transport.Also can adopt detonation flame spraying or plasma spraying in air, or so spraying in vacuum chamber or pressurizing chamber.But, coated material preferably adopts the flame plating rifle to come coated surfaces.The powdered coated material can along flame kernel or around flame by and by hot gas such as warm air beating.If select for use correct condition to comprise temperature and granularity, then powder can be enough to make its softening or fusion but be heated by flame ignition.Can determine by customary experiment any given optimum granularity of powder.Only size range depends on the setting of used spray gun under any particular case.

When applying this coated material by hot spray process, the material that forms matrix can be introduced mould by any suitable method, for example by injecting body material making under the body material fused temperature, perhaps by introduce a slice body material from slide glass or precast body, this material can contain for example a kind of strongthener such as glass fibre, and if desired or require, before introducing mould, can heat (what use body material may be to share from slide glass or prefabricated component to making as floor tile or top board brick) in advance.In general, coated material is before body material is introduced mould or be coated on the die surface simultaneously basically.Coated material and body material can be made goods of the present invention by any suitable molding methods moulding, as passing through jet molding or compression molding.In moulding process, need, can apply auxiliary heat.Molding finishes, and if desired, can allow moulded product cooling or make its cooling, takes out from mould then.

The applicant unexpectedly finds, when adopting above-mentioned method, can obtain durable coating on plastic substrate, even with the high speed injection body material.Apply coated material with for example electrostatic gun at die surface, when at full speed injecting body material, often cause in powder, forming the line trace that flows.The feasible uniform coating that may obtain institute's required thickness of thermospray.The thickness of coating can be regulated by selecting the spraying condition.

Specified as this specification sheets front, this coated material can contain the metallic substance of one or more pulverizing, as particle, and fiber or thin slice.Have been found that if in above-mentioned hot spray process used coating material, contain metallic material particles when being used for making the injection-molded product of band coating, particle is extruded the surface of coating, obtain excellent decorative encasing thus.When making the compression molding product, find that metallic particles is extruded the interface to coating and matrix with same coated material.This electromagnetic interference shield to electron device can be useful.

The present composition makes may for example obtain high-quality durable coating on the thermoplastic matrix, these matrixes such as polypropylene or polyethylene, and they can not apply with rational cost satisfactorily in order to the composition of prerequisite confession.Can obtain the satisfactory coating bounding force and do not need to improve the surface (as flame treating, corona discharge, chemical corrosion or Cement Composite Treated by Plasma) of matrix or improve whole polymkeric substance with the inventive method with pre-treatment.Can be with the short production that realizes the matrix of band coating cycling time, and in the low occasion of the surface energy of used coating, can be at die surface without release agent.In addition, because coated material can be to be in softening or molten state when contacting with mould, usually can from the mould that has moulded product, remove any excessive material, clean thereby mould is seldom needed or do not need, even mould is used for the goods of different color and lusters.Said composition can be used for the complicated goods of production shape.

A special advantage of the present composition is, it makes (occasion that especially adopts high polishing mould) might make the goods that the colored paint layer has enough high glossiness, as the Motor vehicles component, and need not be for further processing, even be used in the high gloss facing occasion that is absolutely necessary.Therefore, said composition embodies very big advantage in the automobile component manufacturing that for example contains the thermoplastic matrix material.

The present composition makes might for example make goods from low-cost thermoplastic material, and these materials comprise twice-laid stuff, and does not need to add the heavy addition agent to give desired performance of integral material and desired outward appearance in this material.And the material of any interpolation can be limited in the scope of coating, needs, and allows that coating composition uses more expensive material such as high-performance engineering polymkeric substance, comprises blend polymer and alloy.Also avoided use solvent-borne type coating method institute inherent problem in addition.If necessary, can select coating composition to make it possible to coating another layer coating such as transparent varnish coating on the coating of making by it,, the present invention avoids as far as possible with this class varnish coating though generally will making.Coating composition can be by solid state, solvent-free, thermoplasticity colored paint (making particulate state or powdery) feed, and does not need to solidify.

When using metallic coating composition, before the applying coatings composition, may on mould, be coated with release agent.If the surface energy of coated material is low, make it not quite easily with the mould adhesion, other coating composition that then is used for making coating can not need to use release agent.

The present invention especially makes may provide such automobile component, and these parts are made by the thermoplastic matrix material and tool is deposited high-quality coating, and this coating a slice coated material that can not need to fit is made to the ready-formed matrix.Therefore the present invention embodies very big advantage in automotive industry, solved one should industry all a difficult problem of studying (making the thermoplasticity automobile component of band coating).

The following example is understood the present invention specifically.Among these embodiment, unless otherwise specified, its percentage number average by weight.

Embodiment 1

A kind of thermoplasticity color paint composition, it comprises:

87.1% polypropylene (melting index 25.0 grams/10 minutes are pressed ISO1133 and measured, and at 230 ℃, load 2.16 kilograms)

10.0% barium sulfate weighting agent

2.0% black pigment

0.5% antioxidant

0.4% ultraviolet screener

Said composition is used for making the polypropylene automotive component (a kind of battery tray) of band coating.Each component of color paint composition is mixed, and with the mixture extruding pelletization, in-80 ℃ of temperature cryogrindings, the powder median size that makes is 120 μ m to pellet in an Alpine UPZ160 mill.

With the inner face of powder flame plating at an open injection molding, this spray gun has a right angle nozzle and the feed hopper that deadweight is little with a hand-held flame plating rifle.This mould is preheating to 80-100 ℃ of temperature, and the compressed air pressure of supplying with spray gun is 2.25 crust (0.225MPa), and the powder velocity of flow of formation is about 25 Grams Per Minutes (about 0.4 Grams Per Seconds).Used fuel gas is oxygen and acetylene.

When mould inside has one when continuous coated, the involution mould is injected into mould with the polypropylene matrix material in about 200 ℃ temperature.After part cooling, from mould, take out thermoplastic molded and make its cool to room temperature.The mean thickness of coating is 150 μ m.In immersion before 24 hours and afterwards, coating is by cross hatch bond test (BS3900E6/ISO2409), spoilage 0%.This coating is also by environment circulation (65/U) test (RES30EE102 Issue 9, this standard is the part of Rover Engineering Standard RES.22.PL.08), also by humid test (BS3900Part F2-168hr), and clean (80 ℃, 80 crust (8MPa), 1 minute (60 seconds)) test.

Embodiment 2

A kind of thermoplasticity color paint composition, it comprises:

79.1%(weight) polypropylene (as the color paint composition of embodiment 1)

20.0%(weight) white pigment

0.9%(weight) antioxidant

On a slice glass fibre enhanced polypropylene, apply the colored paint layer with said composition.Adopt the spray gun of embodiment 1 same-type and the device of rifle, on open compression mould (Hounsell press) internal surface, this mould is preheating to 80-100 ℃ temperature the colored paint powder flame plating of mean particle size 120 μ m.When described mould inner surface has continuous coating, the matrix prefabricated component of a slice preheating is placed on the surface that sprayed in the mould.Close mold then, stamp out desired shape thus.After the part cooling, from mould, take out moulded piece and make its cool to room temperature.Coating mean thickness 150 μ m are high-quality coatings.

When repeating this embodiment, but, also can obtain the quality coating of thickness 150 μ m at spray-on coating material on the body material rather than on die surface.

Embodiment 3

99.25 weight % polymeric amide/polypropylene alloy (trade mark with Orgalloy R60ES is sold)

0.50 weight % carbon black masterbatch

0.25 weight % antioxidant

Above material is pressed embodiment 1 described mixing, extrude and grind, to make the thermoplasticity color paint composition (in this masterbatch, carbon black is with polypropene blended on a small quantity) that increases equal particle diameter 120 μ m.With embodiment 1 described flame plating rifle with the inside of this composition flame plating at injection molding.

When mould inside has when continuous coated, injection nylon 66 body materials in the mould, injection temperature is about 250-300 ℃.The mean thickness of final thermoplastic article coating is 150 μ m, and coating is good with the body material bonding.

Embodiment 4-8

A kind of thermoplastic paint composition, it comprises:

91.6% polypropylene (as the color paint composition of embodiment 1)

0.5% antioxidant

0.4% ultraviolet screener

The polyolefinic ionomer of 5.0% acrylic acid or the like modification

With this composition (embodiment 4), adopt embodiment 1 described universal method to make a kind of thermoplastic article (matrix of band coating), polypropylene is as body material.

Among the embodiment 5-7, use a kind of reversible crosslink styrene-ethylene/butylene-styrene rubber (trade names of sale are Kraton) of 5% respectively, a kind of lower molecular weight ionomer, and a kind of polyolefinic ionomer replaces acrylic acid modified polyolefinic ionomer.Among the embodiment 8, a kind of polypropylene, polyethylene blend with 96.6% replaces polypropylene and acrylic acid modified polyolefinic ionomer.The body material of each embodiment is a polypropylene among the 5-8.

Among each embodiment of 4-8, the coating that the goods that make comprise, its thickness is no more than 150 μ m, and has excellent performance.When adopting the regenerated polyolefine to make body material repetition embodiment 4, obtain similar result.

Embodiment 9

Adopt same body material and following coated material to repeat embodiment 1 described coating method:

87% polypropylene (as the color paint composition of embodiment 1)

0.5% antioxidant

0.4% ultraviolet screener

The aluminium (mean particle size 75 μ m) that 4% fine powder is broken

The aluminium (mean particle size 200 μ m) that 2% fine powder is broken

4.1% styrene-ethylene/butylene-styrene reversible crosslink rubber

Make a kind of thermoplastic article, the thickness of its metal shape coating is less than 150 μ m, and coating has excellent outward appearance and performance, comprises the electromagnetic interference (EMI) shielding properties.Therefore the broken aluminium of fine powder avoided oxidation below the coatingsurface that exposes.

Embodiment 10

With the homopolymer polypropylene sample of pellets in a flat mixer with various component pre-mixings.Polyacrylic weight-average molecular weight MW is 200,000-280, the 000(gel permeation chromatography), melt flow index is 25 grams/10 minutes (pressing ISO1133 measures), various components are a kind of styrene-ethylene/butylene-styrene crosslinkable rubber, a kind of hindered phenol antioxidant (selling with trade names Irganox1010), two kinds of ultraviolet screeners, strip is transparent contains mica titanium dioxide and a kind of pigment composition.

The ratio of various components is as follows:

Parts by weight

Polypropylene 2028

Styrene-ethylene/butylene-styrene can be handed over

Connection rubber 250

Irganox1010 12.5

Phthalocyanine green (BASFL8730) 25

Phthalocyanine blue (BASFL6920) 25

Special black 4A(carbon black) 1.35

Scribble TiO ₂Superfine flash of light mica 82.5

Scribble TiO ₂Flash of light mica 12.5

Outdoor use high brightness blue (band chromium oxide coating

Contain mica TiO ₂) 50.0

Ultraviolet screener 13.50

With 200 rev/mins (rpm), length-to-diameter ratio is 16 to extrude this mixture, 160 ℃ of temperature in readings, 160 ℃ of barrel temperature readings, 180 ℃ of head temperature readings with a thermoplasticity forcing machine.Sudden cold in water-bath at the monofilament that head makes, and the colored paint pellet of long 5mm diameter 2mm is made in granulation.

Use pellet to make coating (mean thickness 300 μ m) on polypropylene matrix with coating process in the mould, the goods of covering with paint are automobile component.

The glossiness of measuring the facing component surface with ASTM D523-67 is 90% at 60 ° of ends.When comparing with the standard automobile panel, the outward appearance of metal shape (giving) by pearlescent material be light and also be A level facing.

The facing component suffer and by following performance test.

Cementation test: BS3900/ISO2409-passes through Gto at 2mm.

Salt spray test: ASTM117B1000 hour-do not have and ftracture or foaming.

The QUV weatherometer: 313 millimicrons of nothing cracking or foamings in mercury lamp B500 hour, former loss of gloss is no more than 50%.

Filth test: gasoline, diesel oil, brake solution, acetic acid 0.1M, HCl0.1M.

The no color and luster in coating back changes

Embodiment 11

The following a kind of coated material of method preparation prescription according to embodiment 10 regulations as embodiment 10:

Parts by weight

Polypropylene 77

Aluminium pigment in the protectiveness resin

(elongated pieces of long 75 μ m) 3

Pearly-lustre white 2

The Scotchlite(trade mark) CIS/250 granulated glass sphere 10

Crosslinkable rubber 8 as embodiment 10

This coating is used for producing the interior coating process of mould of automobile component.This body material is and used identical of embodiment 10.

Make a kind of thermoplasticity automobile component of feeling quite pleased coating that have thus.This coating is 130-160 μ m at the thickness of this component outside surface, and Biao Mian thickness is 20-40 μ m within it, and this coating is by the pointed test of embodiment 10, and weather-proof (QUV) test that is used for embodiment 11 was carried out 300 hours.Aluminium pigment in the coating near the surface but protected by one layer of polymeric.Needle-like aluminium is orientated in coating.

Embodiment 12(contrasts and uses)

Prepare a typical powder coating prescription by the following component of premix: a kind of thermosetting resin that contains triglycidyl group isocyanuric acid ester (TGIC), a kind of flow promotor, and make the st-yrax that degassing auxiliary agent is used.Then mixture is extruded at 120 ℃ with a WernerPfleiderer forcing machine.

The gained extrudate is broken into small pieces, grinds to form the following fine powder of size distribution again:

100% greater than 15 μ m

55% greater than 32 μ m

0% greater than 100 μ m

Sneak into mixture or be bonded on the surface of powder particle aluminium powder is dried.Then powder is coated on the aluminium sheet by an electrostatic gun, and 200 ℃ of heating 10 minutes.

Gained colored paint film is exposed under embodiment 10 described salt fogs and the weather resistance test condition (QUV), finds that paint film degenerates very soon.The flash effect that is reached is low-quality, and this paint film does not have A level automobile facing.

Usually find,,, then can obtain excellent performance if the material that adopts contains reversible crosslink plastic material hot in nature when (comprising thermoplastic alloy) though all the foregoing descriptions of the present invention can both make satisfactory coating.

Embodiment 13

Present embodiment is understood a kind of manufacture method that is applicable to the present composition specifically.

The sour grafted polypropylene of a kind of usefulness (trade names with Polybond2015 are sold) sample is extruded and granulation, the pellet cryogrinding is become fine powder.Use an APU forcing machine (screw speed 250rpm, moment of torsion 55-60% then; 200 ℃ of barrel temperatures) with this powder and 10%NaHCO ₃(weight is by sour graft polypropylene weight) blend, and be shaped to a slice decorative sheet, with it 200 ℃ store 10 minutes before and check with infrared spectrometer afterwards.Use 1% and 5% NaHCO in addition respectively ₃Also make decorative sheet (extrusion temperature is respectively 148 ℃, 185 ℃).When large-scale processing, can save the cryogrinding operation for example carrying out blend in a forcing machine.

Infrared measurement shows that the acidic group in the sodium ion neutralizing acid graft polypropylene generates ionic cross-linked bond between polymer chain.As the NaHCO that adopts higher proportion ₃The time, reach the crosslinked of higher density.After extruding operation, salt is incomplete with the reaction between the polymkeric substance, therefore requires storage procedure to be reacted completely.

The ionomer of gained is specially adapted to be mixed in together with polypropylene, is used to be applicable to the coated material of polypropylene matrix.

Claims

1, a kind of coating composition, be applicable to coating process in the mould, it comprises thermoplastic, polymeric materials that first kind thermoplastic, polymeric materials, second class can reversible crosslinks and at least a material that is selected from broken pearlescent material, ultraviolet screener and antioxidant of coloured material, fine powder broken metallic substance, fine powder.

2, composition according to claim 1, wherein first kind thermoplastic, polymeric materials comprises alfon or multipolymer.

3, a kind of coating composition that is used for coating process in the mould comprises a kind of thermoplastic alloy and at least a material that is selected from broken pearlescent material, ultraviolet screener and antioxidant of coloured material, fine powder broken metallic substance, fine powder.

4, composition according to claim 3, wherein said thermoplastic alloy comprise the first kind and the second analog thermoplastic polymer materials and their intermiscibility dose.

5, according to claim 3 or 4 described compositions, wherein said thermoplastic alloy comprises polypropylene and polymeric amide.

6, a kind of thermoplasticity color paint composition, comprise alfon or multipolymer, coloured material and at least a material that is selected from broken pearlescent material, ultraviolet screener and antioxidant of the broken metallic substance of fine powder, fine powder, said composition are applicable to coating process in the mould of the goods that production is made of polypropylene matrix and the coating that is formed by said composition thereon.

7, a kind of thermoplasticity color paint composition, comprise alfon or multipolymer, ultraviolet screener and at least a coloured material that is selected from, the metallic substance that fine powder is broken, the pearlescent material that fine powder is broken and the material of antioxidant, said composition is applicable to coating process in the mould of the goods that production is made of polypropylene matrix and the coating that formed by this group things thereon, the ratio of contained ultraviolet screener and described material should make after coating is subjected to defined QUV test to handle 200 hours in the composition, press the test of ASTM D523-67 method, its gloss reduction is no more than 50% of former level, and coating does not chap, chalking or do not have crazing not.

8, a kind of thermoplasticity color paint composition, comprise alfon or multipolymer and at least a material that is selected from broken pearlescent material, ultraviolet screener and antioxidant of coloured material, fine powder broken metallic substance, fine powder, said composition is applicable to coating process in the mould of the goods that production is made of polypropylene matrix and the coating that formed by said composition thereon, this coating has wear resistance, can finish 250 circulations by Taber test as ASTM D1044 defined.

9, a kind of thermoplasticity color paint composition, comprise alfon or multipolymer and at least a material that is selected from broken pearlescent material, ultraviolet screener and antioxidant of coloured material, fine powder broken metallic substance, fine powder, said composition is applicable to coating process in the mould of the goods that production is made of polypropylene matrix and the coating that formed by said composition thereon, these goods have shock resistance, press BS 3900,1973, the PartE3 standard testing is at least 2J, is lower than the polypropylene matrix measured value and is no more than 10%.

10, according to each described composition of claim 1 to 9, the coloured material that comprises is a pigment.

11, according to each described composition of claim 1 to 10, comprise a kind of electro-conductive material, and be suitable for producing the EMI screen layer.

12,, also comprise a kind of material of energy reversible crosslink according to each described composition of claim 3 to 11.

13, according to claim 1 or 12 described compositions, the material of wherein said energy reversible crosslink is a kind of ionomer.

14, according to claim 1 or 12 described compositions, the material of wherein said energy reversible crosslink is a kind of thermoplastic elastomer.

15, according to each described composition of claim 1 to 14, be suitable for applying with hot spray process.

16, according to each described composition of claim 1 to 15, be suitable for applying with flame spraying.

17, according to each described composition of claim 1 to 14, be suitable for being used for injection-moulding device.

18, according to each described composition of claim 1 to 14, also be applicable in the coextrusion equipment.

19,, be powder or particulate material shape according to each described composition of claim 1 to 18.

20, according to each described composition of claim 1 to 19, as described herein substantially.

21, according to each described composition of claim 1 to 20, the application in the mould of the goods that the coating that production is formed thereon by thermoplastic substantially matrix and said composition constitutes in the coating process.

22, contain larger proportion alfon or multipolymer and be used to produce the application of the goods that polymeric matrix and the coating that is formed by said composition constitute than the small proportion ionomer thereon.