CN1532004A - Method for producing composite coating - Google Patents

Method for producing composite coating Download PDF

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Publication number
CN1532004A
CN1532004A CNA2004100326017A CN200410032601A CN1532004A CN 1532004 A CN1532004 A CN 1532004A CN A2004100326017 A CNA2004100326017 A CN A2004100326017A CN 200410032601 A CN200410032601 A CN 200410032601A CN 1532004 A CN1532004 A CN 1532004A
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China
Prior art keywords
coating
temperature
acid
resin
time
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CNA2004100326017A
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CN100339163C (en
Inventor
藤田孝行
广
垣井拓广
一
渡边正一
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Nippon Paint Automotive Coatings Co Ltd
Nippon Paint Holdings Co Ltd
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Nippon Paint Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
    • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/57—Three layers or more the last layer being a clear coat
    • B05D7/572—Three layers or more the last layer being a clear coat all layers being cured or baked together
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0209—Multistage baking

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

The preparation method of a coated composite film comprises the steps of: forming an electrically coated film on a substrate, applying an intermediate paint, a base paint and a transparent paint continuously in a wet-on-wet process and then baking and hardening the applied three layers at one time, wherein the baking and hardening comprises a low temperature heating step for heating at a temperature of 25 to 80% of a hardening temperature for a time of 5 to 30% of a hardening time and a high temperature heating step for heating at a temperature of 80 to 120% of a hardening temperature for a time of 30 to 130% of a hardening time.

Description

A kind of method of producing the coating compelx coating
Technical field
The present invention relates to a kind of method of producing the coating compelx coating, particularly a kind of three coatings of coating compelx coating, method of first drying of producing.
Background technology
Producing the coating compelx coating has two kinds of methods, and a kind of is that the oven dry of filming after each layer coating is made its curing; Another kind is to be coated with two-layer or layered coating without solidifying, and then one-step solidification.For example form the method that metal coating adopts twice coating, first drying often.JP-A No.11-114489 discloses a kind of method of producing the coating compelx coating, this method comprises that continuous formation is three-layer coated: the colored base of one deck is filmed, and the layer of metal base is filmed, and layer of transparent is filmed, trilamellar membrane baking and curing simultaneously then, the outward appearance of filming with raising.
Use middle the filming of method formation one deck of three coatings, first drying, one deck matrix is filmed and layer of transparent is filmed, can save and be used for the oven that cured interlayer is filmed, thereby reduced the energy and the operating time that is consumed, and obtained economically with Environmental compatibility on huge advantage.
Yet, compare with the method for traditional continuous drying method or twice coating, first drying, in the method for three coatings, first drying, three layers of coating are filmed and are capped from level to level under wet or leather hard, thereby reduce and limited the discharge mode of solvent, so that improved the content of non-volatile component in the coating compelx coating.As a result, contained solvent can be transferred in adjacent the filming in the coating film, especially when heating.This solvent shifts very easy certain phenomenon of generation, and it is called as in the baking and curing process mutually and mixes, the wherein adjacent dissolving mutually of filming, and the composition that is comprised in correspondingly respectively filming also mixes mutually.When mixing generation mutually, resulting composite membrane outward appearance is obviously destroyed, and the glossiness of coating compelx coating is affected adversely.
On the other hand, JP-A No.2000-84463 has proposed a kind of method of finishing the baking and curing process under two step heating conditions, and it is a kind of good method of filming of solvent-based thermal solidity coating material production flatness of using.In this method, avoided the coarse of film coated surface by the solvent that comprises in an amount of evaporation coating.
Yet, the problem that the method for three coatings, first drying is listed below for example having.
Film and can peel off in some cases, such as the vehicle in is advanced pressed cobblestone make its hit can cause when filming so-called cracked.In the method for traditional production coating compelx coating, as dry the method for the method of each coating and twice coating, first drying, baking and curing independently of one another that slubbing is filmed and film in the centre.Therefore adopt on film in the centre or below add the method that one deck shatter-resistant is filmed, perhaps by adjusting outer film and middle brightness of filming forms one deck and do not see the method for filming in cracked centre, as the countermeasure that solves cracked problem.
For example, JP-A No.2002-249699 and JP-A No.9-208882 have narrated a kind of chip subbing coating composition, and the formation method that shatter-resistant is filmed in the coating composite membrane.
In addition, among JP-A No.6-256714 or the JP-A No.6-254482, studied the improvement of shatter-resistant character, but its improved level is not enough for the method that is used for three coatings, first drying from the angle of middle coating composition.
Summary of the invention
The invention solves many traditional problems, its purpose provides a kind of method of producing the coating compelx coating with good bright and clean outward appearance, special glossiness and good cracking resistance by the method for three coatings, first drying.
The invention provides a kind of method of producing the coating compelx coating, comprise the steps: that forming one deck plating in substrate earlier films, the mode that goes up the humidification layer by wet layer is coated with the middle coating of one deck in succession then, one deck matrix coating and layer of transparent coating, first drying solidifies this three coating that is applied then, wherein baking and curing comprises two stages, comprise the low-temperature heat stage, the temperature of this moment is 25～80% of a solidification temperature, time is 5～30% of hardening time, and the high temperature heating period, the temperature of this moment is 80～120% of a solidification temperature, and the time is 30～130% of hardening time.
The formation of filming
In the method for formation coating compelx coating of the present invention, film and formed by middle coating in the centre, and basement membrane is formed by matrix coating, and transparent coating is formed by clear dope, and the continuous mode that goes up the humidification layer with wet layer of trilamellar membrane is attached in the substrate.
When during as substrate,, on the car body steel plate, forming electrodeposition coating in advance as anticorrosive filming (being often referred to " bottom is filmed ") with car body.In the method for using middle coating, can use the rapid rubbing method of multistep, preferably with two step rubbing methods of air electrostatic spraying coating, or with air electrostatic spraying coating and/or with the rotary atomizing electrostatic coating machine that is called " μ μ (micron micron) bel ", " μ (micron) bel " or " metabel ".
The thickness of filming after the drying that is formed by middle coating is according to required purposes and difference.In many occasions, operable thickness is 10～60 μ m.Prescribe a time limit above last when thickness, the definition of imaging can reduce, and can take place in coating such as the inhomogeneous and defective of subsiding under some situation; And be lower than down in limited time when thickness, the surface may be by hidden, and uneven coating occurs.
Be coated with in the method for compelx coating in formation of the present invention, on filming in uncured centre,, film and transparent coating to form matrix with a wet layer of mode coated substrates coating and a clear dope of going up the humidification layer.
Form the matrix employed matrix coating of filming and can adopt electrostatic sprayer or rotary atomizing electrostatic coating machine, as metabel, μ μ bel, μ bel or the like.Dried coating thickness can be arranged in 5～35 μ m, preferably 7～25 μ m.When the matrix coating thickness surpassed 35 μ m, the definition of imaging can reduce, and can occur inhomogeneous under some situation and subsided; And when thickness was lower than 5 μ m, uneven coating (the discontinuous membrane stage that is coated with) can appear under the shaded surface deficiency, certain situation.
When matrix is filmed when having inhomogeneities or containing luminous color pigment, just need to form transparent coating and film to form protection, to hide consequent thin projection.The selection of coating process is preferably especially and uses the rotary atomizing electrostatic coating machine, as μ μ bel, μ bel etc.
The thickness of dried transparent coating is preferably between about 10～80 μ m, more preferably in about 20～60 μ m.When dry thickness surpasses last prescribing a time limit, can occur during some applications such as protruding and the defective of subsiding; And prescribe a time limit down when thickness is lower than, the inhomogeneities on surface is difficult for being hidden.
Solidify this coating compelx coating by heating simultaneously.The method is generally known as three coatings, first drying method.In the time of many, the thickness of coating compelx coating is 30～300 μ m, preferred 50～250 μ m.Prescribe a time limit above last when thickness, the physical property of filming reduces such as the temperature cycle test meeting; And prescribe a time limit down when thickness is lower than, the intensity of filming reduces.
In order fully to solidify the coating that is applied on the substrate surface, condition of cure is set to heat curing coating.If under the condition that can not satisfy condition of cure, carry out the curing of heat curing coating, can make the crosslinked deficiency of coating compelx coating, its character will reduce.Generally, the condition of cure of heat curing coating comprise be provided with solidification temperature (℃) and hardening time.
Solidification temperature is meant the residing environment temperature of coating compelx coating when filming baking and curing in the traditional step heating.Generally be for wherein having inserted the set temperature of drying oven of coating compelx coating.Solidification temperature is decided by the reaction temperature of cross-linking system and the actual production line equipment that is adopted in the coating compelx coating.
Be meant hardening time under solidification temperature solidify the coating compelx coating in case of necessity between.The optimum value of hardening time is to determine by experience according to the thickness of coating type with the coating compelx coating.Consider the form and the solidification temperature of practical application production line, hardening time is for obtaining coating compelx coating required time of necessary performance in fact.
In the inventive method, the step of three layers of coating of baking and curing is divided into low-temperature heat stage and high temperature heating period, and each stage is carried out the predefined time.Carry out the short period when the low-temperature heat stage, then whole heat time heating time is very not long, and work is renderd a service and also do not reduced.Think that simultaneously because the low-temperature heat stage can increase the deposition of labile element, this method also can avoid layer phase mixing phenomena to take place.
In the low-temperature heat stage of the present invention, the heat curing coating layer that will form on substrate surface under preferred 35～60% the temperature conditions, reaches 5～30% of hardening time in 25～80% of solidification temperature, under preferred 10～20% the time conditions, and heating.When solidification temperature and hardening time surpassed this scope, technique effect was not enough.For example, when solidification temperature was 140 ℃, the low-temperature heat temperature was 35～112 ℃, preferred 49～84 ℃.When solidification temperature was 100 ℃, the low-temperature heat temperature was 25～80 ℃, preferred 35～60 ℃.In addition, when being 30 minutes between when solidified, the low-temperature heat time is 2～9 minutes, preferred 3～6 minutes.When being 60 minutes when solidified, the low-temperature heat time is 3～18 minutes, preferred 6～12 minutes.
In the high temperature heating period, the heat curing coating layer further is heated, and its temperature range is 80～120% of a solidification temperature, and is preferred 90～110%, and time range is 30～130% of hardening time, and preferred 50～100%.When solidification temperature and hardening time surpass last in limited time, can the cumulative stress strain, on the coating compelx coating crackle appears sometimes.For example, when solidification temperature was 140 ℃, the high temperature heating-up temperature was 112～168 ℃, preferred 126～154 ℃.When solidification temperature was 100 ℃, the high temperature heating-up temperature was 80～120 ℃, preferred 90～110 ℃.In addition, when being 30 minutes between when solidified, high temperature heat time heating time is 10～40 minutes, preferred 15～30 minutes.When being 60 minutes when solidified, high temperature heat time heating time is 18～78 minutes, preferred 30～60 minutes.
Heating operation can adopt the method known to those skilled in the art.Usually, the object that scribbles thermohardening lacquer can be placed in the drying oven that is adjusted under the heating-up temperature.
This method especially may further comprise the steps:
The coated article spare that has been coated with thermohardening lacquer is placed in the drying oven under the temperature that is controlled at low-temperature heat, keeps the time of certain low-temperature heat, the temperature of adjusting drying oven then is to the temperature of high temperature heating and keep certain high temperature heat time heating time;
Preparation is in tunnel chamber for drying that the import at two ends and outlet are all opened wide, by ribbon conveyer material is sent into hothouse and carry out drying, inside, tunnel chamber for drying is divided into low-temperature space and high-temperature region, the temperature of adjusting low-temperature space under the temperature of low-temperature heat and the whole temperature of warm area of heightening under the temperature of high temperature heating, at first object is continued one low-temperature heat period by low-temperature space, then it is continued one period high temperature heat time heating time by the high-temperature region;
Prepare the drying oven under first temperature that is adjusted at low-temperature heat, be adjusted at drying oven under the temperature of high temperature heating with second temperature, the coated article spare with the thermohardening lacquer coating be placed on put into the lasting certain high temperature of second drying oven heat time heating time after continuing certain low-temperature heat time in first drying oven.
Film in the centre
In the formation method that the present invention films, in the middle of being used to form, middle coating films, middle coating comprises the mylar that (a) is urethane-modified, (b) melmac, (c) blocked isocyanate compounds, (d) have the non-water-dispersed resin of nucleocapsid structure and (e) flake pigment.This centre coating also can contain the various colouring agents and the filler pigment of organic or inorganic.
Urethane-modified mylar (a) can make by the mylar and the reaction of aliphatic isocyanic acid compound of hydroxyl group.
General, mylar can by acid constituents for example the polycondensation reaction of carboxylic acid, acid anhydrides and acyl chlorides and monohydroxy or polyhydroxy-alcohol prepare.The content that the mylar of the hydroxyl group that the present invention is used is included in the isophthalic acid in the acid constituents that polycondensation reaction uses 80mol% or more than, by the total mole number of acid constituents.When the content of the isophthalic acid in the acid constituents was lower than 80mol%, the mylar glass transition temperature (Tg) of gained hydroxyl group can be lower than desirable scope.
The example of the acid constituents except isophthalic acid also comprises phthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydro-phthalic acid, hexahydro phthalic anhydride, the methyltetrahydro phthalic acid, the methyltetrahydro phthalic anhydride, the himic acid anhydrides, trihemellitic acid, the trihemellitic acid acid anhydride, PMA, the PMA acid anhydride, terephthalic acids, maleic acid, maleic anhydride, fumaric acid, methylene succinic acid, adipic acid, azelaic acid, decanedioic acid, succinic acid, succinic anhydride, the dodecyl succinic acid, dodecyl succinic anhydride and other be acid similarly.In addition, as acid constituents except that the carboxylic acid and acid anhydrides of multivalence, also comprise other acid that is usually used in preparing mylar.The example of this class acid comprises monocarboxylic acid and hydroxycarboxylic acid.As the acid of the mylar that is used to prepare hydroxyl group, isophthalic acid can use separately or mix use with other acid.
The example of polyhydroxy-alcohol comprises ethylene glycol, tirethylene glycol, polyethylene glycol, propane diols, two propane diols that contract, polypropylene glycol, neopentyl glycol, 1, the 2-butanediol, 1, the 3-butanediol, 1, the 4-butanediol, 2, the 3-butanediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 4-cyclohexanediol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxy propionate, 2,2,4-trimethyl 1, the 3-pentanediol, polytetramethylene ether glycol, the PCL polyalcohol, glycerine, sorb (sugar) alcohol, mannitol (annitol), trimethylolethane, trimethylolpropane, tri hydroxy methyl butane, hexanetriol, pentaerythrite, (one contracts) dipentaerythritol and other are alcohol similarly.
In the preparation of the mylar of hydroxyl group, except acid constituents and polyhydroxy-alcohol, can also use other component that can react with these components.These other components comprise the growth of sour growth, epoxides and drying oil, semi-drying oil and the aliphatic acid of acyl chlorides, lactone.Lactone can form grafted chain by the open loop addition on the mylar of polyvalent carboxylic acid and polyhydroxy-alcohol.The example of lactone comprises β-Bing Chunsuanneizhi, dimethyl propiolactone, butyrolactone, gamma-valerolactone, 6-caprolactone, γ-Ji Neizhi, γ-Xin Neizhi, crotons lactone (crotolactone), δ-Wu Neizhi, δ-caprolactone etc.Particularly, 6-caprolactone most preferably.Specific embodiment comprises monoepoxide for example Carjula E (being prepared by shell chemistry Co., Ltd) and lactone.
The glass transition temperature of the mylar of hydroxyl group (Tg) is 40-80 ℃, preferred 45-75 ℃.When glass transition temperature (Tg) was lower than 40 ℃, hardness of film can reduce.When being higher than 80 ℃, anti-crushing performance also can reduce.
The example of aliphatic isocyanate compound comprises 1, hexamethylene-diisocyanate, trimethyl hexamethylene diisocyanate, cyclohexane-1,4-vulcabond, double-hexyl methane-4,4-vulcabond, Methylcyclohexyl diisocyanate and IPDI.
Usually, consider the anti-crushing performance and the weather-resistant performance of coating compelx coating, preferably use 1, hexamethylene-diisocyanate or trimethyl hexamethylene diisocyanate.Buret, isocyanuric acid ester and their addition compound product also can use.
The mylar of hydroxyl group and the reaction of aliphatic isocyanate compound can be carried out according to the method that those skilled in the art use always.
The number-average molecular weight (Mn) of urethane-modified mylar (a) is 1500-3000, preferred 1700-2500.When number-average molecular weight was lower than 1500, workability and curing performance were lower.When number-average molecular weight was higher than 3000, the non-volatile content during coating was too low, and workability also reduces on the contrary.Here, number-average molecular weight is that benchmark adopts the GPC method to measure with the polystyrene.
The hydroxyl value (OHV) of urethane-modified mylar (a) preferred 30-180, more preferably 40-160.When hydroxyl value surpassed 180, the water repelling property of coating compelx coating reduced.When hydroxyl value was lower than 30, coating compelx coating curing performance reduced.In addition, the acid number of resin (AV) is preferably 3-30mgKOH/g, more preferably 5-25mgKOH/g.When acid number surpassed 30mg KOH/g, the water repelling property of coating compelx coating reduced.When acid number was lower than 3mgKOH/g, the curing performance of coating compelx coating reduced.
The content of urethane-modified mylar (a) accounts for the 40-56% (wt) of resin solid weight content in the coating in the middle coating, preferred 43-50% (wt).When content was lower than 40% (wt), anti-crushing performance can be not enough, and when surpassing 56% (wt), the hardness of coating compelx coating can reduce.
It is believed that when containing urethane-modified mylar as component in the middle coating, the elasticity of coating compelx coating improves, and anti-crushing performance also improves.
Melmac (b) and blocked isocyanate compounds (c) are as described below to be to be used for the component of mylar (a) of cured urethane modification.
Melmac (b) is not subjected to limit especially, comprises the melmac of methylated melmac, butylated melmac or methyl-butylation mixed type.Example comprises " Cymel-303 ", " Cymel 254 " sold by MitsuiToatsu, " Urban 128 " and " Urban 20N60 " and by Sumitomo Chemical Co., " the Sumimar Series " that Ltd sells.
The amount of the melmac (b) that contains in the middle coating accounts for resin solid weight 10-30% (wt) in the coating, preferred 15-25% (wt).When melmac content is lower than 10% (wt), the curing meeting deficiency of coating compelx coating, when surpassing 20% (wt), the coating compelx coating can be frangible too firmly.
Blocked isocyanate compounds (c) can obtain by use end-capping reagent on the aliphatic isocyanates or derivatives thereof.When blocked isocyanate compounds was heated, end-capping reagent decompose to produce isocyanate groups, and the oh group of it and urethane-modified mylar reacts curing material.
The example of aliphatic isocyanates and its derivative comprises the compound that is used to prepare urethane-modified mylar.The example of end-capping reagent comprises the compound that contains the active methylene group group, for example pentanedione, ethyl acetoacetate and malonic acid ethyl ester.By using end-capping reagent, the elasticity of coating compelx coating improves, and anti-crushing performance also improves.
Blocked isocyanate compounds is by for example Asahi Chemical Industry Co., and Ltd sells as active methylene group type blocked isocyanate " Duranate MF-K60X ".
The amount of the blocked isocyanate compounds (c) that contains in the middle coating accounts for the 15-30% (wt) of resin solid weight in the coating, preferred 17-25% (wt).When its content was lower than 15% (wt), the curing performance of coating compelx coating can be not enough, and when surpassing 30% (wt), filming of curing can be frangible too firmly.
The dispersion resin of non-water (d) has nucleocapsid structure, but can prepare by the resin of copolymerization stable dispersion in containing the mixed solution of organic solvent and the monomer of copolymerization, obtain the resin of non-crosslinked resin particle form, it is insoluble to described mixed solution.In order to obtain the non-crosslinked resin grain, under dispersed stable resin existence condition, monomer that can copolymerization is had no particular limits, as long as it is the unsaturated monomer that radical polymerization can take place.
For synthesizing stable dispersion resin and nonaqueous dispersion, the preferential polymerisable monomer that adopts with functional group, this be because non-aqueous dispersion have mutually can with the functional group of curing agent reaction, dispersion stabilizing resin contains functional group and can form three-dimensional cross-linked coating compelx coating simultaneously.
Dispersion stabilizing resin is provided with special restriction, as long as can in organic solvent, stablize synthetic nonaqueous dispersion.Especially, preferably use acrylic resin, mylar, polyether resin, polycarbonate resin, polyurethane resin etc., their hydroxyl value is 10-250, preferred 20-180, and acid number is 0-100mgKOH/g, preferred 0-50mgKOH/g.Number-average molecular weight is 800-100,000, and preferred 1,000-20,000.Prescribe a time limit above last when above-mentioned parameter, the serviceability of resin reduces, and the serviceability of non-aqueous dispersion phase also reduces.When above-mentioned parameter is lower than down in limited time, film and may desorb get off, when making the coating compelx coating, the stability of particle also can reduce.
The method of synthesizing stable dispersion resin is not subjected to specific limitation, comprises preferably obtaining the method for resin by radical polymerization in the presence of free radical polymerization initiator and passing through method of condensing or the method for addition reaction acquisition resin.In addition, the monomer that is used to prepare dispersion stabilizing resin can suitably be selected according to the characteristic of resin, but preferred the use contained functional group, oh group for example, the monomer of acidic-group etc., as mentioned below, they own for polymerisable monomer, be used for synthetic nonaqueous dispersion, and if desired, can use to have for example monomer of functional groups such as propylene oxide base, isocyanates.
In addition, the weight ratio of dispersion stabilizing resin and polymerisable monomer can at random be selected according to purpose.For example, preferred dispersion stabilizing resin is 3-80% (wt), particularly 5-60% (wt), and polymerisable monomer is 97-20% (wt), and 95-40% (wt) particularly is based on the gross weight of two components.And dispersion stabilizing resin and the polymerisable monomer total concentration in organic solvent is preferably 30-80% (wt), is preferably 40-60% (wt) especially, based on gross weight.
But nonaqueous dispersion can obtain by the monomer of polymerization radical polymerization under the dispersion stabilizing resin existence condition.In described nonaqueous dispersion, preferred hydroxyl value 50-400, more preferably 100-300, preferred acid number is 0-200mgKOH/g, more preferably 0-50mgKOH/g, and average particulate diameter (D 50) be 0.05-10 μ m, preferred 0.1-2 μ m.Prescribe a time limit when these parameters are lower than down, coating of particles is difficult to keep.Prescribe a time limit above last when above-mentioned parameter, its stability reduces in the time of in being dispersed in coating.
The typical example that typically is used for the polymerisable monomer that contains functional group of synthetic nonaqueous dispersion comprises the monomer that contains oh group, for example the addition compound product of (methyl) acrylic acid hydroxyethyl ester, (methyl) acrylic acid hydroxy-propyl ester, (methyl) acrylic acid hydroxybutyl ester, (methyl) acrylic acid hydroxymethyl ester, allyl alcohol and (methyl) acrylic acid hydroxyethyl ester and 6-caprolactone.
On the other hand, the example that contains the monomer of acidic-group comprise have carboxyl, the polymerisable monomer of sulfonic group etc.Has example Bao Zhi (methyl) acrylic acid, butenoic acid, ethylacrylic acid (ethylacrylic acid), propyl group acrylic acid, isopropylacrylic acid, methylene succinic acid, maleic anhydride, fumaric acid of the monomer of carboxyl or the like.Example with sulfonic polymerisable monomer comprises tert-butyl group acrylamide sulfonic acid etc.When use had the polymerisable monomer of acidic-group, the preferred acidic group partly was a carboxyl.
In addition, the example that contains the polymerisable monomer of functional group comprises the unsaturated monomer that contains glycidyl, glycidyl (methyl) acrylate for example, the unsaturated monomer that contains isocyanate groups, for example-and isopropenyl-α, α-Er Jiajibianji isocyanates, ethyl isocyanate base acrylate or the like.
The example of other polymerisable monomer comprises (methyl) alkyl acrylate, (methyl) methyl acrylate for example, (methyl) acrylic acid ethyl ester, (methyl) acrylic acid isopropyl esters, (methyl) acrylic acid n-pro-pyl ester, (methyl) n-butylacrylate, (methyl) acrylic acid tertiary butyl ester, (methyl) acrylic acid isobutyl, (methyl) acrylic acid (2-ethylhexyl) ester, (methyl) acrylic acid n-octyl ester, (methyl) acrylic acid Lauryl Ester, (methyl) stearyl acrylate base ester and (methyl) tridecyl acrylate, fatty acid and acrylic acid addition reaction product or have the methacrylate monomers (for example addition reaction product of stearic acid and methyl propenoic acid glycidyl base ester etc.) of ethylene oxide structure, contain the oxirane compound of C3 or longer alkyl group and the addition reaction product of acrylic or methacrylic acid, styrene, AMS, o-methyl styrene, between methyl styrene, p-methylstyrene, right-tert-butyl styrene, (methyl) acrylic acid benzyl ester, 2-methylene-succinic acid ester (methylene succinic acid dimethyl esters), maleate (maleic acid dimethyl esters), fumarate (fumaric acid dimethyl esters), and other polymerisable monomer acrylonitrile for example, methacrylonitrile, methyl isopropenyl ketone, vinylacetate, Veoba Monomer (is prepared by shell chemistry Co., Ltd, trade name), vinyl propionate base ester, the trimethylace tonitric vinyl salt, ethene, propylene, butadiene, acrylic acid-N, N-dimethyl aminoethyl ester, methacrylic acid-N, N-dimethyl aminoethyl ester, acrylamide and vinylpyridine.
The polymerisation that obtains nonaqueous dispersion preferably takes place in the presence of free radical polymerization initiator.The example of free radical polymerization initiator comprises azo group initator for example 2,2 '-azodiisobutyronitrile and 2, and 2 '-azo two (2, the 4-methyl pentane nitrile), benzoyl peroxide, lauryl peroxide, tert-butyl are crossed caprylate or the like.The content of these initators is wished the weight portion for 0.2-10, and preferred 0.5-5 weight portion is by the gross weight of per 100 parts of polymerisable monomers.The polymerisation that obtains nonaqueous dispersion was preferably reacted 1-15 hour down at about 60-160 ℃ in the organic solution that contains the decentralized stable resin.
In addition, nonaqueous dispersion is a kind of particle component that is different from cross-linked polymer particle in coating, and has the feature that does not constitute coating compelx coating particle structure.That is to say that the particle that nonaqueous dispersion is different from cross-linked polymer is that because there is not crosslinked place in the particle, grain shape changes in curing, and this can become the resin component.
Further, for example also can use the resin particle that is known as NAD, at " coloured material ", the 48th volume (1975) is talked about NAD (non-aqueous dispersions) and is used for NAD coating in the 28-34 page or leaf.
NAD resin (d) content that contains in the middle coating accounts for 4～15%, preferred 5～12% of matrix resin solid content weight.When weight content less than 4% the time, the outward appearance of coating compelx coating is bad; When weight content surpassed 15%, anti-fragmentation performance reduced.
By using NAD resin (d) can easily prevent mixing mutually and improve outward appearance between the coating.
Flake pigment (e) comprises mica, alumina, talcum and silica.From the angle of shatter-resistant, preferably talc.
It is 1～10 μ m that preferred flake pigment (e) is of a size of major diameter, and average particulate diameter is 2～6 μ m.When major diameter went beyond the scope, appearance of film was relatively poor, and can not get enough cracking resistances.When the number average particle diameter exceeds this scope, similar, coating compelx coating outward appearance is relatively poor, also can not get enough cracking resistances.
When coating resin weight solid content was 100 parts, the content of flake pigment (e) was 0.4～2 part, preferred 0.5～1.5 part.When content exceeds this scope, can reduce the caking property of filming, and can not get enough cracking resistances with bottom.
Be not specially limited and comprise other resin, but comprised acrylic resin, mylar, alkyd resins and epoxy resin etc. in the example.Two or more are used but these resins can use also separately.
The example of coloring pigment comprises that azo chelate group pigment, insoluble azo group pigment, the azo group pigment that condenses, phthalocyanine dye base pigment, indigo pigment, perinone base pigment, perylene base pigment, alkyl dioxin pigment, quinoline a word used for translation (two) ketone group pigment, isoindoline ketone group pigment and metal composite pigment etc. are as organic facies.Inorganic chrome yellow, iron oxide yellow, iron oxide red, carbon black and the titanium dioxide etc. of adopting mutually.Filler pigment be can use in addition, calcium carbonate, barium sulfate, aluminium powder and kaolin etc. comprised.
As standard, grey color base coloring pigment comprises that carbon black and titanium dioxide can be used as main pigment and uses.Also can use the coloring pigment compatible and the assembly of various pigment in addition outward with the tone of filming.
In addition, mix mutually with outer coating film and maintenance coating operability, in middle coating, add rheological agent for preventing coating.The example of this rheological agent comprises generally having thixotropic material, and polyamide-based reagent for example is as the swelling dispersion of phosphate of fatty acid amide, acid amides aliphatic acid, long-chain polyaminoamide etc.; Polyvinyl reagent is as the gluey swelling dispersion of PEO etc.; The organobentonite base auxiliary agent covers unsticking soil, covers unsticking soil etc. as organic acid; Inorganic pigment is as alumina silicate, barium sulfate etc.; Exhibition viscosity is by the flake pigment of the shape control of pigment, crosslinked resin particle etc.
The used middle coating solid content total amount of the present invention is 30～80% (wt), preferred 35～65% (wt).When exceeding this scope, can reduce the stability of coating.Total amount surpasses last prescribing a time limit, and viscosity is too high, and the outward appearance of coating compelx coating is bad.If total amount is lower than lower limit, viscosity is too low, makes cosmetic damage, as it is mixed inhomogeneous mutually interlayer to occur being coated with.
Except that above composition, can other additive that generally is added in the coating be included in the middle coating of the present invention as surface conditioner, antioxidant, anti-foaming agent etc.These amount of substances are in those skilled in the art's known range.
In addition, in urethane-modified mylar, also comprise other resin.These resins do not have particular restriction, can comprise acrylic resin, mylar, alkyd resins and epoxy resin etc.They can use separately or two or more are used.
The processing technology of the coating composition that preparation the present invention is used comprises that the back is with the processing technology of mentioning, do not have particular restriction, but some technologies that forefathers have grasped are mediated the blend of pigment and are disperseed as using kneader, cylinder machine and SG rolling mill.
Matrix is filmed
The present invention's matrix coating that uses in the formation method of filming is used for constituting the outer coating film of clear dope.Matrix coating comprises film formation resin, curing agent, coloring pigment, if necessary, comprises that also the coating of compositions such as luminous pigment is filmed.
The formation resin of filming that comprises in the matrix coating does not have particular restriction, and its preferred example is acrylic resin, mylar, alkyd resins, epoxy resin and urethane resin etc.They can use separately or two or more are used.
The formation resin of filming can be used with curing agent.From the film angle of cost performance of gained, preferably use polyamide and/or blocked isocyanate resin.
The weight content of curing agent is preferably to film and forms 20～60% of resin solid content, is more preferably 30～50%.When content less than 20% the time, the state of cure deficiency.When content greater than 60% the time, filming after the curing is too hard and frangible.
In addition, also can comprise coloring pigment, as the coloring pigment of being given an example in the middle coating.
The shape that arbitrarily is included in the luminous color pigment in the matrix coating does not have particular restriction.Luminous color pigment can be further painted.For example preferred its average grain diameter (D 50) be 2～50 μ m, thickness is 0.1～5 μ m.In luminous color pigment sensation with aspect being suitable for more, average particle size range is good at the luminous color pigment of 10～35 μ m.The concentration of luminous color pigment (PWC) is generally 20.0% weight or lower in the coating.Prescribe a time limit when concentration surpasses on this, can reduce the outward appearance of filming.Concentration range is preferably 0.01～18.0%, and preferred 0.1～15.0%.When luminous color pigment content surpasses 20.0%, can destroy the outward appearance of filming.
The luminous pigment example comprises the luminous color pigment of the metal of colourless or coloured metal or alloy, as aluminium, copper, zinc, iron, nickel, tin and aluminium oxide and their mixture.Simultaneously, also can related use disturb pigments, mica, white pigments, mica, graphite and other coloured or colourless flake pigment.
Luminous color pigment and the total concentration (PWC) of other all pigment in coating are 0.1～50% (wt), preferred 0.5～40% (wt), more preferably 1.0～30% (wt).Prescribe a time limit above last when concentration, appearance of film is not good.
Further, in middle coating,, be preferably in and add the viscosity rheological agent in the matrix coating for guaranteeing the coating operability.Rheological agent is to be used to form not have inhomogeneous and filming of subsiding, and generally contains thixotropic agent.The example of this auxiliary agent in middle coating to illustrate.
Except that above composition, generally be added on the additive in the coating, can be included in the matrix coating of the present invention as surface conditioner, rheological agent, antioxidant, ultraviolet inhibitor and anti-foaming agent etc.The consumption of these materials is in those skilled in the art's ken.
The total solid content of the matrix coating of using among the present invention is 10～60% (wt), preferred 15～50% (wt).When it is higher than the upper limit or is lower than down in limited time the paint stability reduction.Content surpasses the upper limit, and viscosity is too big, and appearance of film is not good; Content is lower than lower limit, and viscosity is too low, makes cosmetic damage, as it is mixed inhomogeneous mutually interlayer to occur.
Transparent coating
Form transparent coating with clear dope.The clear dope kind does not have particular restriction, but can use the clear dope that contains film forming thermosetting resin and curing agent.The form of clear dope for example is aqueous, watery and powdery.
For guaranteeing the transparency and antiacid corrosivity, the preferred embodiment of aqueous clear dope comprises combination, acrylic resin and/or mylar and the combination of isocyanate compound, the acrylic resin that contains carboxylic acid-epoxy curing systems and/or the mylar of acrylic resin and/or mylar and amino resins.
In addition, the example of watery clear dope comprises and containing in the useful alkali and the coating of a kind of resin that the film-forming resin of aqueous clear dope illustrated obtains, so that make coating become watery.Neutralization is finished by add tertiary amine such as dimethyl ethanolamine and triethylamine before and after polymerization.
On the other hand, transparent powder coating can use traditional powder-type coating, as thermoplasticity and thermosetting powder-type coating.For obtaining that filming of better physical property arranged, preferably use the thermosetting powder-type coating.The example of thermosetting powder-type coating comprises epoxy radicals base, acrylic and polyester resin-based transparent powder coating, and preferred weatherability is the acrylic transparent powder coating preferably.
As the used transparent powder coating of the present invention, especially preferably contain acrylic resin/polyvalent carboxylic acid's original washing powder shape coating of epoxy radicals, because it does not produce volatile material in solidification process, and can obtain outward appearance preferably, and occur the yellowing phenomenon hardly.
Further, identical for guaranteeing the coating operability with middle coating, preferably in clear dope, add rheological agent.Generally contain thixotropic agent in the rheological agent.The example of rheological agent illustrates in middle coating.If be necessary, wherein also can contain curing catalysts, surface conditioner etc.
Substrate
Coating compelx coating formation method can be advantageously used in various substrates among the present invention, as metal, plastics, foamed material etc.Preferable alloy and moldings.This method is specially adapted to carry out the metallic article of cation electrodeposition coating.
The example of metallic article comprises iron, copper, aluminium, tin, zinc etc. and contains the alloy of these metals.The part that specifically comprises car body and automobile, truck, motorcycle and bus etc.Preferred especially in advance with the metal of chemical treatments such as phosphate and chromate.
In addition, being coated with the substrate of using in the composite membrane-forming method about the present invention, can be to form electrostatic precipitation to film on the steel plate that the chemistry formation is handled.As being used to form the electrostatic precipitation coating that electrostatic precipitation is filmed, cationic and anionic all can use, and preferred cationic type electrostatic precipitation coating composition is because it has given the more outstanding corrosion resistance of filming.
The specific embodiment
Describe the present invention in detail with following embodiment, but the present invention is not limited only to these embodiment.Here, " part " and " % " all by weight.
Preparation embodiment 1
The preparation of urethane-modified mylar (a)
With 440 parts of isophthalic acids, 20 parts of hexahydro-phthalic acids, 40 parts of azelaic acids, 300 parts of trimethylolpropanes and 200 parts of neopentyl glycols be placed on be furnished with nitrogen ingress pipe, in the 2L reactor of the condenser pipe of agitator, thermoregulator, charging hopper and band decanter, after raw material dissolves in heating with under stirring, add 0.2 part of Dibutyltin oxide, begin to stir, and in 3h, make the conversion zone temperature rise to 220 ℃ by 180 ℃ gradually.The condensation water that produces is distilled from system.When temperature reaches 220 ℃, keep 1h, in conversion zone, add 20 parts of dimethylbenzene gradually, in the presence of solvent, allow condensation reaction to carry out.When resinous acid value reaches 10mgKOH/g, material is cooled to 100 ℃, added 100 part 1 gradually, hexamethylene-diisocyanate with 30 minutes.Further keep this temperature 1h, add 200 parts of dimethylbenzene and 200 parts of butyl acetates, obtain urethane-modified mylar, solid content is 70%, and number-average molecular weight is 2000, and acid number is 8mgKOH/g, and hydroxyl value is 120, and resin Tg is 60 ℃.
Preparation embodiment 2
The preparation of non-watery dispersion
(a) preparation of dispersion stabilizing resin
90 parts of butyl acetates are joined be furnished with agitator, in the reactor of thermoregulator and reflux condenser.Then, add solution shown in 20 parts the table composed as follows:
Table 1
Methyl methacrylate 38.9 part
Stearyl methacrylate 38.8 part
Acrylic acid 2-hydroxyl ethyl ester 22.3 part
Azodiisobutyronitrile 5.0 part
Stir heat temperature raising down.110 ℃ with the residue that dropwise added 85 portions of mixed liquors in 3 hours, the solution with 0.5 part of azodiisobutyronitrile and 10 parts of butyl acetates dropwise added in 30 minutes then.Reaction solution refluxed stir 2 hours down improving resin reaction speed, reaction can obtain when finishing that solid content is 50%, number-average molecular weight is 5600, the SP value is 9.5 acrylic resin.
(b) preparation of nonaqueous dispersion
The acrylic resin that 90 parts of butyl acetates and 60 parts (a) are made adds and has in the reactor of agitator, condenser and thermoregulator.Be formulated as follows composition solution:
Table 2
Styrene 7.0 part
Methacrylic acid 1.8 part
Methyl methacrylate 12.0 part
Ethyl acrylate 8.5 part
Acrylic acid 2-hydroxyethyl ester 40.7 part
Azodiisobutyronitrile 1.4 part
This solution was dropwise added in 3 hours, and the solution with 0.1 part of azodiisobutyronitrile and 1 part of butyl acetate dropwise added in 30 minutes then.Continue stirring reaction liquid 1 hour, and obtained solid content and be 60%, particle diameter is the emulsion of 180nm.This emulsion is diluted with butyl acetate, obtain nuclear-shelly butyl acetate dispersion liquid, its nonaqueous dispersion content is 40%, and viscosity is 300cps (25 ℃), and particle diameter is 180nm.The Tg of this nonaqueous dispersion resin is 23 ℃, and hydroxyl value is 162, and the SP value is 11.8.The shell part of dispersion stabilizing resin differs 2.3 with this whole nonaqueous dispersion resin on the SP value.
Embodiment 1
Middle coating
107 parts of fronts are prepared the urethane-modified mylar that obtains among the embodiment, 280 parts of CR-97 (by the titanium oxide of Ishihara Sangyo Kaisha company production), 13 parts of MA-100 (by the charcoal blacks of MitsubishiChemical Co., Ltd production), 7 parts of LMS-100 (by the flakey mica of Fuji Talc production), 47 parts of butyl acetates and 47 parts of dimethylbenzene join in the 1L reactor, add GB503M (particle diameter is the glass microballoon of 1.6mm) with the same quantity of feeding quantity, at room temperature material was disperseed 3 hours, obtain the gray paint pastel with desk-top SG mill.The grinding standard of particle diameter is 5 μ m or littler after disperseing to finish.Filter out glass microballoon, obtain pigment paste.Pigment paste is made composition middle coating as shown in table 3.Mixed solvent with ethoxyethyl propionate/S-100 (Exxon produce aromatic solvent)=1: 1 is diluted to 19s/20 ℃ with this coating in No. 4 Ford cups.Non-volatile material content is 49% during use.
Table 3
Middle coating composition Pigment paste 100 parts
Mylar 130 parts
Nonaqueous dispersion 53 parts
Melmac (trade name Uban 128, produced by Mitsui Cyteck) 71 parts
Blocked isocyanate (trade name Duranate MF-K60X is produced by Asahi Chemical Industry Co., Ltd) 71 parts
The resin solid content rate Mylar/nonaqueous dispersion/melmac/blocked isocyanate 50/10/20/20
Pigment ratio Titanium oxide/carbon black/mica 28/1.3/0.7
PWC 30％
Matrix coating
Mixed solvent with ethoxyethyl propionate/S-100 (aromatic solvent that Exxon produces)/toluene=1/1/2 is diluted to 17s/20 ℃ in No. 3 Ford cups---by " the Orga TO H600 18J green metal " of ippon coating Co., Ltd production---with acrylic melamine fund attribute matrix coating.During use in the coating non-volatile material content be 31%.Non-volatile material content is 65% during deposition.
Clear dope
---by " Mack O-1600 is transparent " of ippon coating Co., Ltd production---mixed solvent with ethoxyethyl propionate/S-100 (aromatic solvent that Exxon produces)=1/1 is diluted to 26s/20 ℃ in No. 4 Ford cups with acid epoxy resin cure base clear dope.Non-volatile material content is 50% in the used coating.In addition, non-volatile material content is 61% during deposition.
Coating compelx coating formation method
It is that 0.8mm, length are that 30cm, width are on 10cm and the SPC steel plate through the trbasic zinc phosphate processing that cation electrodeposition coating " Power Top V-20 " (being produced by ippon coating Co., Ltd) electricity is coated on a thickness, forming thickness is the dry coating of 20 μ m, dries 30 minutes down at 160 ℃ then.This steel plate with the electro-deposition coated film is being sticked on the movable body, using the middle coating of " microbel " (rotating atomizing type electrostatic applications machine) coating at the volley, forming thickness is the coating of the dry coating of 20 μ m.This setting was carried out 10 minutes.
Use " microbel " and " metabel " to use matrix coating in two stages then, making its dry back coating thickness is 15 μ m.In administered twice, interval 2.5min.After using for the second time, keep this to be provided with 8 minutes.Using " microbel " once to be coated with clear dope then, to make its dry back coating thickness be 35 μ m.Keep this to be provided with 10 minutes.The condition of cure of resulting lamination coating compelx coating is 140 ℃ of solidification temperatures, 30 minutes hardening times.
The coated panel of preparation like this is placed in first drying oven of 40 ℃ 5 minutes earlier, transfers in second drying oven of 140 ℃ 20 minutes again.Take out coated panel then, be cooled to room temperature.
(1) solidifies the quality that the coating compelx coating outward appearance of finishing is passed through its glossiness of visual assessment.Test result sees Table 5.
Table 4
Evaluation criteria
3 Gloss appearance is good, seems that clear dope thickness is enough.
2 Gloss appearance is poor slightly, seems that clear dope thickness is thin slightly.
1 Gloss appearance is poor, seems uncoated clear dope.
(2) then, the surface state that the back is coated with compelx coating is solidified in coating compelx coating outward appearance tester " length scanning DOI " test that utilizes Big Chemie to produce.Test result sees Table 5.
Measured value Wa is illustrated in the numerical value of roughness in the surface curvature in 0.1～0.3mm, the gloss appearance of expression coating compelx coating.Wc is illustrated in that roughness shows the shaded surface that is coated with compelx coating at 1～3mm in the surface curvature.Wd is illustrated in the surface curvature roughness at 3～10mm, shows that the coating compelx coating is smooth.Along with numerical value diminishes, measured value improves each time.
(3) and then, following method has been estimated the cracking resistance of gained coated panel.Test result sees Table 5.
Adopting glabero tester (being produced by Suga test apparatus Co., Ltd), is 3.0kgf/cm from the 35cm distance in air pressure with 300 No. 7 roundstones 2Film with 45 ° of bumps down.Dry after washing then, peel off test, afterwards, observe extent of exfoliation with the term peel diameter with peeling off to count, and estimate by vision with the industrial adhesive tape that Nichiban produces.
Embodiment 2 to 4
Adopt the same quadrat method of describing among the embodiment 1, just press the data shown in the table 5 and change solidification temperature and hardening time, the coating compelx coating that preparation and test are solidified.Test result sees Table 5.
The comparative example 1
Adopt the same quadrat method of describing among the embodiment 1, just the baking and curing step with uncured coating compelx coating changes into 140 ℃ of one step heating 30 minutes, the coating compelx coating after preparation and test are solidified.Test result sees Table 6.
The comparative example 2
Adopt the same quadrat method of describing among the embodiment 1, coating changes " Orga TO H870 ash " polyester-melamine-based middle coating of producing with ippon coating Co., Ltd into just, press and change solidification temperature and hardening time shown in the table 6, coating compelx coating after preparation and test are solidified.Test result sees Table 6.
Reference example 1
It is that 0.8mm, length are that 30cm, width are on 10cm and the SPC steel plate through the trbasic zinc phosphate processing that cation electrodeposition coating " Power Top V-20 " (being produced by ippon coating Co., Ltd) electro-deposition is coated on a thickness, forming thickness is the dry coating of 20 μ m, dries 30 minutes down at 160 ℃ then.This steel plate with the electro-deposition coated film is being sticked on the movable body, using the middle coating of " microbel " (rotating atomizing type electrostatic applications machine) coating at the volley, forming thickness is the dry coating of 20 μ m.Use finish after, keep this to be provided with 10 minutes.
This coated panel is placed in 140 ℃ of drying ovens 20 minutes.Then, taking-up is cooled to room temperature.Matrix coating among the embodiment 1 and clear dope are coated on the coated panel, obtain being coated with compelx coating.
The coated panel that makes was like this put into 140 ℃ of drying ovens 30 minutes.Take out then and be cooled to room temperature.Test the coating of the curing compelx coating that obtains with method similarly to Example 1.Test result sees Table 6.
Reference example 2
Adopt the method same with reference example 1, just middle coating is changed into " Orga TO H870 ash " polyester-melamine-based middle coating that ippon coating Co., Ltd produces, solidification temperature and hardening time press shown in the table 6, and back coating compelx coating is solidified in preparation and test.Test result sees Table 6.
Table 5
The embodiment sequence number ????1 ?????2 ????3 ????4
Middle coating compelx coating Kind Embodiment 1 Embodiment 1 Embodiment 1 Embodiment 1
Oven dry ?- ??- ??- ??-
The oven dry of coating compelx coating Low temperature 40 ℃ * 5 minutes 60 ℃ * 3 minutes 60 ℃ * 5 minutes 100 ℃ * 5 minutes
High temperature 140 ℃ * 30 minutes 140 ℃ * 30 minutes 140 ℃ * 30 minutes 140 ℃ * 30 minutes
Outward appearance (visual assessment) ?3 ??3 ??3 ??3
Surface state Wa ?16.3 ??14.7 ??13.6 ??16.6
Wc ?13.4 ??14.4 ??12.2 ??16.2
Wd ?8.7 ??8.2 ??7.3 ??10.3
Cracking resistance Peel diameter ?2mm ??1.8mm ??1.7mm ??2mm
Peel off number ?20 ??18 ??16 ??19
Table 6
Sequence number The comparative example 1 The comparative example 2 Reference example 1 Reference example 2
Middle coating compelx coating Kind Embodiment 1 ?Orga?TO Embodiment 1 ?Orga?TO
Oven dry ?- ?- 140 ℃ * 30 minutes 140 ℃ * 30 minutes
The oven dry of coating compelx coating Low temperature ?- 60 ℃ * 5 minutes ?- ?-
High temperature 140 ℃ * 30 minutes 140 ℃ * 30 minutes 140 ℃ * 30 minutes 140 ℃ * 30 minutes
Outward appearance (visual assessment) ?2 ?1 ?3 ?3
Surface state Wa ?23.1 ?45.3 ?13.1 ?12.9
Wc ?21.0 ?61.4 ?11.5 ?11.4
Wd ?18.5 ?35.6 ?8.4 ?9.1
Cracking resistance Peel diameter ?2mm ?3.5mm ?2.0mm ?2.5mm
Peel off number ?20 ?106 ?16 ?30
In the embodiments of the invention, in addition when the gloss appearance performance of the coating compelx coating that adopts three coating first drying methods to obtain with adopt that to be coated with the gloss appearance that two-stage drying can reach for three times identical.In addition, although reduced the oven dry number of times, the coating compelx coating that the cracking resistance of the coating system that the present invention taked and three times coating two-stage drying obtains quite.

Claims (4)

1. produce the method that is coated with compelx coating for one kind, be included in the substrate and form electropaining cloth and film, be coated with the middle coating of one deck, one deck matrix coating and layer of transparent coating in succession with the wet humidification method of going up then, at last three coating first dryings are solidified, wherein baking and curing comprises that heating-up temperature is solidification temperature 25～80%, heat time heating time is the low-temperature heat stage of hardening time 5～30%, and heating-up temperature is solidification temperature 80～120%, heat time heating time to be the high temperature heating period of hardening time 30～130%.
2. the method for claim 1, wherein said in the middle of coating comprise:
(a) the urethane-modified mylar of 40～56% (wt), its number-average molecular weight is 1500～3000, be that mylar reaction by aliphatic isocyanates compound and hydroxyl makes, the glass transition temperature of this mylar (Tg) is 40～80 ℃, makes by comprising 80% (mol) or the acidic components of more isophthalic acid and the polycondensation reaction of polyalcohol;
(b) melmac of 10～30% (wt);
(c) blocked isocyanate compounds of 15～30% (wt);
(d) nonaqueous dispersion resin of the nucleocapsid structure of 4～15% (wt); (a)～(d) content is based on the weight solid content of resin and counts;
(e) flake pigment of 0.4～2 part of weight content is counted based on 100 parts of weight resin solid contents.
3. method as claimed in claim 2, wherein said blocked isocyanate compounds are with the compound end-blocking that contains the active methylene group group.
4. the coating compelx coating that forms according to any one method of claim 1～3.
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CN109776837A (en) * 2018-12-18 2019-05-21 合肥乐凯科技产业有限公司 A kind of anti-blue light protective film
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