CN107531018A - Precoated metal sheet - Google Patents
Precoated metal sheet Download PDFInfo
- Publication number
- CN107531018A CN107531018A CN201580078996.0A CN201580078996A CN107531018A CN 107531018 A CN107531018 A CN 107531018A CN 201580078996 A CN201580078996 A CN 201580078996A CN 107531018 A CN107531018 A CN 107531018A
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- CN
- China
- Prior art keywords
- film layer
- coating film
- primer coating
- metal sheet
- precoated metal
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B05D7/58—No clear coat specified
-
- 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
-
- 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
- B05D7/24—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 for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
-
- 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
- B05D2301/00—Inorganic additives or organic salts thereof
- B05D2301/10—Phosphates, phosphoric acid or organic salts thereof
-
- 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
- B05D2508/00—Polyesters
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The precoated metal sheet of the present invention has：Metallic plate；Base coating film layer, it is arranged on the metallic plate and does not contain chromate；Primer coating film layer, it is arranged on the base coating film layer and does not contain chromate；And top paint film layer, it is arranged on the primer coating film layer, wherein, break limit elongation by the film layer of the primer coating film layer and the top paint film layer altogether is 10%~25%, the glass transition point temperature of the primer coating film layer is more than 50 DEG C and less than 100 DEG C, the top paint film layer contains resin component, the resin component contains acrylic resin or polyester modification acrylic resin, when to precoated metal sheet progress 2T closely sealed bending machinings, into in the range of the 1mm length of vertical direction centered at the top of bending head and with bending direction, it is described top paint film layer produce add up to 5~30 width be below 0.1mm crackle.
Description
Technical field
The present invention relates to automobile using, household electrical appliances use, building materials use, building use, machinery use, furniture use, container with etc. used in
Precoated metal sheet, it is related to end face film fissility, the precoated metal sheet of corrosion resistance excellent after stain resistance, processing.
Background technology
The precoated metal sheet for the film that household electrical appliances have been coloured with, building materials with, automobile using etc. using being coated with is conventional to substitute
It is processed the rear application product of rear application.The precoated metal sheet is to coat coating to implementing the metallic plate of metal pre-treatment
Form, in general, cut off after coating is coated with, carry out compressing and used.
Precoated metal sheet is carried out to shape processing after application and used, therefore typically coats higher soft of elongation
Film, on the other hand, for such resin, polluter permeates to film, the situation of physical attachment is more, anti-pollution
Property difference is shortcoming.In the case of especially without waiting use, following problem be present：The dirt such as contained discharge gas in air
Surface is attached to, rain striped is produced due to being moistened by rain.
In general, will produce rain striped is referred to as raindrop pollution.For the producing cause of raindrop pollution, the water of film connects
Relation between feeler and raindrop pollution is mentioned, and teaching has that the hydrophily of film is higher, then resistance to raindrop contaminative is more excellent.But
It is, if dirt is influenceed by light, wind, rain etc. under the conditions of being attached to without and deteriorates the film of (weatherability deterioration), dirt
Can physically it get deeply stuck in into film.Accordingly, there exist following problem：Even if such as film has hydrophily, it is also difficult to by as
Dirt removes, even the film that hydrophily is higher, also due to weatherability deteriorates and resistance to raindrop contaminative is deteriorated.Therefore, it is
The resistance to raindrop contaminative for making precoated metal sheet long-term is improved, and not only to assign film hydrophily, it is necessary to be in metal
Set on plate it is long during have excellent weather resistance and polluter to the permeating of film, the stain resistance that physical attachment is less applies
Film.
But on the other hand, such stain resistance film is hard, thus exist the processability of film itself compared with
The problems such as low, processing department film adaptation (adhesiveness) is relatively low.Therefore, such precoated metal sheet is easy in shearing
Film is produced near cut-out end face portion to peel off.The film after stripping is attached to product surface, therefore produces following problem：
When carrying out press process, it is formed at as the indenture caused by the pellicula peeled off from the end face portion on film, damages U.S. of product
See.In this way, in the case where having used such stain resistance film, problem as the film fissility variation of end face be present.
The precoated metal sheet excellent on stain resistance, also there is some reports before this.For example, disclosed in patent document 1
A kind of pre-coated steel plate pre-coated steel plate excellent as stain resistance, in the pre-coated steel plate, in the surface treatment of surface of steel plate
Formed with being 10000~35000 relative to number-average molecular weight and 100 weight of polyester resins that hydroxyl value is 50~5 are matched somebody with somebody on overlay film
The film that the parts by weight methyl-etherified hexamethylol melamine resin of 20 parts by weight~50 forms is closed.But disclosed film
Containing melamine, therefore there are the following problems：It is decomposed because of heat, acid, film limbers up, because dirt is physically got deeply stuck in
Enter long-term stain resistance is deteriorated.
In addition, it is used as processability and stain resistance by the use of paint composite is applied Patent Document 2 discloses one kind precoating
Excellent coating constituent, the precoating with apply paint composite be characterised by, containing number-average molecular weight be 2000~
6000 polyester resin and number-average molecular weight is 1500~8000 acrylic resin.With regard to patent document 2 paint composite and
Speech, although it is believed that by being improved bendability containing polyester resin, but due to being mixed with harder acrylic resin,
Therefore end face film fissility is not up to eliminated.
In addition, Patent Document 3 discloses a kind of excellent coated metal plate of end face film fissility, its feature exists
In it is less than 30 DEG C of soft priming paint to have glass transition point temperature (Tg) in lower floor's combination of harder external coating.But
For the method for stress when making soft priming paint absorb processing, on top, paint film is acrylic resin, polyester modification propylene
It is insufficient in the mitigation of stress caused by the paint film of top in the case of acid resin, in the case of such coating structure, end face
Film fissility is still problem.
In this way, in technology disclosed at present, do not disclose and obtain stain resistance, end face film fissility and anti-corrosion
The technology of the excellent precoated metal sheet of property.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 10-314664 publications
Patent document 2：Japanese Unexamined Patent Publication 2008-201842 publications
Patent document 3：Japanese Unexamined Patent Publication 2006-175826 publications
The content of the invention
Invent problem to be solved
The present invention is formed in view of the above problems, and it is an object of the present invention to provide a kind of long-term stain resistance, the stripping of end face film
From property, the precoated metal sheet of corrosion resistance excellent.
Means for solving the problems
The inventors of the present invention have made intensive studies, and as a result contemplate：By by the acrylic resin of hard or poly-
Ester modified acrylic resin is applied to the resin of top paint film, so as to ensure long-term stain resistance.In addition, contemplate：
By using resin of the epoxy modified polyester resin as primer coating film layer so that adaptation (adhesiveness) of the film for steel plate
Improve.
In addition, it is contemplated：By primer coating film layer and top will be painted to the break limit of the film layer of film layer altogether
Elongation is set as 10%~25%, the glass transition point temperature of primer coating film layer is set greater than to 50 DEG C and 100 DEG C with
Under so that the primer coating film layer crackle trickle with top paint film layer generation should to relax when in compacting, film is by die drawn
Power.In addition, the result is that contemplate：Adaptation between harder top paint film and steel plate is ensured that film itself is not peeled off
And improve end face film fissility.And then by regarding any of magnesium phosphate, calcium phosphate, aluminum phosphate, trbasic zinc phosphate as antirust
Pigment is used for primer coating film layer so that even if cracking, can also suppress to produce the oxide (white rust) of zinc from crackle, make long-term
Corrosion resistance is improved.Its reason is estimated to be：Due to the dissolution of the rust resisting pigment composition containing phosphorus composition, with foring of zinc
Compound, it is suppressed that the dissolution of zinc.
The present invention is completed based on the opinion, and purport of the invention is as follows.
(1) a kind of precoated metal sheet, it has：Metallic plate；Base coating film layer, it is arranged on the metallic plate and is free of
There is chromate；Primer coating film layer, it is arranged on the base coating film layer and does not contain chromate；And top paint film layer, its
It is arranged on the primer coating film layer, wherein, by the film layer of the primer coating film layer and the top paint film layer altogether
Break limit elongation is 10%~25%, and the glass transition point temperature of the primer coating film layer is more than 50 DEG C and 100 DEG C
Hereinafter, the top paint film layer contains resin component, and the resin component contains acrylic resin or polyester modification acrylic acid tree
Fat, when carrying out the closely sealed bending machinings of 2T to the precoated metal sheet, centered at the top of bending head and with bending direction into
In the 1mm length ranges of vertical direction, produced in the top paint film layer and add up to 5~30 width as below 0.1mm's
Crackle.
(2) precoated metal sheet according to above-mentioned (1) or：The break limit elongation of the primer coating film layer
Rate is 40%~50%, and the break limit elongation of the top paint film layer is 5%~10%, and the primer coating film layer contains anti-
Rust pigment and resin component, the rust resisting pigment contain at least one or more in magnesium phosphate, calcium phosphate, aluminum phosphate or trbasic zinc phosphate,
The resin component in the primer coating film layer contains epoxy modified polyester resin.
(3) precoated metal sheet according to above-mentioned (1) or (2) or：The primer coating film layer contains antirust face
Material, the concentration of the rust resisting pigment are the mass parts of 10 mass parts~160 relative to 100 mass parts resin solid contents.
(4) precoated metal sheet according to any one of above-mentioned (1)~(3) or：The top paint film layer is not
Contain melmac.
(5) precoated metal sheet according to any one of above-mentioned (1)~(4) or：The top paint film layer
The coefficient of kinetic friction on surface is 0.06~0.25.
(6) precoated metal sheet according to any one of above-mentioned (1)~(5) or：In 50 DEG C, 95%RH
The water contact angle on the surface of the top paint film layer after being placed 72 hours under moist environment is less than 60 degree.
(7) precoated metal sheet according to any one of above-mentioned (1)~(6) or：The top paint film layer contains
There is organosilicate.
(8) precoated metal sheet according to above-mentioned (7) or：The organosilicon in the top paint film layer
The resin solid content that the content of hydrochlorate paints film layer relative to top described in 100 mass parts is the mass parts of 0.1 mass parts~20.
(9) precoated metal sheet according to any one of above-mentioned (1)~(8) or：The base coating film layer contains
Have at least one kind of in silica particle, silane coupler, tannic acid.
(10) precoated metal sheet according to any one of above-mentioned (1)~(9) or：The primer coating film layer
Thickness be 3 μm~10 μm, it is described top paint film layer thickness be 5 μm~25 μm.
Invention effect
In accordance with the invention it is possible to provide a kind of stain resistance, processing after end face film fissility, corrosion resistance excellent it is pre-
Matel coated plate.
Brief description of the drawings
Fig. 1 is to be shown schematically in have carried out the closely sealed bending machinings of 2T to the precoated metal sheet of embodiments of the present invention
Split when vertically having carried out cut-out centered on bending head top and with bending direction afterwards, having carried out section observation to section
The figure of the appearance of line.
Fig. 2 is to schematically show to have carried out the closely sealed bending machinings of 2T to the precoated metal sheet of embodiments of the present invention
The figure of appearance, and the figure that bending head near top is amplified, schematically shows the appearance of crackle caused by the part.
Embodiment
Hereinafter, the preferred embodiment of the present invention is described in detail referring to the drawings.
The precoated metal sheet of embodiments of the present invention has：Metallic plate；Base coating film layer, its be arranged on metallic plate and
Chromate is not contained；Primer coating film layer, it is arranged on base coating film layer and does not contain chromate；And top paint film layer, its
It is arranged on primer coating film layer.
Base coating film layer and primer coating film layer do not contain chromate.Chromic acid is not contained in base coating film layer and primer coating film layer
Salt, it is phosphatic in the case of, be excellent without using being brought to environment, human body on this aspect of dysgenic material.
Break limit elongation by the film layer of primer coating film layer and top paint film layer altogether is 10%~25%.Such as
Fruit is less than 10%, then the crackle of film layer is larger, and corrosion resistance is deteriorated, produces film stripping at processing department.In addition, more than 25%
When, stain resistance is deteriorated.
The glass transition point temperature of primer coating film layer is more than 50 DEG C and less than 100 DEG C.Additionally, it is preferred that more than 60 DEG C and
Less than 80 DEG C.
It can use and peel off or cut the film to get off, transition temperature assay method (the JIS K7121 according to plastics
1987) means of differential scanning calorimetry measure (DSC methods) obtains glass transition point temperature.
It is preferred that the break limit elongation of primer coating film layer is 40%~50%.Thus, following effect can be obtained：Top paint applies
The stress of film is alleviated, produced the crackle of appropriateness, further suppresses film stripping.
It is preferred that the break limit elongation of top paint film layer is 5%~10%.Thus, top paint film can be made harder so that
The stain resistance of precoated metal sheet is excellent.
The break limit elongation of each film layer can be carried out as follows measure：For example, for surface abreast by cutting into slices
The film that machine etc. cuts thin slice and forms each layer separation, implement tension test using small desk testing machine.
It is not only to be applied by priming paint for primer coating film layer and top are painted into the break limit elongation of film layer altogether
The respective break limit elongation of film layer is painted to determine in film layer and top, and primer coating film layer is closely sealed with the interface of top paint film layer
Property can also have an impact to it.This can for example lead to the break limit elongation of primer coating film layer and top paint film layer altogether
The concentration of rust resisting pigment is crossed to be adjusted.If the concentration of rust resisting pigment is to be relative to 100 mass parts resin solid contents
More than 10 mass parts, then the adaptation of primer coating film layer and top paint film layer improves, moreover, by by the fracture of primer coating film layer
Ultimate elongation is set as 40%~50%, the break limit elongation for pushing up paint film layer is set as into 5%~10% etc. so that
The break limit elongation of the film layer of primer coating film layer and top paint film layer altogether is turned into 10%~25%.
In this way, the construction feature of the film of the present invention is, by the film of primer coating film layer and top paint film layer altogether
The break limit elongation of layer is 10%~25%, and this feature can be by primer coating film layer and the top paint respective fracture of film layer
Ultimate elongation, concentration of rust resisting pigment etc. are properly selected to obtain.
Table 1
Table 1 is that the top being directed in present embodiment paints film layer, primer coating film layer and applies primer coating film layer and top paint
The film layer of film layer altogether, the table for the concentration that break limit elongation and rust resisting pigment are taken together.It is generally acknowledged that：Principle
On, to using higher (softness) film of elongation as the top paint film layer for deforming larger upper strata, to smaller as deforming
The primer coating film layer of lower floor use relatively low (harder) film of elongation.But the application uses opposite design, its feature
It is：To top paint film layer using relatively low (harder) film of elongation, elongation higher (softness) is used to primer coating film layer
Film.
That is, if the elongation for pushing up paint film layer and primer coating film layer is set as above-mentioned scope, even if to upper strata
Top paint film layer using the relatively low film of elongation, can will also push up paint film layer and the laminated overall elongated of primer coating film
Rate is set to higher.Now, it is known that the elongation of top paint film layer is to the contribution that overall elongated rate is brought than generally small.By
This, it was found that：Can while overall elongation is ensured, will when carrying out the closely sealed bending machinings of 2T after having carried out film
The width of crackle suppresses in below 0.1mm caused by the processing department of top paint film layer.
As shown in figure 1, being provided with primer coating film layer 3 and top paint film layer 2 on metallic plate and base coating film layer, exist
Crackle is only in situation caused by the paint film layer 2 of top and in top paint film layer 2 and the caused situation of both primer coating film layers 3.
The width 1 of crackle can be measured by the following method caused by processing department in top paint film layer 2：That will scheme
The width of precoated metal sheet 4 after processing shown in 2 carries out mode and the bending direction (precoating after 2T bend tests of 10 deciles
The length direction of metallic plate 4) abreast cut off, 10 sections are observed.The width 1 of crackle to top paint by applying
The most top layer of film layer 2 is measured to obtain (reference picture 1).In addition, paint the width of crackle caused by the processing department of film layer 2 on top
Degree 1 can also be by being observed to determine the film coated surface of precoated metal sheet 4.
The Breadth Maximum of crackle is set as：In 10 sections to centered at the top of bending head and with bending
Direction is measured into the width 1 of the crackle of top paint film layer contained in the scope A of the 1mm length of vertical direction, and its is complete
Maximum in portion's measured value.
The number of crackle is set as：To centered at the top of bending head and and bending direction in 10 each sections
The number of the crackle of contained top paint film layer is added up in into the scope A of the 1mm length of vertical direction, in its aggregate value
Maximum.
Top in example of the present invention in the embodiment discussed later is painted in the combination of film layer and primer coating film layer, to each
From the relation of elongation and overall elongation carried out multiple correlation analysis.
As a result, in the scope of example of the present invention, become as following formula (1), Y (top paint film layer) is stretched
Contribution of the long rate to the elongation of entirety becomes considerably less.
Z=-1.7+0.46X+0.03Y (1)
X is the elongation of primer coating film layer
Y is the elongation of top paint film layer
Z is overall elongation
On the other hand, in the scope of comparative example, become as following formula (2), the elongation of top paint film layer
Contribution to the elongation of entirety is larger.
Z=-3.5+0.61X+0.32Y (2)
In this way, between example of the present invention and comparative example, tribute of the elongation to overall elongation as top paint film layer
Offer the main reason for different, it is believed that：Species resin, the top paint film layer caused by the difference of construction and primer coating film
Influence of adaptation between the influence of adaptation, primer coating film layer and base coating film layer between layer etc..
When carrying out the closely sealed bending machinings of 2T to the precoated metal sheets of embodiments of the present invention, if painting film layer on top
Produce add up to 5~30 width be below 0.1mm crackle, then stress moderately relaxed, therefore primer coating film with
Excellent adhesion after the processing of steel plate.If the width of crackle is bigger than 0.1mm, the adaptation of primer coating film and steel plate becomes
Difference, the adaptation after processing are deteriorated.In addition, if the width of crackle is bigger than 0.1mm, then the dissolution effect of rust resisting pigment can not be obtained
Fruit, therefore processing department corrosion resistance is deteriorated.If the number of crackle is less than 5, stress is not alleviated, therefore adaptation after processing
It is deteriorated.If crackle, more than 30, the adaptation of primer coating film and steel plate is deteriorated, and the adaptation after processing is deteriorated.
It is in this way, by the glass transition point temperature to primer coating film layer and primer coating film layer and top paint film is laminated
The break limit elongation of the film layer to get up is adjusted so that and precoated metal sheet has the elongation of adaptation and appropriateness,
When cutting processing, press process, trickle crackle is produced when film is by die drawn and stress is relaxed, therefore
The film fissility of end face is excellent.
If the break limit elongation of primer coating film layer improves, it is affected by, primer coating film layer and top paint is applied
The break limit elongation of the film layer of film layer altogether also improves, as a result, as the fracture than top paint film layer in itself
The taller value of ultimate elongation.
Top paint film layer contains resin component, and the resin component contains acrylic resin or polyester modification acrylic acid tree
Fat.Thus, precoated metal sheet is also excellent to stain resistance, particularly weatherability, therefore long-term stain resistance is excellent.
Acrylic resin is to make the acrylic monomers or methacrylic acid monomer with hydroxyl using well-known method
The copolymer for carrying out heating response with acrylate or methacrylate etc. and obtaining.As the above-mentioned propylene with hydroxyl
Acid monomers or methacrylic acid monomer, it is, for example, possible to use methacrylic acid -2- hydroxyl second fat, acrylic acid -2- hydroxyl second fat, methyl
Hydroxypropyl acrylate, hydroxypropyl acrylate etc., these monomers can be both used alone, and also these monomers can be subjected to multiple combinations
To use.In addition, as above-mentioned acrylate or methacrylate, it is, for example, possible to use methacrylate, acrylic acid second
The own fat of ester, isopropyl acrylate, n-butyl acrylate, acrylic acid-2-ethyl, methymethacrylate, EMA,
Isopropyl methacrylate, n-BMA, methacrylic acid -2- ethyl hexyl fat etc., both can be independent by these monomers
Use, also these monomers can be subjected to multiple combinations to use.
Polyester modification acrylic resin can use make polyester and acrylic acid Composite, copolymerization or utilize other crosslinkings
Agent makes polyester and acrylic acid be crosslinked resin formed etc..Especially, if polyester modification acrylic resin is lactones is modified third
The resin that olefin(e) acid system polyalcohol and carboxylic vinyl monomer are polymerized, then stain resistance is excellent, is more suitable for.Lactones is modified
Acrylic acid series multiple alcohol is by compound in being added to acrylic resin and anti-without open loop addition is carried out under catalyst
Should and obtain, the acrylic resin be by the vinyl monomer to hydroxyl, carboxylic vinyl monomer and other
Vinyl monomer mixture carried out using common radical polymerization initiator and in common organic solvent it is usual
It is free-radical polymerized and obtain.As carboxylic vinyl monomer, for example, can include：Acrylic acid, methacrylic acid,
Maleic acid, fumaric acid, citraconic acid, itaconic acid, the vinyl monomer of the hydroxyl and phthalic anhydride or hexahydro neighbour's benzene
Addition body of dicarboxylic acid anhydride etc..
It is preferred that primer coating film layer contains rust resisting pigment and resin component.Rust resisting pigment is contained by primer coating film layer, so as to
Can be to the laminated break limit elongation of top paint film layer and primer coating film be adjusted.Moreover, split even if producing
Line, the oxide (white rust) of zinc is produced from crackle can be also suppressed, and instead rust resisting pigment is dissolved, therefore corrosion resistance is good
It is good.In order to assign prolonged erosion, preferably described rust resisting pigment contains in magnesium phosphate, calcium phosphate, aluminum phosphate, trbasic zinc phosphate at least
More than a kind.In addition, the resin component in the primer coating film layer preferably comprises (1) epoxy resin and polyester resin or (2) ring
Oxygen modified polyester resin.The adaptation of film and steel plate determines by the adaptation of primer coating film layer and base coating film layer, in order to
Improve the adaptation, the resin component in preferably described primer coating film layer contains epoxy modified polyester resin.
As epoxy modified polyester resin, preferably include：For example, the carboxyl as polyester resin and the tree containing epoxy radicals
The reaction product of fat, the hydroxyl in the hydroxyl and epoxy resin in polyester resin tied by polyisocyanic acid compound
Close and formed reaction is reacted by addition, condensation, grafting of polyester resin and epoxy resin etc. as product formed etc.
Product.
As polyester resin, the various polyester obtained by known esterified method from multivalence alcohol and polyacid can be included
Resin.Wherein, as multivalence alcohol, can include：For example, ethylene glycol, diethylene glycol (DEG), propane diols, neopentyl glycol, Isosorbide-5-Nitrae-butane two
Alcohol, 1,5- pentane diols, 1,6- hexane diols, A Hydrogenated Bisphenol A, the ethylene oxide adduct of bisphenol-A or PPOX addition
Thing, glycerine, trimethylolethane, trimethylolpropane, pentaerythrite etc., in addition, as polyacid, it can include：For example,
Phthalic anhydride, M-phthalic acid, phthalic acid, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, azelaic acid, the last of the ten Heavenly stems
Diacid, maleic anhydride, fumaric acid, trimellitic anhydride, pyromellitic dianhydride etc., and then, as needed, can also and with benzene first
The monoacid such as acid, p-tert-butyl benzoic acid.
As epoxy resin, can include：For example, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenolic aldehyde type ring
Oxygen tree fat etc..
As polyisocyanic acid compound, can include：For example, toluene diisocyanate, dimethylbenzene diisocyanate resin
(Xylene diisocyanate), diphenylmethane diisocyanate resin, naphthalene diisocyanate resin, hexamethylene diisocyanate, front three
Base hexa-methylene diisocyanate resin, isophorone diisocyanate fat, ENB diisocyanate resin, the isocyanide of hydrogenated methylene diphenyld two
Sour fat, hydrogenated xylylen diisocyanate resin and/or their adduction body, biuret body, isocyanuric acid ester body etc., wherein, especially
It is preferred that the non-yellow stain type such as hexamethylene diisocyanate, tri-methyl hexamethylene diisocyanate resin, isophorone diisocyanate fat
Adduction body, biuret body or the isocyanuric acid ester body of polyisocyanic acid compound.These polyisocyanic acid compounds both can be with
Using a kind, can also be applied in combination two or more.
Aluminum phosphate for rust resisting pigment can use the generally known aluminum phosphate such as reagent, and aluminium dihydrogen tripolyphosphate can be with
Use generally known aluminium triphosphate.Commercially available aluminium dihydrogen tripolyphosphate, such as the work of TAYCA Co. Ltd. systems can be used
" K-WHITE " (registration mark) for aluminium dihydrogen tripolyphosphate etc..
Calcium phosphate can use the generally known calcium phosphate such as reagent.Calcium particularly preferably has been carried out to aluminium dihydrogen tripolyphosphate
The calcium phosphate formed is handled, it is, for example, possible to use " K-WHITE/Ca650 " (Calcium treatment) of TAYCA Co. Ltd. systems etc..
Magnesium phosphate can use generally known magnesium phosphate.The aluminium dihydrogen tripolyphosphate of magnesium processing is particularly preferably implemented,
It is, for example, possible to use " the K-WHITE/K- as the aluminium dihydrogen tripolyphosphate for implementing magnesium processing of TAYCA Co. Ltd. systems
G105 " etc..
Trbasic zinc phosphate can use the generally known trbasic zinc phosphates such as reagent.Zinc particularly preferably has been carried out to aluminium dihydrogen tripolyphosphate
The trbasic zinc phosphate formed is handled, it is, for example, possible to use " K-WHITE/#105 " of TAYCA Co. Ltd. systems etc..
The glass transition point temperature of primer coating film layer is more than 50 DEG C and less than 100 DEG C.If glass transition point temperature
Spend for less than 50 DEG C, then in compacting film by die drawn when will not produce trickle crackle, end face film fissility is deteriorated,
Therefore it is not preferred.If for glass transition point temperature more than 100 DEG C, caused crackle is excessive, the film of part is peeled off,
Therefore end face film fissility is deteriorated, so not preferred.
The glass transition point temperature of primer coating film layer can pass through the glass for the epoxy modified polyester resin for being used as main resin
Glass transition point temperature controls.Particularly, for the glass transition point temperature of primer coating film layer, polyester resin can be made
Partial glass transition point temperature change is controlled.
Top paint film layer does not preferably contain melmac.On top, paint film layer does not contain the situation of melmac
Under, deterioration is less particularly as caused by acid rain, therefore weatherability is more excellent.In addition, because it is to prevent that dirt is physically attached
, so stain resistance is more excellent.
The coefficient of kinetic friction of the pre-coated metal plate surface of embodiments of the present invention is painted the dynamic friction of film layer surface by top
Coefficient determines, preferably 0.06~0.25, more preferably 0.06~0.13.As long as the coefficient of kinetic friction is more than 0.06, then exist
The volume that collapses will not be produced in the case that precoated metal sheet is made into coiled material, therefore preferably.As long as in addition, the coefficient of kinetic friction be 0.25 with
Under, then in compacting, film will not produce cut, and briquettability will not be deteriorated, therefore preferably.
The coefficient of kinetic friction can be adjusted using general wax used and by the wax to the addition of top paint film layer
It is whole.
It is preferred that the precoated metal sheet of embodiments of the present invention placed 72 hours under 50 DEG C, 95%RH moist environments
The water contact angle on the surface of top paint film layer afterwards is less than 60 degree.Water contact angle under this condition is less than 60 degree of feelings
Under condition, dirt is easier to by rain-out.The size of water contact angle under the conditions of this is the smaller the better, and lower limit does not limit especially
It is fixed.The water contact angle can use known sensing equipment to be measured.As the water contact angle made under the conditions of this for 60 degree with
Under method, it is contemplated that to top paint film addition organosilicate method but it is also possible to be method in addition.Top paint applies
Film layer preferably comprises organosilicate.
Organosilicate is the compound containing hydrolyzable silicon substrate, is the chemical combination shown in as following general expressions (1)
Thing or part thereof decomposes condensation product.
(in formula (1), R1~R4Expression can be with mutually the same or different from each other organic group.In addition, n represents more than 1
Integer.)
The content of contained organosilicate paints the tree of film layer preferably with respect to 100 mass parts tops in the paint film layer of top
Fat solid constituent is the mass parts of 0.1 mass parts~20, the mass parts of more preferably 5 mass parts~15.If organosilicate contains
Measure for more than 0.1 mass parts, then stain resistance improves, therefore preferably.In addition, if the content of organosilicate is than 20 mass parts
More (more than 20 mass parts), then easily produce bad order.
In addition, the rust resisting pigment concentration in primer coating film layer is 10 matter preferably with respect to 100 mass parts resin solid contents
Measure the mass parts of part~160, the mass parts of more preferably 50 mass parts~160.If rust resisting pigment concentration is more than 10 mass parts,
Corrosion resistance improves, therefore preferably, if rust resisting pigment concentration, more than 160 mass parts, resin portion is less, therefore end face film
Fissility is deteriorated.
As the rust resisting pigment for the primer coating film layer for being coated on precoated metal sheet, known rust resisting pigment, example can be used together
Such as, calcium ion-exchanged silica can be used, magnesium silicate compounds, non-6 valency chromium system antirust agent, for example, molybdate, vanadic acid/
Phosphoric acid and with pigment (commonly referred to as VP pigment) etc..These can also use commercially available product.Calcium ion-exchanged silica refers to one
As the known silanol groups for making silica surface the calcium ion-exchanged titanium dioxide of the type that ion exchange forms is carried out with calcium
Silicon, commercially available calcium ion-exchanged silica can also be used.As the commercially available silica of calcium ion-exchanged silica,
It can include " SHIELDEX " (registration mark) of GRACE Co., Ltd.s etc..
It is at least one kind of in silica particle, silane coupler, tannic acid by containing base coating film layer so that the bottom of with
The excellent adhesion of the epoxy modified polyester resin of film layer is painted, therefore more preferably.
The adhesion amount of base coating film layer does not have special provision, but if all solids composition quality is 10mg/m2~
1000mg/m2Scope, then more preferably.If the adhesion amount of base coating film layer is less than 10mg/m2, then corrosion resistance be possible to be deteriorated,
End face film fissility is likely to decrease, therefore not preferred.In addition, if the adhesion amount of base coating film layer is more than 1000mg/m2,
Then film fissility in end face is likely to decrease, therefore not preferred.
If the addition of tannic acid is 2g/l~80g/l, more preferably.When the addition of tannic acid is less than 2g/l,
Rust-proof effect, film adaptation can not fully be obtained, on the other hand, if the addition of tannic acid more than 80g/l, on the contrary
Rust-proof effect, film adaptation can be reduced, be not dissolved in the aqueous solution.
As the silane coupler that can be used, can include：For example, γ-(2- aminoethyls) aminopropyl trimethoxy silicon
Alkane, γ-(2- aminoethyls) aminopropyltriethoxy dimethoxysilane, γ-(2- aminoethyls) aminopropyl triethoxysilane, γ-(2-
Aminoethyl) aminopropyltriethoxy diethoxy silane, γ-(2- aminoethyls) aminopropyltriethoxy dimethoxysilane, γ-metering system
Acryloxypropylethoxysilane trimethoxy silane, γ-methacryloyloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl
Base propyl-triethoxysilicane, γ-methacryloyloxypropyl methyl diethoxy silane, N- β-(N- vinyl benzyl ammonia
Ethyl)-γ-aminopropyltrimethoxysilane, N- β-(N- vinyl benzyls aminoethyl)-γ-aminopropyltriethoxy dimethoxy silicon
Alkane, N- β-(N- vinyl benzyls aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- β-(N- vinyl benzyls aminoethyl)-
γ-aminopropyltriethoxy diethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl
Dimethoxysilane, γ-glycidoxypropyl group triethoxysilane, γ-glycidoxypropyl diethoxy silane,
γ mercaptopropyitrimethoxy silane, γ-mercaptopropyi methyl dimethoxysilane, γ-Mercaptopropyltriethoxysilane,
γ-mercaptopropyi methyldiethoxysilane, MTMS, dimethyldimethoxysil,ne, methyl triethoxy
Silane, dimethyldiethoxysilane, vinyltriacetoxy silane, γ-r-chloropropyl trimethoxyl silane, γ-chloropropyl
Methyl dimethoxysilane, γ-chloropropyl triethoxysilane, γ-chloropropyl diethoxy silane, the silicon nitrogen of hexamethyl two
Alkane, γ-anilino- propyl trimethoxy silicane, γ-anilino- hydroxypropyl methyl dimethoxysilane, γ-second of anilino- propyl group three
TMOS, γ-anilino- hydroxypropyl methyl diethoxy silane, vinyltrimethoxy silane, vinyl methyl dimethoxy
Silane, VTES, vinyl methyl diethoxy silane, octadecyldimethyl (3- (trimethoxy first silicon
Alkyl) propyl group) ammonium chloride, octadecyldimethyl (3- (methyl dimethoxy epoxide silicyl) propyl group) ammonium chloride, octadecyl
Dimethyl (3- (triethoxysilyl) propyl group) ammonium chloride, octadecyldimethyl (3- (methyl diethoxy monosilanes
Base) propyl group) ammonium chloride, gamma-chloropropylmethyldimethoxysilane, γ-mercaptopropyi methyl dimethoxysilane, methyl trichlorine
Silane, dimethyldichlorosilane, trim,ethylchlorosilane etc.,
For film adaptation, corrosion resistance this point consider, if the content of silane coupler is 2g/l~80g/l, more
It is preferred that.
In the present embodiment, silica particle refers to be dispersed in water in order to have a case that fine particle diameter
The silica of water dispersity can be stably maintained down.As above-mentioned silica particle, such as can use
" SNOWTEX N ", " SNOWTEX C ", " SNOWTEX UP ", " SNOWTEX PS " (being Nissan Chemical Industries company system),
" silica dioxide gel commercially available ADELITE AT-20Q " (Asahi Electro-Chemical Co. Ltd's system) etc. or AEROSIL#300 (Japan
AEROSIL company systems) etc. ground silica etc..Silica particle performance needed for suitably select.
In addition, the drying baking method in application can use air drier, straight fire type drying machine, far infrared drying
The generally known dry baking method such as machine, induction heating type drying machine.
The primer coating film layer of present embodiment and the thickness of top paint film layer are respectively preferably 1 μm~30 μm.It is small in thickness
When 1 μm, it is possible to the function (such as coloring etc.) as film layer can not be obtained, when thickness is more than 30 μm, in application
It is possible to produce the painting defect for being referred to as foaming during baking.
Metallic plate used in the precoated metal sheet of embodiments of the present invention can use generally known metal material.
The metal material can also be alloy material.As such metal material, can include：For example, steel plate, stainless steel plate, aluminium
Plate, aluminium alloy plate, titanium plate, copper coin etc..It can implement various plating on the surface of these materials.
As the species of plating, can include：For example, it is zinc-plated, aluminize, copper facing, nickel plating etc. or their alloy
Plating.In the case of steel plate, hot-dip galvanized steel sheet, plated steel sheet, zinc-nickel alloy coated steel sheet, melting conjunction can be applicable
The generally known steel plate and coated steel sheet such as aurification galvanized steel plain sheet, aludip, aluminum-zinc alloy coated steel sheet, stainless steel plate.
Particularly in the case of electrogalvanized steel plate, corrosion resistance more improves, therefore more preferably.Here, electrogalvanized steel plate refers to
It is zinc-plated that hot-dip galvanized steel sheet, plated steel sheet etc. are plated with the galvanized steel plain sheet of zinc, zinc-nickel alloy coated steel sheet, molten alloyization
The alloy plating steel plate of the zinc such as steel plate, aluminum-zinc alloy coated steel sheet and other metals.In these electrogalvanized steel plates, especially
It is larger with the sacrifice corrosion protection result of galvanized steel plain sheet as hot-dip galvanized steel sheet, plated steel sheet, and corrosion resistance is more excellent, therefore
More preferably.In addition, if the plating adhesion amount of these electrogalvanized steel plates is per one side 40g/m2~90g/m2, then can take into account and add
Work and corrosion resistance, therefore more preferably.Plating adhesion amount per one side is less than 40g/m2When, corrosion resistance is possible to be deteriorated, and exceedes
90g/m2When, it is possible to produce plating crackle in processing, processability is deteriorated.
The coating process of each film layer is not particularly limited, and generally known coating process can be used, for example, roller coat, woods
Grignard roller coat (Wringer roll), aerial spraying, airless spraying, infusion process etc..And then if there are these coating dresses complete
Put be commonly referred to as coil painting production line, sheet material paint line continuous paint line on be coated, then application
Operating efficiency is good, can largely be produced, therefore more preferably.
【Embodiment】
Hereinafter, embodiment is described in detail.
1. metal raw sheet
Hot-dip galvanized steel sheet " NS SILVER ZINC (the NS シ ル バ ー ジ of Nippon Steel ＆ Sumitomo Metal Corporation are used
Application Network) (registration mark) " (hereinafter referred to as GI), plated steel sheet " NS ZINKOTE (the NS ジ of Nippon Steel ＆ Sumitomo Metal Corporation
ン コ ー ト) (registration mark) " (hereinafter referred to as EG), the zinc-nickel alloy coated steel sheet " NS of Nippon Steel ＆ Sumitomo Metal Corporation
It is ZINKLITE (NS ジ Application Network ラ イ ト) (registration mark) " (hereinafter referred to as ZL), aluminium sheet " JIS3004 " (hereinafter referred to as Al), stainless
Steel plate " SUS430 " (hereinafter referred to as SUS), Zn-Al alloy coated steel sheet " Galvalume (the ガ Le of Tie Zhujin steel plates society
バ ニ ウ system) (registration mark) " (hereinafter referred to as GL), the zinc-al-mg-si alloy plating steel of Nippon Steel ＆ Sumitomo Metal Corporation
Plate " SUPER DYMA (ス ー パ ー ダ イ マ) (registration mark) " (hereinafter referred to as SD), Nissin Steel Co., Ltd. zinc-
Aluminium-magnesium alloy coated steel sheet " ZAM (registration mark) " (hereinafter referred to as ZAM) is used as raw sheet.The thickness of slab for having used raw sheet is 0.6mm
Raw sheet.
Used ZL plating adhesion amount is one side 20g/m in this experiment2, the nickel amount in coating is 12 mass %.
In addition, it is one side 60g/m that GI, SD, GL, ZAM, which have used plating adhesion amount,2Steel plate, it is one side that EG, which has used plating adhesion amount,
20g/m2Steel plate.
2. coating
In the present embodiment, following precoated metal sheet has been made：On metallic plate (raw sheet), on a face (surface)
With the base coating film layer for not containing chromate, there is primer coating film layer on the base coating film layer, in the primer coating film layer
On there is top paint film layer, totally 3 coating film, have on another face (back side) with surface identical base coating film layer,
On the base coating film layer have with surface identical primer coating film layer, there is back side film layer on the primer coating film layer.
(base coating film coating)
Base coating 1：Japanese PAINT Co. Ltd. systems EC2000
Base coating 2：Silane coupler (γ-glycidoxypropyltrime,hoxysilane), 1.0g/L containing 5g/L
Water dispersible silicone colloidal sol (Misao Kusano's system " SNOWTEX-N "), 25g/L water system polyester resin (Japan spin strain formula
Commercial firm MD-1100) the aqueous solution
(primer coating film coating)
Using the resin described in table 2 as main resin, make its molten in a manner of resin solid content concentration turns into 30 mass %
In organic solvent, (use is by quality ratio cyclohexanone to solution：Solvesso 150=1：1 solvent mixed).
In the case of mixing two kinds of main resins, 50 mass % main resin is respectively mixed with.The glass transition point temperature of resin described in table 2
Degree is determined by means of differential scanning calorimetry determination method.
Then, as crosslinking agent, the melamine tree of Cytec Industries Co. Ltd. systems is with the addition of to main resin
Fat " CYMEL (registration mark) 303 ".The addition of melmac is calculated as main tree with the mass ratio according to resin solid content
Fat solid constituent：Melmac solid constituent=80：20 mode is added.Further, to the polyester resin and
The acidic catalyst of 0.5 mass % Cytec Industries Co. Ltd. systems is with the addition of in the mixed solution of melmac
" Catalyst (the few ス ト of キ ヤ タ) (registration marks) 600 " is simultaneously stirred to these, so as to obtain varnish paint for agent.Connect
, the aluminium dihydrogen tripolyphosphate " K- of the desired amount of TAYCA Co. Ltd. systems as rust resisting pigment is with the addition of into the coating
WHITEG-105 " (hereinafter referred to as P-A1), " SHIELDEX C303 " are (following for the calcium ion-exchanged silica of GRACE company systems
Referred to as Ca-Si), trbasic zinc phosphate system rust resisting pigment " EXPERT (registration mark)-NP500 " (hereinafter referred to as P-Zn), phosphoric acid of reagent
Dihydro magnesium (hereinafter referred to as P-Mg), reagent calcium phosphate (hereinafter referred to as P-Ca) and be stirred, so as to obtain primer base
(with reference to Table 3 below).The glass transition point temperature of resin described in table 3 is determined by means of differential scanning calorimetry determination method.
Table 2
| Resin types | Tg(℃) | |
| B1 | Epoxy modified polyester resin | 40 |
| B2 | Epoxy modified polyester resin | 50 |
| B3 | Epoxy modified polyester resin | 55 |
| B4 | Epoxy modified polyester resin | 70 |
| B5 | Epoxy modified polyester resin | 100 |
| B6 | Epoxy modified polyester resin | 110 |
| B7 | Epoxy resin | 65 |
| B8 | Polyester resin | 55 |
| B14 | Polyester resin | 79 |
Epoxy modified polyester resin：Bisphenol A type epoxy resin and polyester (Co. Ltd. system Vylon each grade is spun by Japan)
Copolymer
Epoxy resin：Bisphenol A type epoxy resin
Polyester resin (glass transition point temperature is 55 DEG C)：Vylon (registration mark) 660
Table 3
In order to be measured to the break limit elongation of primer coating film layer, tension test is implemented.In tension test,
Adhere to 100mg/m on GI raw sheets2Base coating 2 after 5 μm of application primer base, using speed be 200mm/ minutes progress
Stretching.The break limit elongation of raw sheet is 60%, equivalent to the elongation of film during less than 60%.
(top paint film coating)
<Main resin>
Using the resin described in following table 4 as main resin.Here, the glass transition point temperature of the resin described in table 4
It is determined by means of differential scanning calorimetry determination method.
Table 4
Acrylic resin (55 DEG C of glass transition temperature)：Udouble (ユ ー ダ Block Le) (registration mark) S-2818
Polyester resin (55 DEG C of glass transition temperature)：Vylon (registration mark) 660
Polyester resin (79 DEG C of glass transition temperature)：Vylon (registration mark) 885
Polyester modification acrylic resin (21 DEG C and 55 DEG C of glass transition temperature)：Above-mentioned copolymer
<Crosslinking agent>
As amino resin crosslinking agent, using three well Cytec Co. Ltd. systems as methylated melamine resins
" CYMEL (registration mark) 303 " (being designated as Me), Sumitomo Bayer Urethane Co. Ltd. systems as carbimide
Desmodur BL-3175 (being designated as BI), the epoxy resin EX-252 (being designated as EP) of Nagasechemtex company systems are according to main tree
Fat：Crosslinking agent is calculated as 80 with mass parts：20 mode is added.Three well Cytec Co. Ltd. systems are used
" Catalyst 602 " is used as catalyst.For the addition of catalyst, add relative to the main resin solid content of 100 mass parts
0.5 mass parts are added.
<Organosilicate>
As organosilicate, methyl silicate 51 (Colcoat Co. Ltd. systems) with the addition of.
<Wax>
The wax that the fusing point for having used Japan Sekiscoat Co., Ltd. is 61 DEG C.Change the coefficient of kinetic friction by the addition of wax.
<Pigment>
Coloured using commercially available titanium oxide and iron oxide, carbon black.Full pigment concentration setting is relative to 100 mass parts
Solid constituent is 20 mass parts.
These materials are mixed, the composition that the top as coating is painted to coating is shown in table 5.In following tables
In 5, the addition of silicate be mass parts relative to 100 mass parts resin solid contents.With resin solid content concentration into
For 30 mass % mode them is dissolved in organic solvent (used is cyclohexanone by quality ratio：Solvesso 150=
1：1 mixture).
Table 5
It is measured to paint the break limit elongation of film layer to top, implements tension test.In tension test,
Adhere to 100mg/m on GI raw sheets2Base coating 2, the top that 5 μm of application afterwards paint coating, enter by 200mm/ minutes of speed
Stretching is gone.The break limit elongation of raw sheet is 60%, equivalent to the elongation of film during less than 60%.
3. the making of precoated metal sheet
By FC-4336 (Japanese Parkerizing Co. Ltd. systems) concentration be 2 mass % 60 DEG C of temperature water
Impregnated 10 seconds in solution, so as to which various metallic plates are carried out into degreasing, its drying is made after washing.Then, existed using roll coater
The two sides coating base coating of metallic plate, makes its drying using air drier.The drying condition of air drier is according to gold
What the arrival plate temperature of category plate was set for 60 DEG C.80g/ is adhered to based on all solids composition by the adhesion amount of non-chromate processing
m2Mode carry out application.
Then, the two sides of the metallic plate of base coating is being implemented respectively to the primer coating film of above-mentioned making using roll coater
Application is carried out in a manner of dry film thickness turns into 5 μm, using the induction heater for being blown into hot blast with the arrival plate temperature of metallic plate
It is set to dry hardening as 210 DEG C of conditions.Dry toast after, using injector make water whisk off application after metallic plate, enter
Water cooling is gone.
And then on primer coating film layer, painted using roll coater by pushing up in a manner of the dry film thickness of coating turns into 15 μm to one
Face carry out top paint coating application, by the dry film thickness of CB coating turn into 5 μm in a manner of to another side application Nippon Fine
" FL100HQ " of the grey as CB coating of coatings Co. Ltd. systems and utilize the induction heater for being blown into hot blast
Baking is dried as 230 DEG C of condition with the arrival plate temperature of metallic plate simultaneously, water cooling is carried out, sample is made for so as to obtain
Pre-coated steel plate.
The composition for the sample surfaces being fabricated to is recorded in table 6 below.
Table 6
The evaluation method of precoated metal sheet is recorded in detail.
1. water contact angle
The precoated metal sheet being fabricated to is placed 72 hours under 50 DEG C, 95%RH moist environments, uses consonance interface
Co. Ltd. system " DM-501 " is learned, the surface that film layer is painted to top is dripped 2.0 μ l water droplet, and water is contacted with the method for θ/2 after 1 second
Angle is determined.5 measure have been carried out, have been averaged value as evaluation object.
2. stain resistance is tested
The sample being fabricated to has been carried out 3 months exposure test field outside the room near the bank positioned at richness Jinshi City of Chiba county
Exposure test.Sample after experiment is evaluated the presence or absence of dirt by visual observation, by completely without the situation of dirt
A is evaluated as, will somewhat observe that the situation of dirt is evaluated as B, it will be clear that observe that the situation of dirt is evaluated as C in ground.Evaluating
In the case of for C, it is judged as that stain resistance is deteriorated.
3. resistance to raindrop contaminative experiment
The sample being fabricated to 12 have been carried out in exposure test field outside the room near the bank positioned at richness Jinshi City of Chiba county
The exposure test of the moon.Sample after experiment is evaluated the presence or absence of dirt containing raindrop vestige by visual observation, will be complete
The situation for not having raindrop imprint mark and dirt is evaluated as A, will locally observe raindrop imprint mark but not have dirt in other entirety
And the situation of good contaminative is evaluated as B, it will locally observe raindrop imprint mark and overall situation about being also dirty is evaluated as C,
It will clearly see raindrop vestige and overall situation about being also dirty be evaluated as D.In the case where being evaluated as D, it is judged as resistance to
Raindrop contaminative is deteriorated.
4. the end face film fissility after processing
The precoated metal sheet being fabricated to is cut off, reused after mould have dropped in lower burr portion along burr direction, will
Adhesive tape is tightly pasted on the film of end face portion, and visually to observe after adhesive tape stripping, the presence or absence of peeling to film is carried out
Investigation.A will be evaluated as without situation about peeling off completely, the situation for finding fraction of cracking in film, peeling off is evaluated as B,
That clearly larger crackle, stripping are evaluated as C to be present in film.In the case where being evaluated as C, after being judged as processing
End face film fissility be deteriorated.
5. process crack evaluation
Carried out to cutting into the test film that width is 5cm with following JIS.G3312 test method in 20 DEG C of atmosphere
2T bendings.Specifically, two and test film identical coated plate are clamped in inner side, make to be coated with the surface of top paint film
The closely sealed bending (reference picture 2) of 180 degree has been carried out in outside.In the adhesive tape (trade name to bending section entirety apposition：(cellophane
Band) セ ロ Ha ン テ ー プ) after, adhesive tape is peeled off, for unstripped test film, the width of test film is carried out 10 etc.
The mode divided abreast is cut off with bending direction, and 10 sections are observed.Applied by being painted to the top shown in Fig. 1
The most top layer of film layer 2 is measured, so as to be determined to the width 1 of crackle.In 10 sections, to bending
Crackle centered on overhead and with bending direction into top paint film layer contained in the scope A of the 1mm length of vertical direction
Width 1 be determined, the maximum in its whole measured value is set as to the Breadth Maximum (mm) of crackle.In addition, every
In individual 10 sections, to the scope A centered on bending head top and with bending direction into the 1mm length of vertical direction
The number of the crackle of interior contained top paint film layer add up to (in the case of figure 2, in the scope A contained by
The number of crackle is 7), the maximum in its aggregate value is set as to the number of crackle.In addition, bending direction refers to 2T bending examinations
The length direction of precoated metal sheet 4 after testing.In following tables 7, the number and maximum of crackle are described for each test film
Width (mm).
6. corrosion resistant test
The sample that 2T bendings have been carried out in the environment of 20 DEG C is implemented according to the method described in JIS K 5400.9.1
Salt spraytest.By brine spray to processing department.For test period, the sample for EG and ZL to be used for raw sheet,
It is set as 240 hours, for the sample for other raw sheets, is set as 500 hours.The white rust area occupation ratio of processing department is carried out
Measure, is evaluated as A by less than 5% situation, less than 20% situation is evaluated as into B, C is evaluated as by less than 50%, will be exceeded
50% situation is evaluated as D.In the case where being evaluated as D, it is judged as that corrosion resistance is deteriorated.
7. the coefficient of kinetic friction
It is φ by 100g, ball pressure head of load using superficiality measuring machine HEIDON-14 types (Xin Dong science society system)
10mm, the condition that translational speed is 150mm/ points are determined.
The evaluation result of above-mentioned experiment is summarized in table 7.
Table 7
In order to be measured to the break limit elongation of the film layer by primer coating film layer and top paint film layer altogether,
Implement tension test.In tension test, adhere to 100mg/m on GI raw sheets2Base coating 2 after 5 μm of application bottom
Coating is painted, the top paint coating of further 5 μm of application, is stretched by 200mm/ minutes of speed.The break limit of raw sheet is stretched
Long rate is 60%, equivalent to the elongation of film during less than 60%.
The precoated metal sheet of embodiments of the present invention has been carried out untill break limit elongation turns into 10%
Tension test, but be cracked without being formed.
It is clear that by above-mentioned table 7：End face film after the stain resistance of the precoated metal sheet of example of the present invention, processing is peeled off
Property, corrosion resistance excellent.
In addition, it is clear that by above-mentioned table 7：The precoated metal sheet of example of the present invention when carrying out the closely sealed bending machinings of 2T,
Into in the scope A of the 1mm length of vertical direction centered at the top of the bending head and with bending direction, on top, paint film layer produces conjunction
The crackle that the width for being calculated as 5~30 is below 0.1mm.
It can be seen that by above-mentioned table 7：In the break limit of the film layer by primer coating film layer and top paint film layer altogether
In situation (level 43) of the elongation less than 10%, compared with example of the present invention, the crackle of film layer is larger, and the end face after processing applies
Film fissility is substantially deteriorated.In addition, understand：In the break limit of the film layer by primer coating film layer and top paint film layer altogether
Elongation has exceeded in 25% situation (level 38,40~42 and 44~48), compared with example of the present invention, stain resistance or processing
End face film fissility afterwards is deteriorated.
In addition, understand：Top paint film layer break limit elongation more than 10% and primer coating film layer break limit
Elongation is that compared with example of the present invention, stain resistance is substantially deteriorated in 40%~50% situation (level 40 and 45~47).
Also, understand：On top, the break limit elongation of paint film layer is 5%~10% and the fracture pole of primer coating film layer
Limit in situation (level 37,43 and 49) of the elongation less than 40%, compared with example of the present invention, the crackle of film layer is larger, processing
End face film fissility afterwards is substantially deteriorated.
It is clear that by above-mentioned table 7：Polyester resin is set in the resin component of primer coating film layer and top paint film layer
And the break limit elongation of the film layer by primer coating film layer and top paint film layer altogether is less than 10% situation (level
49) under, compared with example of the present invention, the end face film fissility after stain resistance and processing is deteriorated.In addition, understand：Applied in priming paint
The resin component of film layer and top paint film layer is set to polyester resin and the break limit elongation of primer coating film layer exceedes
In 50% situation (level 48), compared with example of the present invention, the end face film fissility after stain resistance and processing is substantially deteriorated.
In addition, understand：Top paint film layer break limit elongation exceeded 10% situation be similarly (level 45~
47), compared with example of the present invention, the end face film fissility after stain resistance and processing is substantially deteriorated.
More than, referring to the drawings embodiments of the invention are explained, but the present invention be not limited to it is above-mentioned
Example.As long as the people with the universal knowledege in the technical field belonging to the present invention, obviously it can just be remembered in claims
Various modifications or fixed case are expected in the category of the technological thought of load, for these contents, it should also be understood as falling within this hair
Bright technical scope.
Industrial applicability
According to the embodiment of the present invention, using the teaching of the invention it is possible to provide a kind of long-term stain resistance, end face film fissility, corrosion resistance
Excellent precoated metal sheet.
Symbol description
The width of 1 crackle
2 top paint film layers
3 primer coating film layers
4 precoated metal sheets
Scope centered on A is at the top of bending head and with bending direction into the 1mm length of vertical direction
Claims (10)
1. a kind of precoated metal sheet, it has：
Metallic plate；
Base coating film layer, it is arranged on the metallic plate and does not contain chromate；
Primer coating film layer, it is arranged on the base coating film layer and does not contain chromate；With
Top paint film layer, it is arranged on the primer coating film layer,
Wherein, the break limit elongation of the film layer by the primer coating film layer and the top paint film layer altogether is 10%
~25%,
The glass transition point temperature of the primer coating film layer be more than 50 DEG C and less than 100 DEG C,
The top paint film layer contains resin component, and the resin component contains acrylic resin or polyester modification acrylic acid tree
Fat,
When carrying out the closely sealed bending machinings of 2T to the precoated metal sheet, centered at the top of bending head and with bending direction into
In the 1mm length ranges of vertical direction, produced in the top paint film layer and add up to 5~30 width as below 0.1mm's
Crackle.
2. precoated metal sheet according to claim 1, it is characterised in that
The break limit elongation of the primer coating film layer is 40%~50%,
The break limit elongation of the top paint film layer is 5%~10%,
The primer coating film layer contains rust resisting pigment and resin component, and the rust resisting pigment contains magnesium phosphate, calcium phosphate, aluminum phosphate
Or at least one or more in trbasic zinc phosphate, the resin component in the primer coating film layer contain epoxy modified polyester resin.
3. precoated metal sheet according to claim 1 or 2, it is characterised in that
The primer coating film layer contains rust resisting pigment, and the concentration of the rust resisting pigment is relative to 100 mass parts resin solid contents
For the mass parts of 10 mass parts~160.
4. according to precoated metal sheet according to any one of claims 1 to 3, it is characterised in that
The top paint film layer does not contain melmac.
5. according to precoated metal sheet according to any one of claims 1 to 4, it is characterised in that
The surface dynamic friction coefficient of the top paint film layer is 0.06~0.25.
6. according to precoated metal sheet according to any one of claims 1 to 5, it is characterised in that
The water contact angle on the surface of the top paint film layer after being placed 72 hours under 50 DEG C, 95%RH moist environments is 60 degree
Below.
7. according to precoated metal sheet according to any one of claims 1 to 6, it is characterised in that
The top paint film layer contains organosilicate.
8. precoated metal sheet according to claim 7, it is characterised in that
The content of the organosilicate in the top paint film layer paints the resin of film layer relative to top described in 100 mass parts
Solid constituent is the mass parts of 0.1 mass parts~20.
9. according to precoated metal sheet according to any one of claims 1 to 8, it is characterised in that
The base coating film layer contains at least one kind of in silica particle, silane coupler, tannic acid.
10. according to precoated metal sheet according to any one of claims 1 to 9, it is characterised in that
The thickness of the primer coating film layer is 3 μm~10 μm, and the thickness of the top paint film layer is 5 μm~25 μm.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2015/062867 WO2016174746A1 (en) | 2015-04-28 | 2015-04-28 | Pre-coated metal plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107531018A true CN107531018A (en) | 2018-01-02 |
| CN107531018B CN107531018B (en) | 2018-11-09 |
Family
ID=56708826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580078996.0A Active CN107531018B (en) | 2015-04-28 | 2015-04-28 | Precoated metal sheet |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5975197B1 (en) |
| KR (1) | KR101839281B1 (en) |
| CN (1) | CN107531018B (en) |
| MY (1) | MY165606A (en) |
| WO (1) | WO2016174746A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110760916A (en) * | 2019-11-18 | 2020-02-07 | 和县科嘉阀门铸造有限公司 | Method for improving corrosion resistance of magnesium alloy valve |
| CN113260464A (en) * | 2019-12-23 | 2021-08-13 | 泰克大洋工业株式会社 | Laminate and method for preventing rust |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7058160B2 (en) * | 2018-03-28 | 2022-04-21 | 三井化学株式会社 | Metal primer, laminate, battery and packaging |
| CN117203052A (en) | 2021-03-31 | 2023-12-08 | 日本制铁株式会社 | Precoated steel sheet and molded article |
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| JPH10314664A (en) * | 1997-05-22 | 1998-12-02 | Nisshin Steel Co Ltd | Precoated steel sheet excellent in resistance to staining |
| CN101232994A (en) * | 2005-07-28 | 2008-07-30 | 新日本制铁株式会社 | Precoated metal plate and process for producing the same |
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| JPS5783449A (en) * | 1980-11-13 | 1982-05-25 | Nippon Paint Co Ltd | Precoated metallic plate |
| JPH01194979A (en) * | 1987-09-25 | 1989-08-04 | Kansai Paint Co Ltd | Method of coating aluminum foil |
| JP3144433B2 (en) * | 1991-12-20 | 2001-03-12 | 日立金属株式会社 | Weatherproof coating film and aluminum wheel formed therefrom |
| JP2000144019A (en) * | 1998-11-06 | 2000-05-26 | Nippon Steel Metal Prod Co Ltd | Coated steel sheet having high hardness and high anticorrosion and excellent in chipping resistance |
| JP2001311038A (en) * | 2000-04-27 | 2001-11-09 | Nippon Yushi Basf Coatings Kk | Primer coating composition |
| JP4398771B2 (en) * | 2004-04-02 | 2010-01-13 | 株式会社神戸製鋼所 | Resin coated metal plate |
| JP4460441B2 (en) * | 2004-12-24 | 2010-05-12 | 新日本製鐵株式会社 | Painted metal plate |
| JP4324093B2 (en) * | 2004-12-24 | 2009-09-02 | 新日本製鐵株式会社 | Precoated metal sheet excellent in workability and stain resistance and method for producing the same |
| JP4874153B2 (en) * | 2007-04-04 | 2012-02-15 | 新日本製鐵株式会社 | Pre-coated metal plate, metal molded body obtained by molding the same, and method for producing pre-coated metal plate |
-
2015
- 2015-04-28 WO PCT/JP2015/062867 patent/WO2016174746A1/en active Application Filing
- 2015-04-28 JP JP2016528032A patent/JP5975197B1/en active Active
- 2015-04-28 KR KR1020177030919A patent/KR101839281B1/en active IP Right Grant
- 2015-04-28 MY MYPI2017703663A patent/MY165606A/en unknown
- 2015-04-28 CN CN201580078996.0A patent/CN107531018B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10314664A (en) * | 1997-05-22 | 1998-12-02 | Nisshin Steel Co Ltd | Precoated steel sheet excellent in resistance to staining |
| CN101232994A (en) * | 2005-07-28 | 2008-07-30 | 新日本制铁株式会社 | Precoated metal plate and process for producing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110760916A (en) * | 2019-11-18 | 2020-02-07 | 和县科嘉阀门铸造有限公司 | Method for improving corrosion resistance of magnesium alloy valve |
| CN110760916B (en) * | 2019-11-18 | 2022-04-05 | 和县科嘉阀门铸造有限公司 | Method for improving corrosion resistance of magnesium alloy valve |
| CN113260464A (en) * | 2019-12-23 | 2021-08-13 | 泰克大洋工业株式会社 | Laminate and method for preventing rust |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5975197B1 (en) | 2016-08-23 |
| WO2016174746A1 (en) | 2016-11-03 |
| CN107531018B (en) | 2018-11-09 |
| KR20170125999A (en) | 2017-11-15 |
| MY165606A (en) | 2018-04-16 |
| KR101839281B1 (en) | 2018-03-15 |
| JPWO2016174746A1 (en) | 2017-05-18 |
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