CN101384427B

CN101384427B - Precoated metal plate

Info

Publication number: CN101384427B
Application number: CN2007800057243A
Authority: CN
Inventors: 服部伸郎
Original assignee: Kobe Steel Ltd
Current assignee: Kobe Steel Ltd
Priority date: 2006-03-27
Filing date: 2007-03-26
Publication date: 2012-09-05
Anticipated expiration: 2027-03-26
Also published as: WO2007116670A1; WO2007116670A9; KR101009869B1; KR20080106303A; CN101384427A

Abstract

This invention provides a precoated metal plate that can prevent the occurrence of defects in an optical disk, and, at the same time, can maintain high peel strength of an adherend to a resin film, and can realize easy adhesion of the adherend to the surface of the resin film. The precoated metal plate comprises a metal plate and a resin film provided on the surface of the metal plate. The resin film comprises an epoxy resin matrix layer and soft beads dispersed in the epoxy resin matrix layer. For the soft beads, the compressive strength at single bead 10% deformation by a microcompression test is not more than 10 MPa. The content of the soft beads is not less than 5% by mass and not more than 50% by mass based on the epoxy resin matrix layer, and the average particle diameter of the soft beads is not less than 1.1 times and not more than 5 times the average thickness of the epoxy resin matrix layer.

Description

Precoated metal sheet

Technical field

The present invention relates to precoated metal sheet, be applicable to that household electrical appliance and automobile carry parts off-grade plate material and member, also have building materials, roof material etc.

Background technology

With steel plate and aluminium sheet or aluminium alloy plate is that the metal sheet (metallic plate) of representative has high intensity and processability concurrently, carries parts, also has various purposes such as building materials applicable to household electrical appliance, automobile through implementing various processing.The processed goods that is applicable to the metallic plate of these purposes is that purpose is carried out surface treatment to improve outward appearance and corrosion resistance etc. sometimes.At present; This surface-treated main flow is that the shape that metallic plate is processed as regulation is carried out coating (post-coat) mode behind the surface-treated later on again; But; Recently, be purpose to improve the environment of plant and simplified processing process and cost reduction etc., also define to have in advance metallic plate is carried out precoating (pre-coat) mode that surface-treated Gu matel coated plate is shaped and is processed as the shape of regulation and uses.In addition; In recent years; Developed such precoated metal sheet: be used to adapt to the diversified and superior of goods, machine and give the functional precoated metal sheet of all function ratio such as anti-finger printing, preventing property of cut (antj-scratched property), ground connection property, thermal diffusivity, thermal insulation, antibiotic property, lubricity etc., and extensively popularize.

In precoated metal sheet, owing under the state of implementing top finishing, form processing, therefore; Aspect coated film; Not only require excellent shaping processability, and require excellent appearance, proterties etc., intactly reach products appearance in order to the outward appearance behind the press molding.For example, motion has following precoated metal sheet in patent documentation 1: on the aluminum alloy plate materials with the thickness of 0.5～10 μ m apply with epoxy resin, urethane resin and allyl resin separately or its mixture be basic resin and contain 5～40%SiO below the particle diameter 0.1 μ m ₂And the coating of 5～60% lubricants, formability and preventing property of cut aspect that coefficient of friction is controlled at below 0.15 are excellent.

The precoated metal sheet of record is made up of aluminum alloy plate materials in the patent documentation 1; But; Usually; With aluminium is raw-material precoated metal sheet well received aspect the purposes of pursuing lightweight, carries box class and framework, bonnet class, the vehicle mounted Denso article of liquid crystal indicator of the CD-ROM drive of usefulness as an example for notebook computer, also is applicable to box class and members such as the interior stereo of ECU (Electronic Control Linit) and automobile, Vehicular navigation system, CD automatic disk changer.Wherein, under the situation that is applicable to CD-ROM drive and CD automatic disk changer, carry CDs such as CD and DVD, still, recently, because the popularizing of erasable type CD-ROM drive, many people begin individual editing music CD etc. and make the self-control CD.In addition, such self-control CD uses with the state that is pasted with the adhesive matter such as identification label that the identification optical disc surface uses sometimes.

But the use of this identification label has produced new problem.For example, having produced must be to peeling off the part of identification label because of the heating of device etc., and the bonding part that exposes thereafter adheres to the danger at each position in the device again and guards against.

In addition, as shown in Figure 4, on existing CD-ROM drive 20, CD 10 device on pan arrest 21, is packed into pan arrest 21 in the box 22.But, illustrate, developing a kind of pan arrest that installs CD recently and do not coming in and going out, only CD is inserted the peristome of CD-ROM drive and the CD-ROM drive of the groove mode inserted.In this groove mode CD-ROM drive, CD is come in and gone out in the position near the inner face of HDDbox.Therefore, the inner face friction of the surface of CD and HDDbox when existing CD to come in and go out an and this problem of slip cut on being prone to draw in order to prevent it, need prevent to draw on the surface of CD the processing of cut.

Therefore, in precoated metal sheet, require to have concurrently following characteristic: and do in the purposes of binding, binding is difficult to adhere to, and dirt and oil is difficult to adhere to, in addition, even contacts such as CD also are difficult to the surface scratch at CD.To such problem; Present inventors have developed following precoated metal sheet: for through to become on the metal sheet surface with the fluorine resin be basic unit and the mixed proportion that urea alkane bead is mixed into regulation, with respect to the resin involucra of ratio such particle diameter in the scope of regulation of leather film thickness and form the precoated metal sheet that processing is used; Have following characteristic concurrently: formability and outward appearance with basic excellence; And and do in the purposes of binding, binding is difficult to adhere to, and dirt and oil are difficult to adhere to; In addition, even contacts such as CD also are difficult to the surface scratch (the special 2005-294109 of hope) at CD.

In addition, in patent documentation 2, disclose precoating aluminum alloy plate with the epithelium that constitutes by the basic resin layer that contains resin beads.But,, therefore, have and preventing that precoating aluminum alloy plate from will injure the problem on surfaces such as CD when the CD of the injured plate of body etc. contacts because disclosed resin beads is the material that is called the comparison hard of propylene or fluororesin in the patent documentation 2.

Patent documentation 1: No. 3388156 communique (paragraph: 0008～0017) of (Japan) special permission

Patent documentation 2: (Japan) spy opens the 2004-98624 communique

But, on the other hand,, also hope parts such as mar-proof preventing property to be sticked on the resin involucra face of precoated metal sheet with double-faced adhesive tape etc. even user expectation is emitting the binding of identification label class to be bonded in the danger on the resin involucra face of precoated metal sheet.

Summary of the invention

Therefore; The present invention develops in view of such problem, and its purpose is to provide a kind of precoated metal sheet, and it can prevent drawing cut on the CD; And have concurrently and can keep peel strength in the highland, be prone to the characteristic of bonding binding on the resin involucra surface with respect to the binding of resin involucra.

In order to solve above-mentioned problem; Constituting of precoated metal sheet of the present invention: possess metallic plate and be formed at its surperficial resin involucra; Wherein, The compressive strength that it is base layer of resin when being scattered in said epoxy and being single bead 10% distortion that is drawn by the slight compression test in the base layer of resin that said resin involucra possesses epoxy is the soft bead below the 10MPa; The containing ratio of said soft bead is that base layer of resin is 5 quality %～50 quality % with respect to said epoxy, and the average grain diameter of said soft bead is that said epoxy is 1.1 times～5 times of average thickness of base layer of resin.

According to such formation; Be scattered in containing ratio and the average grain diameter that said epoxy is the soft bead in the base layer of resin (resin involucra) through control; Even CDs etc. contact; Also, therefore, be difficult to draw cut on surfaces such as CDs through resin involucra because soft bead plays a role as padded coaming.In addition, it is resin that the basic unit of the main component through will becoming epithelium makes epoxy, can keep the peel strength with respect to the binding of resin involucra in the highland, and therefore, the engaging force when utilizing adhesive tape etc. to stick on parts on the epithelium face is good.

In the said precoated metal sheet, the precoated metal sheet that said soft bead can be used as urea alkane bead constitutes.

Owing to even the especially difficult matter property of urea alkane bead in the soft bead is high, therefore, if so use urea alkane bead, then bead is brought into play the effect height of function as padded coaming, can further prevent the phenomenon of the surface scratch of CD.

Said precoated metal sheet wherein, can constitute: said epoxy is that base layer of resin is to utilize heat to make host that is made up of bisphenol A type epoxy resin and the curing agent that is made up of urea based compound or phenol system compound carry out crosslinked epithelium.

The epoxy of this combination is that resin not only makes it be dissolved in the coatingization that organic solvent forms easily, and, at normal temperatures; The coating life-span is the long-life; And carry out sclerous reaction at short notice easily, the dispersiveness of soft bead and other additive is also good, also has excellent covering with paint property; Therefore, the coating to the epithelium of metal sheet surface is easy.In addition, the sclerous reaction that is caused by heat makes the engaging force of resin involucra and metallic plate further strong in order to ensure forming necessary three-dimensional mesh configuration as the intensity of epithelium simultaneously.

In the said precoated metal sheet, can constitute: as the additive of giving lubricity, said epoxy is that base layer of resin contains the fluorine base lubricant.

According to such formation, as lubricant,, do not make preventing property of cut reduction to CD through selecting softer fluorine base lubricant, can improve lubricity.The motion of the CD self when consequently coming in and going out CD and the action of CD-ROM drive can be carried out sleekly.

In the said precoated metal sheet, can constitute: said fluorine base lubricant is the precoated metal sheet of tetrafluoroethylene.

According to such formation,, can bring into play the function that lubricity improves to greatest extent through using the high tetrafluoroethylene of fluorine containing ratio.

In the said precoated metal sheet, can constitute: the addition of said fluorine base lubricant is with following formula (1)

A(％)＝{F/(F+C+O+N)}×100…(1)

(in the formula, A is the ratio of fluorine concentration, and F is fluorine quality %, and C is carbonaceous amount %, and O is oxygen quality %, and N is nitrogen quality %)

During the ratio of the fluorine concentration on surface, the ratio of its fluorine concentration is in the scope below 10% to the epithelium that calculates said resin involucra.

According to such formation, be controlled at below the regulation through ratio the fluorine composition in the epithelium, can the highland keep peel strength with respect to the binding of resin involucra, therefore, the engaging force in the time of can avoiding with adhesive tape etc. parts being sticked on the epithelium face reduces.

Preferably constitute: the average grain diameter of said soft bead is that said epoxy is more than 1.5 times below 4 times of average thickness of base layer of resin.

According to such formation, can improve of the effect of soft bead as padded coaming, through resin involucra, can further prevent to draw cut on surfaces such as CDs.

Said precoated metal sheet wherein, can constitute: the containing ratio of said soft bead is for being more than the base layer of resin 10 quality % below the 40 quality % with respect to said epoxy.

According to such formation, improve of the effect of soft bead as padded coaming, through resin involucra, on surfaces such as CD, be difficult to further draw cut.In addition, in order to form resin involucra, be applying coating when the metal sheet surface with the epoxy that soft bead is disperseed, the adjustment epoxy be the viscosity of coating in prescribed limit, cover with paint, lacquer, colour wash, etc. property in order to improve.

Said precoated metal sheet wherein, can constitute: between said metallic plate and said resin involucra, have the corrosion resistance epithelium.

According to such formation, improve the corrosion resistance of precoated metal sheet, and resin involucra and metallic plate engage more strongly.

Said precoated metal sheet wherein, can constitute: said metallic plate is aluminium sheet or aluminium alloy plate.

According to such formation, compare during with other metallic plates of use, can realize lightweight.

According to precoated metal sheet of the present invention; Utilization is formed at the resin involucra of metal sheet surface; The precoated metal sheet that uses for being shaped processing not only has formability, the outward appearance of basic excellence, and the containing ratio and the average grain diameter of the soft bead through will being scattered in resin involucra (epoxy is a base layer of resin) are the most suitably changed; Even under the situation of sliding on optical disc surface and resin involucra surface, also can prevent to draw on the CD and go up cut.In addition; Owing to can keep peel strength in the highland with respect to the binding of resin involucra; Engaging force when with double-faced adhesive tape etc. parts being sticked on the epithelium face is good, therefore, can provide to have the precoated metal sheet that is prone to the characteristic of bonding binding on the resin involucra surface concurrently.

Description of drawings

Fig. 1 is the profile of pattern ground expression precoated metal sheet structure of the present invention;

Fig. 2 is the microscope picture of judgement to the CD cut sample of the preventing property of cut of CD, (a) for the excellent cut sample of preventing property of cut, (b) is the good cut sample of preventing property of cut;

Fig. 3 is the microscope picture of judgement to the CD cut sample of the preventing property of cut of CD, (a) for the inferior good cut sample of preventing property of cut, (b) is the bad cut sample of preventing property of cut;

Fig. 4 is the stereogram that diagrammatical is represented CD-ROM structure.

Symbol description

1 precoated metal sheet

2 metallic plates

3 resin involucras

4 epoxies are base layer of resin

5 soft beads

10 CDs

20 CD-ROM drives

21 pan arrests

22 boxes

The specific embodiment

Below, the present invention's embodiment is at length explained.

1, precoated metal sheet

As shown in Figure 1, it is metallic plate 2 and the resin involucra 3 that is formed at metallic plate 2 surfaces that precoated metal sheet 1 of the present invention possesses basic material.Wherein, resin involucra 3 is a base layer of resin 4 with being scattered in this epoxy by epoxy is that soft bead 5 in the base layer of resin 4 constitutes, and the containing ratio of soft bead 5 and average grain diameter are controlled so as to and are setting.At this, so-called surface just is meant at least one face in the metallic plate 2.Below, each structure is described.

(1) metallic plate

For using the not special restriction of metallic plate among the present invention; Except that prevailing cold prolonging the steel plate; Various steel plating plates such as hot-dip galvanized steel sheet, plated steel sheet, alloy galvanized steel plate and copper plated steel, tin plate also have nonferrous metal plates such as alloy-steel plate, aluminum or aluminum alloy plate and copper or copper alloy plate such as stainless steel etc. all to be suitable for.At this, carry box class and the frame clsss of liquid crystal indicator of the CD-ROM drive of usefulness, the box of vehicle mounted Denso article etc. for notebook computer and require light purposes, preferably aluminum or aluminum alloy plate.Be that the Al-Mg of representative is an alloy especially preferably with 5052 and 5182 of JIS regulation.

(2) resin involucra

Resin involucra 3 is a base layer of resin 4 with being scattered in this epoxy by epoxy is that soft bead 5 in the base layer of resin 4 constitutes, and is formed at the surface of above-mentioned metallic plate 2.

(2-1) epoxy is a base layer of resin

Epoxy is that base layer of resin 4 preferably utilizes heat to make host that is made up of bisphenol A type epoxy resin and the curing agent that is made up of urea based compound or phenol system compound carry out crosslinked preparation.This combined epoxy is that resin makes not only that to be dissolved in the coatingization that organic solvent obtains easy, and at normal temperatures, the coating life-span is the long-life; And when heating, carry out sclerous reaction at short notice easily, the dispersiveness of soft bead and lubricant is also good; Also has excellent coating; Therefore, epithelium is easy to the coating on metallic plate 2 surfaces, in addition; The sclerous reaction that is caused by heat forms to be guaranteed as the intensity of epithelium and necessary three-dimensional mesh configuration, and to make the bonding force of resin involucra 3 and metallic plate 2 more strong be easy.In addition, the urea based compound is being used under the situation of curing agent, because the variable color of the heat can suppress sclerous reaction and carry out the time, so more preferably.

What in addition, epoxy was that base layer of resin 4 also can contain ormal weight is the fluorine base lubricant of representative with the tetrafluoroethylene.

(2-2) soft bead

For when the discrepancy of CD etc. and the position of directly sliding such as CD use precoated metal sheet 1, need to suppress through sliding the cut of on CD etc., drawing.At this, in order to prevent to draw cut on the CD etc., must resin involucra 3 is softening.Usually, as the method that resin involucra 3 is softening, method that the glass transformation temperature with resin reduces and the method that suppresses the cross-linking reaction of resin and curing agent are arranged.Will resin involucra 3 be carried out effectively softeningly, it is the most effective that the main component of resin involucra 3 is that the matrix resin softens, in fact, and through can resin involucra 3 being softened with these methods to the matrix resin.

But, when utilizing these methods to carry out softization of resin involucra 3, as side effect; Adhesivity will appear on resin involucra 3; Therefore, the lubricity of resin involucra 3 significantly reduces, the motion of the CD self when producing injury discrepancy CD and this problem of action of CD-ROM drive.On the other hand; Not only that the matrix resin of resin involucra 3 is softening; And when being that soft bead 5 is when being added in the resin involucra 3 (epoxy is a base layer of resin 4) with soft particulate; Can the glass transformation temperature of matrix resin be reduced, also can resin involucra 3 is all softening even perhaps do not suppress cross-linking reaction.Therefore, can not hinder the lubricity of resin involucra 3, and can guarantee preventing property of cut CD etc.

So-called soft bead 5 of the present invention soft be meant with the single bead of slight compression test and when making it 10% distortion takes place the compressive strength of when bead 10% distortion (single) be the situation of the following degree of 10MPa.

As the testing machine that carries out slight compression test, the slight compression testing machine MCT-W500 of Shimadzu Seisakusho Ltd.'s corporate system for example etc. is arranged, through using this testing machine, can carry out compression test to the single bead about particle diameter 1 μ m～100 μ m.More specifically; With particle diameter is that single little ball device about 5～10 μ m, preferred 8 μ m is on the increased pressure board of the bottom of testing machine; The top pressure head that pressurizes is depressed on the limit; The limit applies compression and measures load simultaneously single bead, and the load in the time of will reducing the time point of bead diameter 10% is made as 10% compression load value.Be P (N) when establishing this 10% compression load value, when the particle diameter of the bead after establishing mensuration is d, the compressive strength St (MPa) (with reference to Japanese mining industry meeting will 81.10.24 (1965)) when utilizing following formula (2) can calculate 10% distortion.In addition, the compressive strength St (MPa) during this 10% distortion is more little, and is soft more as bead.In the present invention, the compressive strength St (MPa) in the time of need making this 10% distortion is for below the 10MPa, more preferably below the 5MPa.

St=2.8P/ (∏ d2) ... Formula (2)

(wherein, in formula (2), ∏ representes pi.)

In addition, as this soft bead 5, can suitably select for example urethane bead, ethylene-methyl methacrylate formicester copolymer (EMMA) bead, low density polyethylene (LDPE) (LDPE) bead etc. for use.In addition, as the urethane bead, can suitably select for use Sanyo to change into the メ Le テ Star Network ス (registration mark) of corporate system, big day refine ダイミ Star Network PVC one ズ (registration mark) of corporate system, ア one トパ, one Le (registration mark) that root is attend industrial group's system etc.In addition, the EMMA bead can suitably be selected Sumitomo refine (SUMITOMO DEIKA CHEMICALS CO, LTD) the soft bead A of corporate system, soft bead B etc. for use.The LDPE bead can suitably be selected the Sumitomo mobile bead (registration mark) of corporate system etc. of refining for use.

(the containing ratio of soft bead: 5 quality %～50 quality %)

In order to improve the preventing property of cut to CD etc., the containing ratio of preferred soft bead 5 is with respect to epoxy resin basic unit more than 4.When the containing ratio less than 5 quality % of soft bead 5, the amount that is fixed in epoxy and is the soft bead 5 in the base layer of resin 4 is few, reduces as the effect of padded coaming, and preventing property of cut is poor.In addition, when improving the containing ratio of soft bead 5, make the viscosity of the coating that soft bead 5 disperses will tackify, therefore, imagination with barrel enamelling etc. with paint spraying under the situation on the metallic plate 2, reduce with the coating of homogeneous film thickness.Can know that by above reason the containing ratio of soft bead 5 is made as 5 quality %～50 quality % with respect to epoxy resin basic unit 4.In addition, guarantee to improve the level that cut prevents performance, the containing ratio of preferred soft bead 5 is more than the 10 quality %, and in order to ensure more stable coating, the containing ratio of preferred soft bead 5 is below the 40 quality %.

(average grain diameter of soft bead: epoxy is 1.1 times～5 times of average thickness of base layer of resin)

In order to utilize soft bead to guarantee the preventing property of cut to CD etc., the average grain diameter of importantly soft bead 5 is that the average thickness of base layer of resin is big than epoxy.Thus; As shown in Figure 1, because being the part that soft bead 5 exists, the cross sectional shape of resin involucra 3 is protruding small concaveconvex shape, therefore; CDs etc. significantly reduce with the contact area of epoxy resin basic unit 4; And the contact site makes soft soft bead 5 work as padded coaming, therefore, can guarantee the preventing property of cut to CD etc.

At this, when the average grain diameter of soft bead 5 surpasses when being 5 times of the average thickness of base layer of resin 4 with respect to epoxy, be in the base layer of resin 4 because the major part of soft bead 5 is difficult to be fixed in epoxy, therefore, prevent the effect of the slip cut of CD etc. is reduced.In addition, when the average grain diameter of soft bead 5 was not enough to be 1.1 times of the average thickness of base layer of resin 4 with respect to epoxy, it was in the base layer of resin 4 that the soft bead 5 that particle diameter is little is prone to buried in epoxy, therefore, prevented the effect of the slip cut of CD etc. is reduced.Thereby the average grain diameter of soft bead 5 is 1.1 times～5 times of average thickness of base layer of resin as epoxy.In addition, more preferably epoxy is 1.5 times～4 times of average thickness of base layer of resin.

As long as the average grain diameter of soft bead 5 and the average thickness that epoxy is base layer of resin 4 remain such relation; The cut that slides on just can preventing on CD etc., to draw, still, even when keeping described relation also to use the soft bead 5 greater than the particle diameter more than necessary; Because epoxy is that the average thickness of base layer of resin 4 must be thick; Therefore, resin involucra 3 thickening degree are for not having economy more than necessary, and are opposite; Under situation about using less than the soft bead 5 more than necessary, the average grain diameter and the epoxy of the soft bead 5 of difficult control are the relation of the average thickness of base layer of resin 4 in industry.Therefore, as the average grain diameter of soft bead 5, preferably utilize the soft bead of 5～30 μ m degree particle diameters, the average thickness that preferred epoxy is a base layer of resin 4 is 3 μ m～10 μ m.In addition, epoxy is that the average thickness of base layer of resin 4 converts as follows: the weight of the resin involucra 3 of mensuration per unit area and to establish proportion be 1 value that converts.

In fact the particle diameter of soft bead 5 exists distribution.For example, distribute from distribute to about the maximum 20 μ m about minimum 1 μ m (with reference to the size distribution (with particle diameter distribution synonym) of ダイミ Star Network PVC one ズ (registration mark) of the homepage of refining big day) for the particle diameter of the bead about accumulative total volume 50% particle diameter and about 8 μ m.Therefore, in the present invention,, adopt average grain diameter as the particle diameter index of soft bead 5.In addition, so-called average grain diameter is meant soft bead 5 is dispersed under the state in the water, with accumulative total volume 50% particle diameter of mensuration such as laser diffraction formula particle size distribution device.

(ratio of the fluorine concentration of resin involucra 3)

Resin involucra 3 is characterised in that, is that base layer of resin 4 contains under the situation that fluorine is an additive at epoxy, with following formula (1)

A(％)＝{F/(F+C+O+N)}×100…(1)

When calculating the ratio of the most lip-deep fluorine concentration of epithelium of resin involucra 3, the ratio of its fluorine concentration is below 10%, more preferably in the scope below 7%.

At this, the ratio of fluorine concentration is used the epithelium of the resin involucra 3 that utilizes ESCA (X linear light electronic analysis device) mensuration, converts the most surperficial fluorine quality %, carbonaceous amount %, oxygen quality % and nitrogen quality % and is calculated with said formula (1).In addition, being meant that the surface of the side that adhesive tape is bonding is the surface of precoated metal sheet 1 in the surface at this said epithelium, is not the interface of resin involucra 3 and metallic plate 2.

Explanation particularly; So-called epithelium the ratio of the fluorine concentration on surface be meant from the surface of precoated metal sheet 1 when inner lateral dominance carries out each elementary analysis with argon sputter driving lateral dominance with ESCA, based on the value that with the argon sputtering time serves as zero each element quality % that state was obtained.That is, owing to utilize whole pick surface such as argon sputter, therefore, can be defined as the state on surface.

In addition, be that the fluorine that contains in the base layer of resin 4 more than the regulation is under the situation of additive at epoxy, the ratio of the fluorine concentration that epithelium is the most surperficial surpasses 10% sometimes.Under this situation, the epithelium that is present in epithelium 3 is surface and to relate to the ratio of fluorine of fissility of binding too high, and therefore, the peel strength when pasting parts etc. with double-faced adhesive tape becomes big, with not guaranteeing stable engaging force.

(corrosion resistance epithelium)

Then, precoated metal sheet 1 of the present invention can be to purchase corrosion resistance epithelium (not shown) between the base layer of resin 4 at metallic plate 2 and the epoxy that contains soft bead 5 also.Through forming the corrosion resistance epithelium, give corrosion resistance to precoated metal sheet 1, and improve the zygosity of metallic plate 2 and resin involucra 3.Being constructed as follows of corrosion resistance epithelium.

As the corrosion resistance epithelium, can suitably use the existing known corrosion resistance epithelium that contains as composition with Cr or Zr is that chromium phosphate hydrochlorate epithelium, chromic acid chromium hydrochlorate epithelium, basic zirconium phosphate epithelium, zirconia are epithelium, coating-type chromate epithelium or coating-type zirconium epithelium etc.In addition, the adhesion amount of corrosion resistance epithelium is with Cr or the preferred 10～50mg/m of Zr scaled value ²When adhesion amount be less than 10mg/m ²The time, coated metal plate 2 is comprehensive equably, is difficult to guarantee corrosion resistance, not anti-permanent use.In addition, surpass 50mg/m when adhesion amount ²The time, in processes such as press molding, on body, produce break (peeling off) at the corrosion resistance epithelium, be difficult to keep for a long time high corrosion resistance.

2, the manufacturing approach of precoated metal sheet

For the manufacturing approach of precoated metal sheet of the present invention, known have with disperseed in the surface applied of metallic plate the epoxy of soft bead be the operation of coating and will apply after epoxy be that coating carries out sintering processes and forms the method for the operation combination of resin involucra.Below, each operation is described.

Initial operation is for to have disperseed the epoxy of soft bead in the surface applied of metallic plate be the operation of coating, and the epoxy of use is that coating preferably makes the host that is made up of bisphenol A type epoxy resin and is dissolved in the coating of organic solvent by the curing agent that urea based compound or phenol system compound constitute.In addition; Be except that must composition being to add native paraffin, pertroleum wax, synthetic wax or their lubricants such as mixture the soft bead in the coating preferably at epoxy; Wherein, preferably in following ranges, use, promptly with following formula (1) with the fluorine base lubricant of tetrafluoroethylene as representative

A(％)＝{F/(F+C+O+N)}×100…(1)

When calculating the ratio of the most lip-deep fluorine concentration of epithelium of resin involucra, the ratio of its fluorine concentration is used in being no more than 10% scope, more preferably no more than 7% scope.In addition, with the dye well pigment that is colored as purpose, the additive such as various inorganic fillers, conductivity additive that is used to improve hardness and the preventing property of cut of resin involucra can freely add in the scope that does not break away from content of the present invention.

As the processing method that to epoxy is coating dispersed urea alkane bead, the ultrasonic Treatment of giving an example, utilize the stir process of magnetic stirring apparatus and impeller-type stirrer, with stir process of high speed agitator, attritor, ball mill, beading grinding machine etc. etc.

Epoxy be coating be coated with application brush, roll coater, curtain formula flow arbitrary methods such as coater, cylinder curtain type coater, electrostatic spraying device, vane type coater, dyestuff coater can; But, the use of the even and roll coater that operation is easy of special preferred coated amount.Coating amount is the mode of base layer of resin with the epoxy that forms average thickness 3～10 μ m on the surface of metallic plate, consider metallic plate transporting velocity, roll coater direction of rotation and rotary speed etc. and suitably set.

Before the coating epoxy is coating, also the degreasing process that the surface of metallic plate is carried out degreasing can be set.For example, to the jet surface aqueous alkali of metallic plate, its after washing also carries out degreasing with the surface of metallic plate.In addition, as stated, be to purchase between the resin involucra under the situation of corrosion resistance epithelium at metallic plate and epoxy, continue degreasing process, be injected in the surface of metallic plate through the chemical synthesis treatment liquid that will contain chromium ion etc., can form the corrosion resistance epithelium.

With epoxy is that the epoxy that applying coating is served as reasons after the operation of metallic plate after applying is the operation that coating forms resin involucra (epoxy that contains soft bead is a base layer of resin); With the epoxy that is coated on metallic plate is that coating carries out sintering processes, and making epoxy is coating sclerosis (crosslinked).And, be coating through sclerosis (crosslinked) epoxy, resin involucra carries out engaging with metallic plate strongly.And then soft bead is fixed in fluorine resin basic unit.

Since sintering temperature, thus the cohesive of the preventing property of CD cut of epithelium and double-faced adhesive tape is unaffected, still; When 200 ℃ of sintering temperature less thaies; Epoxy is that the sclerosis (crosslinked) of coating is insufficient, and when sintering temperature surpassed 300 ℃, epoxy was the hot deterioration of coating (decomposition); Therefore, preferred 200 ℃～300 ℃.Preferred 20～60 seconds of sintering processes time.In the time of 20 seconds, sintering is prone to insufficient in the processing time less than, and when surpassing 60 seconds, the sintering processes overlong time is prone to reduce the productivity ratio of unit interval.In addition, sintering for example utilizes hot-blast stove, induction heater, near-infrared line oven, far infrared line oven, energy line hardening furnace and carries out.

Embodiment

Below; To in precoated metal sheet of the present invention; Under the situation that the ratio of the surperficial fluorine concentration that the kind and the average thickness of the basic unit that will utilize resin involucra, the kind that is scattered in the bead of basic unit, hardness (compressive strength during 10% distortion), containing ratio, average grain diameter and tetrafluoroethylene addition are adjusted changes, confirm the preventing property of cut of CD etc. and the embodiment and the comparative example of binding fissility and covering with paint property are described.

(embodiment 1～12)

As embodiment 1～12, make precoated metal sheet according to described manufacturing approach.Respectively being constructed as follows of precoated metal sheet.

(metallic plate)

5052-H34 aluminium alloy plate in used thickness 0.5mm, the JIS regulation.

(corrosion resistance epithelium)

Form chromium phosphate hydrochlorate epithelium on the two sides of aluminium alloy plate.The adhesion amount of chromium phosphate hydrochlorate epithelium is scaled 20mg/m with Cr ²

(resin involucra)

Making the soft bead of the compressive strength when having 10% distortion of stipulating among the present invention and the epoxy that the tetrafluoroethylene powder disperses in the surface applied of chromium phosphate hydrochlorate epithelium is coating; Carry out sintering processes for 250 ℃ with sintering temperature (the highest maximum temperature of metallic plate), form resin involucra (fluorine resin basic unit).At this,, use the urethane bead as soft bead.In addition, with regard to the embodiment 10 that surperficial fluorine concentration is 0%, do not add the tetrafluoroethylene powder.

At this, be coating as epoxy, make the host that constitutes by bisphenol A type epoxy resin and be coating by the simple substance epoxy urea that the curing agent that the urine based compound constitutes is dissolved in organic solvent.In addition, use the coating of big Japanese ink chemical industrial company system specifically, still, the same coating of forming can be ordered the coating of Northwest paint company system, the coating of Nippon Paint Co., Ltd.'s system etc.

(comparative example 1～12)

As the contrast of said embodiment 1～12, made the precoated metal sheet of comparative example 1～12.Comparative example 1 is the situation of coating for using the epoxy that does not contain soft bead; Comparative example 2 and 3 is the situation of scope of the claim of the discontented unabridged version invention of the containing ratio of soft bead; Comparative example 4 and 5 is the situation of scope of the claim of the discontented unabridged version invention of relation between the average thickness of average grain diameter and epoxy resin basic unit of soft bead; Comparative example 6 and 7 for the result of addition who has strengthened the tetrafluoroethylene powder be to be the situation of the scope of the claim of the discontented unabridged version invention of ratio of the fluorine concentration on surface of epithelium; Comparative example 8,9 is the situation of different coating for the kind of using base layer of resin and epoxy; Comparative example 10 is the situation of the scope of the discontented unabridged version of ratio of different coating and the fluorine concentration claim of inventing for the kind of using base layer of resin and epoxy; Comparative example 11 and 12 situation for the bead that uses the compressive strength when not having 10% distortion of stipulating among the present invention (, be not soft bead).

Then, to the resin involucra of embodiment 1～12, comparative example 1～12 precoated metal sheet, the ratio of the fluorine concentration that the epithelium of mensuration resin involucra is the most surperficial is shown in table 1 with its result.In addition, the assay method of each characteristic is following.

(ratio of fluorine concentration)

The epithelium of measuring resin involucra with ESCA (Shimadzu Seisakusho Ltd.'s system) is the most surperficial to obtain fluorine, carbon, oxygen, nitrogen four atoms of elements %.Use each atoms of elements amount to be scaled quality % their atom %.Use this fluorine quality % (F), carbonaceous amount % (C), oxygen quality % (O) and nitrogen quality % (N), calculate the ratio (A (%)) of fluorine concentration with following formula (1),

A(％)＝{F/(F+C+O+N)}×100…(1)

At this, epithelium surface is meant with intact state to be that the argon sputtering time is the surface of state on the surface of the precoated metal sheet made in said of zero state estimating.

In addition, be that the resin involucra that base layer of resin and bead constitute is the uneven epithelium of microcosmic by epoxy.Thereby when using esca analysis, when the area of analyzing the surface is crossed when narrow, otherwise can obtain the information that the dense position of local ring epoxy resins basic unit and local bead are dense position, therefore, worry that every mensurations moment of ratio of fluorine concentration is uneven.Thereby establishing the area of analyzing the surface with the mode of the information of the evenness that obtains resin involucra is 3mm Ф.At this, it is self-evident that surface of epithelium and epithelium inside all select not receive the position of pollutions such as oils to measure.

Then, the preventing property of cut and the adhesive tape cohesive to CD of embodiment 1～12, comparative example 1～12 precoated metal sheet are measured, estimated, its result is shown in table 1.In addition, the fusible mensuration of preventing property of cut and adhesive tape, evaluation method are following.

(to the preventing property of CD cut)

The recording surface that makes commercially available CD contact with the resin involucra of precoated metal sheet surface, the limit with the reciprocal to the left and right wiping of light finger flicking flanging 10 times after, the cut of visual valuation optical disc surface.At this moment, the CD cut sample of map 2～Fig. 3, the selected near cut sample of cut state is with the result of determination of the preventing property of cut that is judged to be precoated metal sheet of cut sample.But, except the cut that the friction of the edge of CD produces, strictly say, only judge the slip cut of resin involucra surface and cd-rom recording surface.

Judge establish preventing property of cut excellent be " ◎ ", establish preventing property of cut good be " zero ", establish preventing property of cut inferior good be " △ ", establish preventing property of cut bad be " * ".

(cohesive of adhesive tape)

The peel strength of adhesive tape utilizes the 180 degree disbonded tests of stipulating among the JISK6854-2 to measure.For adhesive tape, use commercially available double-faced adhesive tape ((strain) スリオ Application テ Star Network (SLIONTEC Corporacion) system double-faced adhesive tape, piece number 5460, band towel 6mm).In addition, as condition determination, use length 100mm * precoated metal sheet of towel 60mm, the adhesive tape of length 100mm * towel 60mm, establishing peel strength is 50mm/min.In addition, the cohesive evaluation in the table 1 under the situation more than the 2.0N/6mm, representes that with " zero " cohesive is excellent in the adhesive tape peel strength, and is under the situation of not enough 2.0N/6mm, bad with " * " expression cohesive.

As shown in table 1, embodiment 1～12 precoated metal sheet all is when the adhesive tape peel strength surpasses 2.0N/6mm, representes excellent adhesive tape cohesive, and also good or excellent to the preventing property of cut of CD.In addition, conclude that the containing ratio of urea alkane bead is many more, the trend of preventing property of cut raising is arranged more, then good if containing ratio surpasses more than the 5 quality % for roughly, if containing ratio is more than the 10 quality %, then represent excellent preventing property of cut.

On the other hand, comparative example 1,2,4,5,11,12 precoated metal sheets all are that the adhesive tape cohesive is excellent, but poor to the preventing property of cut of CD when the adhesive tape peel strength surpasses 2.0N/6mm.In addition, comparative example 6～10 all is excellent to the preventing property of cut of CD, but when adhesive tape peel strength deficiency 2.0N/6mm, the adhesive tape fissility is poor.In addition, comparative example 3 exceeds the example of scope of the present invention when being 60 quality % for the containing ratio of soft bead, and therefore, epoxy is that the viscosity of coating significantly increases, and is difficult to have covering with paint property.

Claims

1. one kind prevents drawing the excellent precoated metal sheet of preventing property of cut of cut on the CD, and it possesses metallic plate and is formed at its surperficial resin involucra, it is characterized in that,

It is that base layer of resin is the soft bead in the base layer of resin with being scattered in said epoxy that said resin involucra possesses epoxy, and the compressive strength that the single bead that this soft bead is drawn by the slight compression test was out of shape 10% o'clock is below the 10MPa,

The containing ratio of said soft bead is that base layer of resin is more than the 5 quality % below the 50 quality % with respect to said epoxy,

The average grain diameter of said soft bead is that said epoxy is more than 1.1 times below 5 times of average thickness of base layer of resin.

2. precoated metal sheet as claimed in claim 1 is characterized in that, said soft bead is a urea alkane bead.

3. according to claim 1 or claim 2 precoated metal sheet is characterized in that, to be base layer of resin be utilize heat to make host that is made up of bisphenol A type epoxy resin and the crosslinked epithelium that gets of curing agent that is made up of urea based compound or phenol system compound to said epoxy.

4. according to claim 1 or claim 2 precoated metal sheet is characterized in that, said epoxy is that base layer of resin contains the fluorine base lubricant as giving the additive of lubricity.

5. precoated metal sheet as claimed in claim 4 is characterized in that, said fluorine base lubricant is a tetrafluoroethylene.

6. precoated metal sheet as claimed in claim 4 is characterized in that, the fluorine concentration ratio of the addition of said fluorine base lubricant with respect to the epithelium of the said resin involucra that calculates with following formula (1) the ratio of the fluorine concentration on surface in the scope below 10%,

A(％)＝{F/(F+C+O+N)}×100…(1)

In the formula, A is the ratio of fluorine concentration, and F is fluorine quality %, and C is carbonaceous amount %, and O is oxygen quality %, and N is nitrogen quality %.

7. according to claim 1 or claim 2 precoated metal sheet is characterized in that, the average grain diameter of said soft bead is that said epoxy is more than 1.5 times below 4 times of average thickness of base layer of resin.

8. according to claim 1 or claim 2 precoated metal sheet is characterized in that, the containing ratio of said soft bead is that base layer of resin is more than the 10 quality % below the 40 quality % with respect to said epoxy.

9. according to claim 1 or claim 2 precoated metal sheet is characterized in that between said metallic plate and said resin involucra, having the corrosion resistance epithelium.

10. according to claim 1 or claim 2 precoated metal sheet is characterized in that said metallic plate is aluminium sheet or aluminium alloy plate.