CN102416727A - Precoating aluminum plate and manufacturing method thereof - Google Patents
Precoating aluminum plate and manufacturing method thereof Download PDFInfo
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- CN102416727A CN102416727A CN2011102772332A CN201110277233A CN102416727A CN 102416727 A CN102416727 A CN 102416727A CN 2011102772332 A CN2011102772332 A CN 2011102772332A CN 201110277233 A CN201110277233 A CN 201110277233A CN 102416727 A CN102416727 A CN 102416727A
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- aluminium sheet
- coating
- precoating
- overlay film
- hard coat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—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
- 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
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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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/025—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
-
- 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
- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
- B05D2202/25—Metallic substrate based on light metals based on Al
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- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
A precoating aluminum plate (10) is formed by covering a hard covering film which has the film thickness of 0.2 to 7 microns on the surface of an aluminum plate (1). The precoating aluminum plate is characterized in that the hard covering film (2) is made of a resin which has 1 to 25% of F and 1 to 50% of Si relative to the total mass of the Si, F, C, O, and N elements, and is formed by sintering the aluminum plate (1) which is covered a coating which has the Si and F elements under the temperature from 210 to 280 DEG C.
Description
Technical field
The present invention relates in the manufacturing of printed board employed intermediate plate, household electricity goods or automobile and carry aluminium sheet and the aluminium alloy plate that is suitable for in the outer sheet material of parts etc. or the structural elements, relate to through being coated with and be contained in the precoating aluminium sheet that surface of aluminum plate is provided with the excellent overlay film of hear resistance, release property and scratch resistance.
Background technology
In the aluminium sheet or aluminium alloy plate that in household electricity goods or automobile carry with the outer sheet material of parts etc. or structural elements, is suitable for; In order to give corrosion resistance, excellent appearance from the teeth outwards and to keep the scratch resistance of this excellent appearance and then, use the precoating plate that is formed with resin coating on the surface corresponding to other characteristics of purposes.For example, in the parts of the disc driver of suction-type, stick on these parts the release property that also can easily peel off even if require to be pasted on the tape stripping of disk.
In addition, as other purposes of precoating aluminium sheet, employed intermediate plate in the manufacturing of printed board is arranged.In general, printed board is made as illustrated in fig. 2.Be used in impregnation in the sheet-like fiber base material that constitutes by glass fibre etc. prepreg 7 clampings of heat-curing resins such as epoxy resin be formed with the two sides of the internal layer core 5 of wiring pattern; Overlapping Copper Foil 6 obtains duplexer 4 on this prepreg 7; Face this duplexer 4 from two and pressurize, about 180 ℃, heat the stipulated time (heating and pressurizing).Through heating and pressurizing, because the heat cure of the resin of prepreg 7, duplexer 4 is bondd each other, obtains printed board 40.In order to improve productivity, will organize duplexer more usually and get up to implement heating and pressurizing for 4 piles, shown in Fig. 2 (a), at duplexer 4, the intermediate plate 10 that constitutes by metallic plate as the interval clamping between 4.As intermediate plate, the thermal conductivity of aluminium sheet is high and preferred, but aluminium sheet is prone to produce cut or concavo-convex from the teeth outwards.When producing cut on the intermediate plate surface, be needed on printed board through the heating and pressurizing cut, because the reduction of the quality of printed board, thereby aluminium sheet can't be reused.But,, developed the intermediate plate of on aluminium sheet, implementing surface treatment and giving hear resistance or release property etc. in order to reuse from the viewpoint that cost reduces.
As the known aluminium sheet (for example patent documentation 1) that the surface has been carried out anodized of this intermediate plate.But anodized is higher owing to processing cost, productivity is poor, thereby has developed the technology (for example patent documentation 2,3) that is formed with the precoating aluminium sheet of resin coating in surface of aluminum plate of using.
Technical literature in the past
Patent documentation
No. 3808406 communique of [patent documentation 1] japanese
[patent documentation 2] TOHKEMY 2001-225341 communique
No. 3273363 communique of [patent documentation 3] japanese
Summary of the invention
The technical problem that invention solves in advance
But; The hybrid resin overlay film of the fluororesin overlay film that patent documentation 2 is put down in writing, the epoxy resin that patent documentation 3 is put down in writing and organic siliconresin also all is that the surface is prone to the band cut; The cut of resin coating also is transferred to printed board, thereby has as the overlay film of intermediate plate and can't fully tolerate reusable problem.Particularly organic siliconresin need be in the long sintering processes of carrying out under the high temperature about 300 ℃ more than 1 minute when overlay film forms; But when sintering is not enough; Can't obtain required hear resistance, and the problem that with precoating aluminium plate in coil coiled coiled type the time, can lump etc., thus with compare as the common polyurethane resin of resin coating or acrylic resin etc.; When making with the coil coating mode, productivity worsens.
The present invention accomplishes in view of the above problems, and the intermediate plate that uses when its purpose is to provide particularly as the manufacturing of printed board can carry out repeated use and release property, the excellent precoating aluminium sheet of scratch resistance under the high temperature.
The method that is used to deal with problems
The inventor etc. further investigate in order to solve above-mentioned problem, and the result has expected the ratio optimization with the fluorine of resin coating and silicon.
Promptly; The precoating aluminium sheet of invention involved in the present invention is characterised in that; It possesses aluminium sheet and the following resin coating of the above 7 μ m of the thickness 0.2 μ m that is formed at its single face or two sides; In the said resin coating, with respect to the gross mass of silicon, fluorine, carbon, oxygen, nitrogen, the ratio of fluorine is 1～25%, the ratio of silicon is 1～50%, pencil hardness is judged to be more than the 4H through scar.Here, when representing, the ratio of said fluorine representes that with the A of following formula (1) ratio of said silicon is represented with the B of following formula (2) to the concentration of each element of the silicon in the said resin coating, fluorine, carbon, oxygen, nitrogen (quality %) with [Si], [F], [C], [O], [N].
A＝[F]/([Si]+[F]+[C]+[O]+[N])×100…(1)
B＝[Si]/([Si]+[F]+[C]+[O]+[N])×100…(2)
So, through processing the overlay film that constitutes by the resin that has limited F, Si concentration, in the heating and pressurizing under can tolerating 180 ℃ high temperature; Release property is excellent; Can be easily the Copper Foil on printed board surface after the heating and pressurizing separate, overlay film has sufficient hardness, is difficult to have cut.
And then said resin coating preferred Si concentration (quality %) in the scope of the degree of depth of surface to 1/4 thickness is higher than F concentration (quality %).
Through so making Si concentration be higher than F concentration near surface, the overlay film surface is difficult to skid, and when when the manufacturing of printed board, using as intermediate plate, the operability when laminated copper foil or prepreg etc. improves.
In addition, the manufacturing approach of the precoating aluminium sheet of invention involved in the present invention is the method that forms resin coating on the single face of aluminium sheet or two sides, it is characterized in that, carries out following operation: the painting process that contains the coating of Si, F in the single face or the two sided coatings of said aluminium sheet; And, in the temperature below 280 ℃ more than 210 ℃ the coating of said coating is carried out sintering processes, form the sintering circuit of said resin coating.
Carry out sintering processes through coating composition like this, dry, the curing of coating forms resin coating.And, through the sintering processes temperature is controlled to be prescribed limit, solidify fully, can obtain the excellent resin coating of release property.
The invention effect
Through precoating aluminium sheet involved in the present invention; Because hear resistance, release property, scratch resistance excellence; Thereby carry outer sheet material or structural elements with parts etc. applicable to household electricity goods or automobile; Intermediate plate during particularly as the manufacturing of printed board is reusable, helps the manufacturing cost of printed board and quality to improve.In addition, through the manufacturing approach of precoating aluminium sheet involved in the present invention, utilize coating and sintering processes productivity to make well.
Description of drawings
[Fig. 1] explains the sectional view of precoating aluminium sheet structure of the present invention.
[Fig. 2] (a) reaches (b) is the side view that the manufacturing approach of printed board is described.
The specific embodiment
Precoating aluminium sheet involved in the present invention is to be sheared into required size and shape and to be used for being formed in the employed intermediate plate of printed board manufacturing, further to form and be processed into household electricity goods or automobile and carry the sheet material with parts off-grade plate material or structural elements.Below explanation is used to realize the mode of precoating aluminium sheet involved in the present invention.
(precoating aluminium sheet)
With reference to Fig. 1, precoating aluminium sheet 10 involved in the present invention is to coat hard coat (resin coating) 2 on the surface of the aluminium sheet that is made up of aluminum or aluminum alloy 1 to form.In the precoating aluminium sheet 10 of the present invention, hard coat 2 can coat on the two sides with aluminium sheet 1 as shown in Figure 1, also can single face be coated (diagram is omitted).Precoating aluminium sheet 10 is processed and the corresponding structure of its occupation mode, and (with reference to Fig. 2) covers hard coat 2 at the bread in the face of (contact) Copper Foil 6 when for example in the manufacturing of printed board, using as intermediate plate.
Below explanation constitutes each key element of precoating aluminium sheet involved in the present invention.
(aluminium sheet)
Aluminium sheet 1 is the base material of precoating aluminium sheet 10, can use 1000 be industrial pure, 3000 Al-Mn that is be that the Al-Mg that alloy, 5000 is is an alloy, can select according to purposes.Particularly when implementing extrusion process or ironing (ironing), recommend A1050, A1100, A3003, the A3004 of JIS (JIS) H4000 defined.In addition, when being used for the high-intensity purposes of requirement, recommend A5052, A5182.Do not have special qualification for modified, thickness of slab, can select according to purposes or purpose.
Aluminium sheet 1 is preferably implemented bottom layer treatment to the surface, and hard coat 2 between form bottom layer treatment layer (diagram is omitted).Through the bottom layer treatment layer, aluminium sheet 1 improves with the adaptation of hard coat 2, the corrosion resistance of aluminium sheet 1 also improves.As the bottom layer treatment layer, can use the overlay film more than a kind of the known in the past Cr of containing, Zr, Ti.For example, chromium phosphate hydrochlorate overlay film, chromic acid chromium hydrochlorate overlay film, basic zirconium phosphate overlay film, zirconia overlay film, titanium phosphate overlay film, application type chromate overlay film, application type zirconium overlay film etc.In addition, also can in these overlay films, contain organic principle as required.From to the viewpoint of the worry of environment in recent years, not chromyl chromium phosphate hydrochlorate overlay film, basic zirconium phosphate overlay film, zirconia overlay film, titanium phosphate overlay film, application type zirconium overlay film etc. are used in expectation.The thickness of bottom layer treatment layer is preferably 10～50mg/m as standard in Cr, Zr, the Ti adhesion amount (Cr, Zr, Ti scaled value) on aluminium sheet 1
2About.When adhesion amount less than 10mg/m
2The time, can't be equably the whole bread of aluminium sheet 1 be covered, can't obtain effect fully.Surpass 50mg/m and work as adhesion amount
2The time, bottom layer treatment layer itself is prone to produce fracture.Cr, Zr, Ti scaled value for example can more simply and quantitatively be measured with the fluorescent X-ray method.Thereby, can not hinder the qualitative control of carrying out aluminium sheet 1 under the productive situation.
(hard coat)
(F：1～25％、Si：1～50％)
The ratio of F, Si can't obtain the release property of hard coat 2 respectively less than 1% o'clock.And the ratio of Si was less than 1% o'clock, and it is not enough that the hardness of hard coat 2 becomes.And when the ratio that makes F respectively surpasses 25%, when the ratio of Si surpasses 50%, the adaptation of 2 pairs of aluminium sheets 1 of hard coat reduces, and when not carrying out the processing of formation resin bottom coating layer or tack coat etc. between aluminium sheet 1 and hard coat 2, can't bond securely.
The ratio that is formed at said F in the hard coat 2 on precoating aluminium sheet 10 surface, Si for example can be measured through x-ray photoelectron spectrum analysis (ESCA) method and obtain.When the thickness degree of depth of the surface that is formed with hard coat 2 to the hard coat 2 of precoating aluminium sheet 10 is measured, detect the composition of hard coats 2 such as Si, as the Al of the composition of aluminium sheet 1 or the interpolation element of aluminium alloy.As the composition detection of hard coat 2 to element can enumerate Si, F and contain C or O, the N in resin usually.Usefulness [Si], [F], [C], [O], [N] expression are measured the atomic ratio (atom %) of these Si, F, C, O, N and are converted into the value (unit: in the time of quality %) of mass concentration (following is concentration); The A that the ratio of F can be used as following formula (1) tries to achieve, and the B that the ratio of Si can be used as following formula (2) tries to achieve.When regarding Si, F, C, O, N as in the hard coat 2 whole composition, the ratio of this F, Si can be close with F, the Si concentration of hard coat 2.
A＝[F]/([Si]+[F]+[C]+[O]+[N])×100…(1)
B＝[Si]/([Si]+[F]+[C]+[O]+[N])×100…(2)
And then hard coat 2 is in the scope of the degree of depth of surface (surface of precoating aluminium sheet 10) to 1/4 thickness, and preferred Si concentration is higher than F concentration.Fluororesin is because lubricity is high, thereby hard coat 2 is when F concentration is above up to Si concentration, and the characteristic of fluororesin strengthens, lubricity increases, gives lubricity to precoating aluminium sheet 10 surfaces.When this precoating aluminium sheet 10 is used as the intermediate plate in the manufacturing of printed board 10 (with reference to Fig. 2), intermediate plate 10 skids in lamination operation, in duplexer 4, be prone to produce depart from, operability reduces.Through making Si concentration be higher than F concentration, precoating aluminium sheet 10 surfaces become suitable lubricity, and in the manufacturing of printed board, operability improves.Lubricity is owing to be the characteristic on surface, thereby the lubricity of hard coat 2 directly depends near surface i.e. Si in the scope of the degree of depth of surface to 1/4 thickness, the magnitude relationship of F concentration.For relatively Si, the F concentration of the near surface of hard coat 2, can use said ESCA method, detect from Si, the F of the degree of depth of 1/4 thickness of surface to the hard coat 2 of precoating aluminium sheet 10, measure atomic ratio, be converted into mass concentration, compare.Explain; The Si of hard coat 2, F concentration do not have tangible deviation in the distribution of the degree of depth (thickness) direction; Particularly, thereby can or be used for it with the ratio of the Si in said hard coat 2 integral body, F and calculate the concentration [Si], [F] that are measured and compare because the magnitude relationship of Si, F concentration can change with the degree of depth hardly.
(hardness: the scar with pencil hardness is judged to be more than the 4H)
The hardness of hard coat 2 is to measure pencil hardness according to the regulation of JIS K5600-5-4, is judged to be more than the 4H through scar.Through making hardness is this value, the release property that performance is excellent.When hardness during less than 4H, through the heating and pressurizing in the manufacturing of printed board Copper Foil is squeezed in the hard coat 2, thereby Copper Foil and hard coat 2 be easy to bonding, release property reduces.
(thickness: the above 7 μ m of 0.2 μ m)
The thickness of hard coat 2 is below the above 7 μ m of 0.2 μ m.Thickness can't obtain the effect of hard coat 2 during less than 0.2 μ m fully in precoating aluminium sheet 10.Even and if thickness surpasses 7 μ m, also be difficult to obtain further effect and improve, the cost of the material of hard coat 2 increases.In addition, be said scope through making thickness, owing to can use roll coater on the aluminium sheet 1 of coiled type, to form hard coat 2 continuously, thereby productivity is excellent, also preferred aspect cost.When thickness surpasses 7 μ m, utilize the enhancing of coating of the pick-up roller of roll coater to become not enough, the inequality of thickness enlarges markedly.On the contrary, when thickness during less than 0.2 μ m, be necessary to improve the pressure between pick-up roller and the coating roll, roll becomes and is easy to abrasion.
The hybrid resin coating that is used to form hard coat 2 obtains for silicon compound, silicon-type resin or silica-based resin are made an addition in the fluorine resin material.And said hybrid resin coating is from the productivity of precoating aluminium sheet 10 or the viewpoint of cost, and expectation can be used roll coater to carry out application continuously, use sintering furnace is curable material through the sintering processes of about 20～60 seconds short time.As this material, PTFE (polytetrafluoroethylene (PTFE)), PVDF (Kynoar), PVF (polyvinyl fluoride), PFA (five Fluoroalkyloxy fluororesin), FEP (tetrafluoroethene hexafluoropropylene copolymer), ETFE (ethylene tetrafluoroethylene copolymer), ECTFE (ethene one chlorotrifluoroethylcopolymer copolymer) are arranged, contain the fluororesin of acrylic acid ester etc. as the fluorine resin material.Can enumerate methyl organic siliconresin, phenyl organic siliconresin, contain the organic siliconresins such as organic siliconresin of acrylic acid ester as organic siliconresin, can enumerate silicate such as silica, aluminium silicate salt or borosilicate salt etc. as silicon compound.The resin material of the copolymer of the fluororesin organic siliconresin that perhaps also can use and form siliceous fluororesin, contains acrylic acid ester etc.
(manufacturing approach of precoating aluminium sheet)
The manufacturing approach of precoating aluminium sheet then, is described.The manufacturing approach of precoating aluminium sheet involved in the present invention is carried out following operation: the painting process that contains the coating of Si, F in the single face or the two sided coatings of aluminium sheet 1; And the coating that is coated with is implemented the sintering circuit that sintering processes forms hard coat (resin coating) 2 in the temperature below 280 ℃ more than 210 ℃.
(painting process)
The coating of coating can be coated with any method such as machine through brushing machine, roll coater, Curtain flow coater, roller shutter type coating machine, static coating machine, knife type coater, mould to be carried out, preferred especially coating weight homogeneous, roll coater simultaneously simple to operate.In addition, according to the mode of the hard coat 2 of the desired thickness that forms 0.2～7 mu m range on the surface of aluminium sheet 1, consider the suitable adjustment coating weight such as direction of rotation and rotary speed of conveyance speed, the roll coater of aluminium sheet 1.
Before carrying out painting process, also can carry out the surface of aluminium sheet 1 is carried out the degreasing process of degreasing.For example, aqueous alkali is sprayed to back, the surface enforcement washing of aluminium sheet 1.
And then, before carrying out painting process, also can carry out forming the bottom layer treatment operation of bottom layer treatment layer on the surface of aluminium sheet 1.For example, the aluminium sheet behind the said degreasing process 1 is implemented the chromium phosphate hydrochlorate handle, form chromium phosphate hydrochlorate overlay film.
(sintering circuit)
In the temperature below 280 ℃ more than 210 ℃ the aluminium sheet 1 that is coated with coating is implemented sintering processes, make said paint solidification.Sintering temperature is meant the Da Wendu that is up to of aluminium sheet 1.Sintering temperature is during less than 210 ℃, and then the curing of coating is insufficient, and it is not enough that the hardness of hard coat 2 becomes.When sintering temperature surpassed 280 ℃, because coating begins decomposition, thereby the hardness of hard coat 2 reduced on the contrary.The sintering processes time is preferably 20～60 seconds.There are the not enough misgivings of sintering the sintering processes time during less than 20 seconds; Even if carry out sintering processes and surpass 60 seconds, do not have further curing yet, the productivity of unit interval reduces.Sintering processes can be used hot-blast stove, induces heating furnace, near-infrared line oven, far infrared line oven, energy-ray curing oven etc. carry out.
[embodiment 1]
More than narrated the mode that is used for embodiment of the present invention, below compared the embodiment of the effect of the present invention of specifically clearly accepting with the comparative example of discontented unabridged version invention important document.Explain that the present invention is defined in this embodiment.
(supplying the making of examination material)
(bottom layer treatment of aluminium sheet)
Use the JIS 5182H18 material of thickness of slab 0.5mm as aluminium sheet 1.Aluminium sheet is implemented the chromium phosphate hydrochlorate and is handled after using aqueous alkali that degreasing is carried out on the surface, on the two sides, forms with the Cr conversion and counts 20mg/m
2Chromium phosphate hydrochlorate overlay film.
(formation of hard coat)
On the single face of the aluminium sheet after the bottom layer treatment, be coated with the coating of the different siliceous fluororesin of Si content.The coating of siliceous fluororesin uses ICP (inducing coupled plasma) ICP Atomic Emission Spectrophotometer method to measure, according to the scope adjustment Si content that reaches F:0.1～10 quality %, Si:0.1～20 quality %.Coating shown in the reference column of confession examination material No.14～18 coating tables 1 is described.Then, under sintering temperature shown in the table 1 (aluminium sheet be up to Da Wendu), carry out sintering processes, make the confession examination material of precoating aluminium sheet.To be the aluminium sheet that is coated with coating move to the continuous sintering mode of outlet from the inlet of stove to the mode of heating of aluminium sheet, makes aluminium sheet pass through time in the stove as heat time heating time, and it is adjusted into 30 seconds.In addition, paste the Da Wendu that is up to that heat label is measured aluminium sheet at aluminium sheet.
Supply the examination material to use the vortex flow film thickness gauge to measure the thickness of overlay film to gained, be shown in table 1.In addition, use the thickness suitable degree of depth of x-ray photoelectron spectrum analysis (ESCA) device ((strain) island Feng makes made), detect Si, F, C, O, N, Al from overlay film surface measurements to the overlay film of confession examination material.Wherein, measure the atomic ratio of Si, F, C, O, N, calculate the ratio (%) of F, Si by said formula (1), (2).The ratio of gained F, Si is shown in table 1 as F, the Si concentration (quality %) of overlay film.
(hardness of hard coat)
Pencil hardness uses scar to judge according to JIS K5600-5-4 and measures.To measure the result and be shown in table 1.
(evaluation)
(heating and pressurizing test)
Simulated the heating and pressurizing test of intermediate plate during the precoating aluminium sheet made as the printed board heating and pressurizing when using.On the overlay film surface that supplies the examination material so that the overlapping Copper Foil of the mode that glassy surface is faced mutually, from the two sides with 30kg/cm
2Pressurize,, after 90 minutes Copper Foil is being separated from supplying the examination material 180 ℃ of heating under this state.The overlapping once more Copper Foil that same confession examination material is carried out 10 times carries out the test of heating and pressurizing equally.After the heating and pressurizing of the 1st time and the 10th time, carry out the evaluation of release property and scratch resistance respectively.
(release property)
To after heating and pressurizing, be easy to from supplying examination material (overlay film) surface isolation person to be shown in table 1 with " zero " by Copper Foil as qualified; Overlay film surface and Copper Foil are bondd, firmly then can't the segregator not be shown in table 1 as bad with " * ".
(scratch resistance)
With visualization surface from the Copper Foil that supplies the examination material separation after heating and pressurizing, scratches visible or distortion person are shown in table 1 as bad with " * "; To there be cut or distortion person to be shown in table 1 with " zero " as qualified.
(caking)
To practise physiognomy between the overlay film to overlapping state, many ground separation supply to try material after heating 1 minute under 90 ℃ with 2 confession examination materials.To supply examination material easy separation person to be shown in table 1 with " zero " as do not lump (qualified); With bonding between the overlay film firmly then can't the segregator as there being caking (bad) to be shown in table 1 with " * ".
As shown in table 1, supply examination material No.1～12 because Si, F concentration, sintering processes and the thickness of overlay film all satisfy scope of the present invention, thereby can obtain the overlay film of abundant hardness, release property and scratch resistance are well, do not lump yet.Particularly, as supplying examination material No.4,, in 10 times heating and pressurizing test, also can obtain release property and scratch resistance even if make the thickness of overlay film be decreased to 0.2 μ m.In addition, through supplying the making and the evaluation of examination material, coating or corrosion resistance have no problem in practicality.
Relative therewith, supply examination material No.13～18th, the composition of overlay film is the outer comparative example of the scope of the invention.Supply examination material No.14 to possess the organic siliconresin overlay film that does not contain F; The sintering processes temperature also has very low situation as organic siliconresin; Particularly the hardness of overlay film is not enough, and release property and scratch resistance are poor in 1 time heating and pressurizing test, is not suitable for as the intermediate plate of the manufacturing usefulness of printed board; And can lump, also improper as precoating plate.The confession examination material No.18 that possesses the overlay film that does not contain F equally is the comparative examples that mix overlay film that likewise form epoxy resin and organic siliconresin with patent documentation 3 disclosed overlay films in the sintering processes temperature for 290 ℃ times; Though being higher than, the hardness of overlay film supplies examination material No.14; But also not enough, in 10 times heating and pressurizing test, do not obtain release property and scratch resistance.And the hardness of the fluororesin overlay film that does not contain Si of confession examination material No.15 is not enough too, in 10 times heating and pressurizing test, does not obtain release property and scratch resistance.
Supplying examination material No.17 is to be the result that coating forms overlay film with the epoxy that does not contain simultaneously Si, F, and the hardness of overlay film is not enough, and release property and scratch resistance are poor in 1 time heating and pressurizing test, is not suitable for as the intermediate plate of the manufacturing usefulness of printed board.
On the contrary, the adaptation of the resin coating that the F of confession examination material No.13 is excessive reduces, and can't directly be bonded on the aluminium sheet, is necessary to be provided with the resin bottom coating layer, and in 10 times heating and pressurizing test, does not obtain release property and scratch resistance.Though the excessive resin coating of Si that supplies the silica-based coating of usefulness of examination material No.16 to form does not obtain release property and scratch resistance, adaptation reduces, and can't directly be bonded on the aluminium sheet, is necessary to be provided with the resin bottom coating layer, becomes the very poor precoating plate of productivity.
Supply examination material No.19～21st, though the composition of overlay film is that the sintering processes temperature is extraneous comparative example in the scope of the present invention.Supply examination material No.20,21 sintering processes temperature curing low, coating hardness not enough, overlay film is not enough.Particularly, the minimum confession of sintering processes temperature examination material No.21 release property and scratch resistance in 1 time heating and pressurizing test is poor, is not suitable for as the intermediate plate of the manufacturing usefulness of printed board, and can lumps, and be also improper as precoating plate.On the contrary, supply the sintering processes temperature of examination material No.19 high, coating begins to decompose during sintering processes, and it is not enough that the hardness of formed overlay film becomes.
Supply examination material No.22, the 23rd, though the composition of overlay film and sintering processes temperature are that thickness is extraneous comparative example in the scope of the present invention.Supply the thickness deficiency of the overlay film of examination material No.22, in 10 times heating and pressurizing test, do not obtain scratch resistance.Though and confession tries material No.23 release property and scratch resistance is no problem, owing to form blocked up overlay film, meeting generation inequality in thickness, bad order becomes.
[embodiment 2]
For the confession examination material No.1,2,4～9 of the scope of the invention of embodiment 1, estimate of the influence of the magnitude relationship of Si in the hard coat, F concentration to lubricity.
In the mensuration of the Si of the overlay film in embodiment 1, the concentration of F, the Si in the zone of the degree of depth (top layer of overlay film) of 1/4 thickness that is defined in overlay film surface to the overlay film that supplies the examination material, the atomic ratio of F are measured.Each supplies the atomic ratio of Si, F of examination material and overlay film integral body there are no significant difference, and Si, F concentration (quality %) can regard equal as.Si, F concentration (quality %) relatively is shown in table 2.The Si of the overlay film of measuring among the embodiment 1, concentration, thickness and the hardness of F are shown in table 2 in the lump.
(evaluation)
(lubricity)
As the evaluation of the lubricity that supplies examination material surface (overlay film surface), use loading method (loading 200g) to measure coefficient of friction.The result is shown in table 2.
[table 2]
By shown in the table 2, F concentration is lower than the confession examination material No.1 of Si concentration in the top layer of overlay film, 2,4～6 coefficient of friction is 0.3～0.5, has suppressed lubricity to a certain extent, becomes manufacturing as printed board with intermediate plate precoating aluminium sheet very preferably.And F concentration is higher than low the reaching below 0.1 of coefficient of friction of confession examination material No.7～9 of Si concentration, as the manufacturing of printed board with intermediate plate it is thus clear that the high tendency of lubricity.
[symbol description]
10 precoating aluminium sheets, intermediate plate
1 aluminium sheet
2 hard coats (resin coating)
Claims (3)
1. precoating aluminium sheet; It is the precoating aluminium sheet that possesses aluminium sheet and resin coating below the above 7 μ m of the thickness 0.2 μ m that is formed at its single face or two sides; It is characterized in that, in the said resin coating, with respect to the gross mass of silicon, fluorine, carbon, oxygen, nitrogen; The ratio of the fluorine shown in the A of following formula (1) is 1～25%, the ratio of the silicon shown in the B of following formula (2) is 1～50%, pencil hardness is judged to be more than the 4H with scar
A＝[F]/([Si]+[F]+[C]+[O]+[N])×100…(1)
B＝[Si]/([Si]+[F]+[C]+[O]+[N])×100…(2)
The mass percent concentration of each element of the silicon in [Si], [F], [C], [O], the said resin coating of [N] expression, fluorine, carbon, oxygen, nitrogen.
2. precoating aluminium sheet according to claim 1 is characterized in that, said resin coating in the scope of the degree of depth of surface to 1/4 thickness, the mass percent concentration of silicon is higher than the mass percent concentration of fluorine.
3. the manufacturing approach of a precoating aluminium sheet, it is the manufacturing approach that forms the precoating aluminium sheet of resin coating on the single face of aluminium sheet or two sides, it is characterized in that, carries out following operation:
The painting process that contains the coating of Si, F in the single face or the two sided coatings of said aluminium sheet; And,
In the temperature below 280 ℃ more than 210 ℃ the coating of said coating is carried out sintering processes, form the sintering circuit of said resin coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-213135 | 2010-09-24 | ||
| JP2010213135A JP5255612B2 (en) | 2010-09-24 | 2010-09-24 | Pre-coated aluminum plate and manufacturing method thereof |
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| Publication Number | Publication Date |
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| CN102416727A true CN102416727A (en) | 2012-04-18 |
| CN102416727B CN102416727B (en) | 2014-07-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201110277233.2A Expired - Fee Related CN102416727B (en) | 2010-09-24 | 2011-09-19 | Precoating aluminum plate and manufacturing method thereof |
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| Country | Link |
|---|---|
| JP (1) | JP5255612B2 (en) |
| KR (1) | KR101325307B1 (en) |
| CN (1) | CN102416727B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104070730A (en) * | 2013-03-26 | 2014-10-01 | 株式会社神户制钢所 | Pre-coated aluminium plate and manufacturing method thereof |
| CN113278349A (en) * | 2021-04-14 | 2021-08-20 | 上海嘉宝莉涂料有限公司 | Matte white finish and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117858927A (en) * | 2021-09-24 | 2024-04-09 | 东丽株式会社 | Silicone resin composition for forming cured film, and method for producing polysiloxane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09324141A (en) * | 1996-06-04 | 1997-12-16 | Nippon Paint Co Ltd | Coating composition and formation of coating film |
| CN101384427A (en) * | 2006-03-27 | 2009-03-11 | 株式会社神户制钢所 | Precoated metal plate |
| WO2011104928A1 (en) * | 2010-02-26 | 2011-09-01 | 住友軽金属工業株式会社 | Conductive precoated aluminum alloy sheet |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3273363B2 (en) * | 1999-10-29 | 2002-04-08 | サン・アルミニウム工業株式会社 | Aluminum intermediate plate for printed circuit board manufacturing |
| JP2001225341A (en) * | 2000-02-17 | 2001-08-21 | Mitsubishi Alum Co Ltd | Intermediate plate for manufacturing resin base substrate |
| JP2001326460A (en) * | 2000-05-15 | 2001-11-22 | Kobe Steel Ltd | Aluminum intermediate plate for manufacturing printed board |
| JP2006001115A (en) * | 2004-06-17 | 2006-01-05 | Fuji Photo Film Co Ltd | Surface-treated aluminum molding |
| JP5085789B2 (en) * | 2010-02-10 | 2012-11-28 | 新日本製鐵株式会社 | Precoated metal plate with excellent formability |
-
2010
- 2010-09-24 JP JP2010213135A patent/JP5255612B2/en not_active Expired - Fee Related
-
2011
- 2011-09-19 CN CN201110277233.2A patent/CN102416727B/en not_active Expired - Fee Related
- 2011-09-22 KR KR1020110095704A patent/KR101325307B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09324141A (en) * | 1996-06-04 | 1997-12-16 | Nippon Paint Co Ltd | Coating composition and formation of coating film |
| CN101384427A (en) * | 2006-03-27 | 2009-03-11 | 株式会社神户制钢所 | Precoated metal plate |
| WO2011104928A1 (en) * | 2010-02-26 | 2011-09-01 | 住友軽金属工業株式会社 | Conductive precoated aluminum alloy sheet |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104070730A (en) * | 2013-03-26 | 2014-10-01 | 株式会社神户制钢所 | Pre-coated aluminium plate and manufacturing method thereof |
| CN113278349A (en) * | 2021-04-14 | 2021-08-20 | 上海嘉宝莉涂料有限公司 | Matte white finish and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5255612B2 (en) | 2013-08-07 |
| JP2012066478A (en) | 2012-04-05 |
| KR101325307B1 (en) | 2013-11-08 |
| KR20120031448A (en) | 2012-04-03 |
| CN102416727B (en) | 2014-07-16 |
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