WO2017206664A1 - 具有装饰图文的金属制品及其制备方法 - Google Patents

具有装饰图文的金属制品及其制备方法 Download PDF

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Publication number
WO2017206664A1
WO2017206664A1 PCT/CN2017/083110 CN2017083110W WO2017206664A1 WO 2017206664 A1 WO2017206664 A1 WO 2017206664A1 CN 2017083110 W CN2017083110 W CN 2017083110W WO 2017206664 A1 WO2017206664 A1 WO 2017206664A1
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WO
WIPO (PCT)
Prior art keywords
metal
metal substrate
micropores
sublimation
treatment
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/083110
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English (en)
French (fr)
Inventor
罗富华
袁江
王继厚
陈梁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BYD Co Ltd
Original Assignee
BYD Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BYD Co Ltd filed Critical BYD Co Ltd
Priority to US16/099,580 priority Critical patent/US20190111728A1/en
Priority to EP17805609.9A priority patent/EP3453539A4/en
Publication of WO2017206664A1 publication Critical patent/WO2017206664A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
    • B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
    • B41M5/0351—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic on anodized aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
    • B44C1/1729—Hot stamping techniques
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1704—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/30—Anodisation of magnesium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/04—Etching of light metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
    • B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82—After-treatment
    • C23C22/83—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present disclosure belongs to the field of metal decoration, and more particularly, the present disclosure relates to a metal article having a decorative graphic and a method of preparing the same.
  • the metal surface realizes graphic decoration.
  • the current technical solution is: the first step is to spray a coating on the metal surface; the second step is to print the sublimation ink onto the sublimation paper; the third step is to print the finished heat.
  • the sublimation paper is in contact with the coated surface on the metal; the fourth step is heating by a heat transfer machine or other heating method, and the coating is used to adsorb the sublimation ink to transfer the image from the sublimation paper to the metal product.
  • the product prepared by the above technical method needs to spray a coating on the metal surface, and the coating on the surface masks the metal texture of the metal, so that the metal product loses its own metal texture.
  • the present disclosure is directed to the above problems, thereby providing a metal article having a metallic texture and a method of producing the same.
  • the present disclosure provides a metal article having a decorative graphic, the metal article comprising a metal substrate having micropores on the surface, a heat-sublimation ink filled in a portion of the micropores, and a sealing layer on the surface of the metal substrate .
  • the present disclosure also provides a method of preparing a metal article having a decorative graphic, the method comprising the steps of:
  • the present disclosure also provides a metal article having a decorative graphic prepared by the method.
  • the graphic ink is filled in the micropores of the metal surface, and then the graphic ink is sealed in the micropores through the sealing hole, and the graphic ink has strong adhesion and is not easy to change color. At the same time, the metallic luster is retained.
  • the thermal sublimation paper to which the graphic is attached is attached to the surface of the metal substrate, and then the sublimation ink is introduced into the micropores of the metal surface by drying, and the image is retained while retaining the image.
  • the original metallic luster of metal is attached to the surface of the metal substrate, and then the sublimation ink is introduced into the micropores of the metal surface by drying, and the image is retained while retaining the image.
  • the present disclosure provides a metal article having a decorative graphic, the metal article comprising a metal substrate having micropores on the surface, a heat-sublimation ink filled in a portion of the micropores, and a sealing layer on the surface of the metal substrate .
  • the size of the micropores is not particularly limited as long as the sublimation ink can be allowed to enter, and in order to facilitate the sublimation ink entry, the D50 of the micropores is optionally 1 nm to 100 ⁇ m, alternatively 5 nm to 20 ⁇ m, for example 10 nm to 1 ⁇ m.
  • the shape of the micropores is not particularly limited, and may be a single layer of pores, or may be a double layer or a plurality of layers, as long as the D50 of the surface micropores is from 1 nm to 100 ⁇ m.
  • the micropores may optionally have a depth of 10 nm to 100 ⁇ m, alternatively 1 ⁇ m to 50 ⁇ m, for example, 5 ⁇ m to 30 ⁇ m.
  • the metal substrate is not particularly limited as long as it is a general common metal, such as one of an aluminum alloy, a stainless steel, and a magnesium alloy.
  • the graphic ink is filled in the micropores of the metal surface, and then the graphic ink is protected in the micropores through the sealing hole, and the graphic ink has strong adhesion and is not easy to change color. At the same time, the metallic luster is retained.
  • the present disclosure also provides a method of preparing a metal article having a decorative graphic, the method comprising the steps of:
  • microporous treatment of the metal substrate there is no limitation on the order of microporous treatment of the metal substrate and the printing of the thermal sublimation ink onto the sublimation paper according to the desired graphic shape.
  • the microporous treatment of the metal substrate may be performed first, and then the thermal sublimation ink may be subjected to The desired graphic shape is printed on the sublimation paper; or the sublimation ink is first printed on the sublimation paper according to the desired graphic shape, and then the metal substrate is subjected to micropore treatment; or the sublimation may be performed simultaneously.
  • the ink is printed onto the sublimation paper in the desired graphic shape and the metal substrate is microporous.
  • the bonding here can be understood as adhering to the surface of the metal substrate, and in order to allow the ink graphic to retain more accurately retain the original graphic shape, the bonding here requires a relatively close fit.
  • the sublimation ink is sublimated under heating, and since the thermal sublimation paper is attached to the surface of the metal substrate, the sublimation ink is sublimated and then enters into the micropores of the corresponding metal substrate surface, so that the surface of the metal substrate can be Form the same decorative text as the text on the sublimation paper.
  • the micropores are sealed again, which can smooth the metal surface on the one hand and better protect the decorative image on the other hand.
  • the metal substrate to which the thermal sublimation paper is attached is placed in the sealing device. And vacuum.
  • the sublimation paper can be smoothly and closely adhered to the surface of the metal substrate of any shape, and the shape of the metal substrate is not limited.
  • the metal substrate can be curved, so that the metal substrate can be used.
  • the surface forms a 3D decorative graphic. 3D decorative graphics can better meet the consumer's aesthetic requirements. Can be widely applied to the outer casing of electronic products.
  • the method of the micropore treatment is not particularly limited, and may be various micropore treatment methods commonly used in the art, as long as the desired micropores can be obtained, such as phosphating.
  • the phosphating treatment is: immersing the metal substrate in a phosphating solution consisting of 40 g/L of dihydrogen phosphate, 20/L of dihydrogen phosphate and 40 g/L of zinc dihydrogen phosphate, pH value It was 2 and treated at 50 ° C for 15 minutes.
  • the D50 of the micropores obtained by the phosphating treatment is generally between several nanometers and several tens of nanometers, and the film thickness is formed from 0.1 ⁇ m to 50 ⁇ m.
  • the silylation treatment is: placing the metal substrate in a 60%-70% ethyltriethoxysilane solution, using a glacial acetic acid condition pH of 8-9, soaking for 30 minutes, taking out and putting it into 80 Bake in a constant temperature oven at °C for 1 hour.
  • the D50 of the micropores obtained by the silylation treatment is generally between several nanometers and several tens of nanometers, and the film thickness is formed from 0.1 ⁇ m to 50 ⁇ m.
  • the anodizing treatment is: immersing the metal substrate in an anolyte (composed of 160 g/L of sulfuric acid), and controlling the current density to be 1.3 A/dm 2 at 25 ° C for 20 minutes.
  • the etching process may be a simple acid etching or alkali etching, and may be anodized after the first acid etching or alkali etching
  • the etching treatment is: with a sulfuric acid solution of the metal base body
  • conditions include sulfuric acid concentration of 10%-15%; voltage of 12-15V; soaking time of 10-20min.
  • Forming an irregular surface corrosion metal substrate, and then placing the pretreated metal substrate in an alkali etching solution for electrochemical corrosion the concentration of the etching solution is 5%-10%, the soaking time is 5-10 min, and the etching hole is A finer hole is formed in the metal substrate.
  • the size of the micropores is not particularly limited as long as the sublimation ink can be allowed to enter, and in order to facilitate the sublimation ink entry, the D50 of the micropores is optionally 1 nm to 100 ⁇ m, alternatively 5 nm to 20 ⁇ m, for example 10 nm to 1 ⁇ m.
  • the shape of the micropores is not particularly limited, and may be a single layer of pores or a double layer or a plurality of layers of pores as long as the D50 of the surface micropores is from 1 nm to 100 ⁇ m.
  • the method of heating the sublimation ink in step S3 is to bake the sealing device, in order to better allow the sublimation ink to enter the micropores, optionally, in step S3,
  • the baking temperature is 80 ° C - 240 ° C
  • the optional baking temperature is 120-180 ° C
  • the baking time is 2-360 minutes
  • the optional baking time is 30 minutes - 1 hour.
  • the method for sealing the pores is not particularly limited, and may be various sealing methods commonly used in the art, such as water sealing holes or sealing agents.
  • the water sealing hole is: the metal substrate having the micropores formed on the surface is immersed in hot water of 95 ° C for 30 minutes.
  • the sealing agent was sealed by using a 6% nickel acetate sealing agent solution and immersing the metal substrate having micropores on the surface at 95 ° C for 20 min.
  • the metal substrate further includes a drying step after the micropore treatment, and the drying function is to ensure that there is no moisture in the micropores, so that the subsequent sublimation ink penetrates into the micropores.
  • the drying temperature is 80-100 °C.
  • the metal substrate is one of metal materials such as aluminum alloy, stainless steel, and magnesium alloy.
  • the heat-sublimation paper to be used is not particularly limited, and various heat-sublimation papers which are commonly used in the art can be used, and for example, a paper having a thickness of 0.09 mm which is commonly used in the art can be selected.
  • the melting point of the sealing device is not particularly limited as long as it is higher than the baking temperature, and optionally, the melting temperature of the sealing device is 260 ° C or higher.
  • the sealing device is not particularly limited as long as it can seal the hot sublimation paper.
  • the sealing device is a vacuum soft silicone sealed bag, and the melting temperature of the silica gel is 260 ° C or higher.
  • the steps of degreasing, decontaminating, and derusting the metal surface are also included.
  • the degreasing, decontamination and rust cleaning can be various methods commonly used in the art, such as: the metal substrate is sequentially immersed in the RC-800 type rust remover solution, then washed with water, and then immersed in the SP-101 type. In the oil solution, finally rinse with pure water.
  • the present disclosure also provides a metal article having a decorative graphic prepared by the preparation method described in the present disclosure.
  • the heat-sublimated paper to which the image is attached is smoothly adhered to the surface of the metal substrate by vacuum, so that the metal substrate is not required, and a curved surface can be formed.
  • the sublimation ink is allowed to enter the micropores of the metal surface by drying without affecting the metallic luster.
  • the magnesium alloy material with curved surface is pre-treated, and the surface of the magnesium alloy is cleaned with oil by SP-101 type degreaser, RC-800 type rust remover and water to expose the surface of the bright magnesium alloy. Then baked at 90 ° C for 30 minutes;
  • Microporous treatment of the cleaned magnesium alloy the specific method of microporous treatment is: immersing the metal substrate into phosphorus composed of iron dihydrogen phosphate, manganese dihydrogen phosphate and zinc dihydrogen phosphate according to 2:1:2 In the chemical solution, the pH was adjusted to 2, and the treatment was carried out for 15 minutes at 50 ° C, and the micropore D50 obtained after the treatment was 1 ⁇ m and the depth was 50 ⁇ m;
  • the sealing device Put the magnesium alloy substrate with the sublimation paper attached to the sealing device, and by vacuuming (the vacuum degree is 0.05pa), the sealing device makes the sublimation paper closely fit on the front and side of the magnesium alloy part. ;
  • the baking temperature is 120 ° C, and the baking time is 240 minutes;
  • the metal product A1 of the present disclosure is obtained by washing with water, baking in an oven at 90 ° C for 30 minutes, and drying.
  • Microporous treatment of the cleaned stainless steel the specific method of microporous treatment is: the metal substrate is placed in a 65% ethyltriethoxysilane solution, the pH is adjusted to 8 with glacial acetic acid, and after being immersed for 30 minutes, the solution is taken out. It was baked in a constant temperature oven at 80 ° C for 1 hour, and the micropore D50 obtained after the treatment was 5 nm and the depth was 10 ⁇ m;
  • the sealing device makes the sublimation paper closely fit in all directions on the front and side of the stainless steel;
  • the baking temperature is 240 ° C, and the baking time is 2 minutes;
  • the aluminum alloy material with curved surface is pre-treated, and the surface of the aluminum alloy is cleaned with SP-101 type degreaser, RC-800 type rust remover and water to expose the bright aluminum alloy surface. Then baked at 90 ° C for 30 minutes;
  • Microporous treatment of the cleaned aluminum alloy is: immersing the metal substrate in the anolyte (composed of 160 g/L of sulfuric acid), and controlling the current density to be 1.3 A at 25 °C. Dm 2 was treated for 20 minutes.
  • the micropore D50 obtained after the treatment is 50 nm and the depth is 5 ⁇ m;
  • the aluminum alloy substrate to which the sublimation paper is attached is placed in a sealing device, and a vacuum is applied (the vacuum degree is 0.05 Pa).
  • the sealing device makes the sublimation paper closely fit in all directions on the front side and the side surface of the aluminum alloy part;
  • the baking temperature is 80 ° C, and the baking time is 360 minutes;
  • the aluminum alloy material with curved surface is pre-treated, and the surface of the aluminum alloy is cleaned with SP-101 type degreaser, RC-800 type rust remover and water to expose the bright aluminum alloy surface. Then baked at 90 ° C for 30 minutes;
  • Microporous treatment of the cleaned aluminum alloy is: pretreatment of the metal substrate with a sulfuric acid solution, the conditions include sulfuric acid concentration of 10%; voltage of 15V; soaking time of 20min. Forming an irregular surface of the corrosion hole metal substrate, and then placing the pretreated metal substrate into the alkali etching solution for electrochemical corrosion, the concentration of the etching solution is 5%-10%, the immersion time is 10 min, and the metal in the corrosion hole A finer pore is formed on the substrate, and the micropore D50 obtained after the treatment is 10 nm and the depth is 30 ⁇ m;
  • the sealing device Put the aluminum alloy substrate with the thermal sublimation paper in the sealing device, and by vacuuming (the vacuum degree is 0.05pa), the sealing device makes the sublimation paper closely fit on the front and side of the aluminum alloy part. ;
  • the baking temperature is 190 ° C, and the baking time is 30 minutes;
  • the first step is to spray a layer of polyurethane coating on the surface of the aluminum alloy, the film thickness is 20 ⁇ m;
  • the second step is to print the sublimation ink onto the sublimation paper
  • the printed sublimation paper is brought into contact with the coated surface on the aluminum alloy
  • the heat transfer sublimation ink is adsorbed by a heat transfer machine, and the coating is used to transfer the thermal sublimation ink to transfer the image onto the metal product from the sublimation paper to obtain the product CA1.
  • the first step is to spray a layer of polyurethane coating on the surface of the aluminum alloy, the film thickness is 20 ⁇ m;
  • the second step is to print the sublimation ink onto the sublimation paper
  • the printed sublimation paper is brought into contact with the coated surface on the aluminum alloy
  • the heat transfer sublimation ink is adsorbed by a heat transfer machine, and the coating is used to transfer the thermal sublimation ink to transfer the image onto the metal product from the sublimation paper to obtain the product CA2.
  • Salt spray metallic feel A1 The image on the surface of the metal substrate is intact Metal texture A2 The image on the surface of the metal substrate is intact Metal texture A3 The image on the surface of the metal substrate is intact Metal texture A4 The image on the surface of the metal substrate is intact Metal texture CA1 The image on the surface of the metal substrate is intact No metal texture

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

一种具有装饰图文的金属制品，包括表面具有微孔的金属基材、填充于部分微孔中的热升华油墨及位于金属基材表面的封孔层。同时还提供了一种具有装饰图文的金属制品的制备方法及由该制备方法制备得到的具有装饰图文的金属制品。

Description

具有装饰图文的金属制品及其制备方法
相关申请的交叉引用
本申请主张在2016年5月30日在中国提交的中国专利申请号No.201610367093.0的优先权，其全部内容通过引用包含于此。
技术领域
本公开属于金属装饰领域，更具体地，本公开涉及一种具有装饰图文的金属制品及其制备方法。
背景技术
随着近年来移动电子技术行业的飞速发展，电子设备的功能已经不是消费者唯一追求的目标，其外观，比如手机外壳也吸引着大众的目光，而往往拥有金属光泽和色彩的手机外壳更能满足人们对美观的要求，因而这些外观工艺的发展成为手机等电子产品装饰不可取代的一部分。
金属表面实现图文装饰，目前的技术方案是：第一步，在金属表面喷涂一层涂层；第二步，将热升华油墨打印到热升华纸上；第三步，将打印完成的热升华纸与金属上的涂层面接触；第四步，通过烫画机或其他加热方法加热，利用涂层来吸附热升华油墨，以达到图文从热升华纸上转印到金属产品上。
上述技术方法制备的产品由于需要在金属表面喷涂一层涂层，表面的涂层掩盖了金属自有的金属质感，从而使金属产品失去自有的金属质感。
发明内容
本公开旨在针对上述存在的问题，从而提供一种具有金属质感的金属制品及其制备方法。
本公开提供了一种具有装饰图文的金属制品，所述金属制品包括表面具有微孔的金属基材、填充于部分所述微孔中的热升华油墨和位于金属基材表面的封孔层。
本公开还提供一种具有装饰图文的金属制品的制备方法，所述方法包括以下步骤：
S1、对金属基材进行微孔处理，得到表面具有微孔的金属基材；并将热升华油墨按照所 需的图文形状印刷到热升华纸上；
S2、将热升华纸上的图文相匹配地贴合于所述金属基材表面；
S3、加热热升华油墨使热升华油墨进入金属基材表面的微孔中形成装饰图文；
S4、去掉热升华纸并进行封孔即得到具有装饰图文的金属制品。
本公开还提供了一种由所述方法制备得到的具有装饰图文的金属制品。
本公开的具有装饰图文的金属制品，图文油墨填充在金属表面的微孔中，然后通过封孔将图文油墨封在微孔中，图文油墨附着力强，不易变色。同时还保留了金属光泽。
本公开的方法中，通过将附着有图文的热升华纸贴合在金属基材的表面，然后通过烘干使热升华油墨进入到金属表面的微孔中，在形成图文的同时保留了金属本来的金属光泽。
本公开的其它特征和优点将在随后的具体实施方式部分予以详细说明。
具体实施方式
为了使本公开所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本公开进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本公开，并不用于限定本公开。
本公开提供了一种具有装饰图文的金属制品，所述金属制品包括表面具有微孔的金属基材、填充于部分所述微孔中的热升华油墨和位于金属基材表面的封孔层。
根据本公开所提供的金属制品，所述微孔的大小没有特别的限制，只要可以让热升华油墨进入即可，为了更有利于热升华油墨进入，可选地，所述微孔的D50为1nm-100μm，可选地为5nm-20μm，例如10nm-1μm。
本公开中，所述微孔的形状没有特别的限制，可以为单层孔，也可以为双层或多层孔，只要表面的微孔的D50为1nm-100μm即可。
根据本公开所提供的金属制品，为了使后面的封孔效果更好，可选地，所述微孔的深度为10nm-100μm，可选地为1μm-50μm，例如5μm-30μm。
根据本公开所提供的金属制品，所述金属基材没有特别的限制，只要是一般的常用金属即可，如可以是铝合金、不锈钢和镁合金中的一种。
本公开的金属制品，图文油墨填充在金属表面的微孔中，然后通过封孔将图文油墨保护在微孔中，图文油墨附着力强，不易变色。同时还保留了金属光泽。
本公开还提供了一种具有装饰图文的金属制品的制备方法，所述方法包括以下步骤：
S1、对金属基材进行微孔处理，得到表面具有微孔的金属基材；并将热升华油墨按照所 需的图文形状印刷到热升华纸上；
对金属基材进行微孔处理及将热升华油墨按照所需的图文形状印刷到热升华纸上的先后顺序没有限制，可以先进行对金属基材进行微孔处理再将热升华油墨按照所需的图文形状印刷到热升华纸上；或者先将热升华油墨按照所需的图文形状印刷到热升华纸上，然后在对金属基材进行微孔处理；也可以同时进行将热升华油墨按照所需的图文形状印刷到热升华纸上和对金属基材进行微孔处理。
S2、将热升华纸上的图文相匹配地贴合于所述金属基材表面；
这里的贴合可以理解为附着在金属基材的表面，为了使油墨图文能够保留更准确地保留原来的图文形状，这里贴合需要比较紧密的贴合。
S3、加热热升华油墨使热升华油墨进入金属基材表面的微孔中形成装饰图文；
热升华油墨在加热的情况下升华，由于热升华纸贴合在金属基材表面，所以热升华油墨升华后相应的进入对应的金属基材表面的微孔中，这样就可以在金属基材表面形成与热升华纸上的图文一样的装饰图文。
S4、去掉热升华纸并进行封孔即得到具有装饰图文的金属制品。
在热升华油墨进入微孔之后，对微孔再进行封孔，一方面可以使金属表面光滑，另一方面可以更好的保护装饰图文。
根据本公开所提供的制备方法，为了使热升华纸与金属基材更紧密的贴合，可选地，在步骤S3之前还包括将贴合有热升华纸的金属基材放入密封装置中并抽真空。通过抽真空，可以使热升华纸平滑的紧密的贴合在任意形状的金属基材表面，对金属基材的形状没有任何限制，如金属基材可以是曲面的，这样就可以在金属基材表面形成3D装饰图文。3D装饰图文更能够满足消费者对美观的要求。可以广泛应用到电子产品的外壳上。
根据本公开所提供的制备方法，所述微孔处理的方法没有特别的限制，可以是本领域常用的各种微孔处理方法，只要能够得到所需要的微孔即可，如可以是磷化处理、硅烷化处理、阳极氧化处理和蚀刻处理中的一种或两种组合处理方法。
本公开中，所述的磷化处理为：将金属基材浸入由40g/L磷酸二氢铁、20/L磷酸二氢锰和40g/L磷酸二氢锌组成的磷化液中，pH值为2，在50℃的条件下处理15分钟。磷化处理得到的微孔的D50一般在几个纳米至几十个纳米之间，形成的膜厚在0.1μm-50μm。
本公开中，所述的硅烷化处理为：将金属基体放入60％-70％乙基三乙氧基硅烷溶液中，用冰乙酸条件pH为8-9，浸泡30min后，取出放入80℃的恒温干燥箱中烘烤1小时。硅烷化处理得到的微孔的D50一般在几个纳米至几十个纳米之间，形成的膜厚在0.1μm-50μm。
本公开中，所述的阳极氧化处理为：将金属基材浸入阳极液中(由160g/L的硫酸组成)，在25℃，控制电流密度为1.3A/dm2处理20分钟。
本公开中，所述蚀刻处理可以是简单的酸蚀刻或碱蚀刻，也可以是先阳极氧化后酸蚀刻或碱蚀刻，本公开中，所述的蚀刻处理为：用硫酸溶液对金属基体进行预处理，条件包括硫酸浓度在10％-15％；电压为12-15V；浸泡时间为10-20min。形成表面不规则的腐蚀孔金属基体，再将预处理后的金属基体放入碱蚀溶液中进行电化学腐蚀，腐蚀溶液的浓度为5％-10％，浸泡时间为5-10min，在腐蚀孔的金属基体上形成更细小的孔。
根据本公开所提供的制备方法，所述微孔的大小没有特别的限制，只要可以让热升华油墨进入即可，为了更有利于热升华油墨进入，可选地，所述微孔的D50为1nm-100μm，可选地为5nm-20μm，例如10nm-1μm。所述微孔的形状没有特别的限制，可以为单层孔，也可以为双层或多层孔，只要表面的微孔的D50为1nm-100μm即可。
根据本公开所提供的制备方法，步骤S3中将热升华油墨加热的方法是对密封装置进行烘烤，为了更好的使热升华油墨进入到微孔中，可选地，步骤S3中，所述烘烤温度为80℃-240℃，可选的烘烤温度为120-180℃，烘烤时间为2-360分钟，可选的烘烤时间为30分钟-1小时。
根据本公开所提供的制备方法，所述封孔的方法没有特别的限制，可以为本领域常用的各种封孔方法，如水封孔或封孔剂封孔。所述水封孔为：将表面已经形成微孔的金属基体放入95℃的热水中浸泡30min。所述封孔剂封孔为：用6％的醋酸镍封孔剂溶液，在95℃下浸泡表面已经形成微孔的金属基体20min。
根据本公开所提供的制备方法，所述金属基材为在微孔处理后还包括烘干步骤，所述烘干的作用是确保微孔中没有水分，以便后续热升华油墨渗入微孔中，所述烘干的温度为80-100℃。
根据本公开所提供的制备方法，所述金属基材为铝合金、不锈钢和镁合金等金属材料中的一种。
本公开中，所用的热升华纸张没有特别的限制，可以为本领域常用的各种热升华纸，如可以选择本领域常用的厚度在0.09毫米热升华纸。
本公开中，所述密封装置的熔点没有特别的限制，只要高于烘烤的温度即可，可选地，密封装置的熔点温度在260℃以上。所述密封装置没有特别的限制，只要是能够起到将热升华纸进行密封即可，本公开中，所述密封装置为：抽真空的软硅胶密封袋，硅胶的熔点温度在260℃以上。
本公开中，在进行微孔处理之前，还包括对金属表面进行去油、去污以及除锈清洗的步骤。所述去油、去污及除锈清洗可以是本领域常用的各种方法，如包括：金属基体依次浸泡在RC-800型除锈剂溶液中，然后水洗，再浸泡在SP-101型除油剂溶液中，最后用纯水冲洗。
本公开还提供了一种由本公开所述的制备方法制备得到的具有装饰图文的金属制品。
本公开的方法中，通过真空将附着有图文的热升华纸很平滑的贴合在金属基材的表面，所以对金属基材没有要求，可以形成曲面的图文。同时通过烘干使热升华油墨进入到金属表面的微孔中，不会影响金属光泽。
下面通过具体实施例对本公开进行进一步的详细说明。
实施例1
在镁合金表面实现3D装饰图文，包括以下步骤：
1)首先对具有曲面的镁合金素材进行前处理，分别用SP-101型除油剂、RC-800型除锈剂和水对镁合金表面进行油污清洗，以露出光亮的镁合金表面。然后在90℃下烘烤30分钟；
2)对清洗后的镁合金进行微孔处理，微孔处理的具体方法为：将金属基材浸入由磷酸二氢铁、磷酸二氢锰和磷酸二氢锌按2：1：2组成的磷化液中，调节pH值为2，在50℃的条件下处理15分钟，处理后得到的微孔D50为1μm，深度为50μm；
3)调节烘箱的温度在90℃，烘烤微孔处理后的镁合金基材30分钟；
4)取一张厚度在0.09毫米左右的热升华纸，将热升华油墨打印在热升华纸，形成所需图文；
5)取烘干的镁合金基材，将热升华纸上的图文位置相匹配地贴合于该镁合金基材上；
6)将贴合有热升华纸的镁合金基材放于密封装置中，通过抽真空(真空度为0.05pa)，密封装置使热升华纸在镁合金件正面和侧面全方位的紧密贴合；
7)将密封装置放入已经加热的烘烤箱中，烘烤温度为120℃，烘烤时间为240分钟；
8)烘烤结束后，自然冷却，将镁合金件取出，去掉贴合的热升华纸，将已转印好的镁合金件放在纯水中，加热95℃进行30分钟封孔处理，然后用水清洗，再在90℃烘箱中，烘烤30分钟，烘干即可得到本公开的金属制品A1。
实施例2
在不锈钢表面实现3D装饰图文，包括以下步骤：
1)首先对具有曲面的不锈钢素材进行前处理，分别用SP-101型除油剂、RC-800型除锈剂和水对铝合金表面进行油污清洗，以露出光亮的不锈钢表面。然后在90℃下烘烤30分钟；
2)对清洗后的不锈钢进行微孔处理，微孔处理的具体方法为：将金属基体放入65％乙基三乙氧基硅烷溶液中，用冰乙酸调节pH为8，浸泡30min后，取出放入80℃的恒温干燥箱中烘烤1小时，处理后得到的微孔D50为5纳米，深度为10μm；
3)调节烘箱的温度在90℃，烘烤微孔处理后的不锈钢基材30分钟；
4)取一张厚度在0.09毫米左右的热升华纸，将热升华油墨打印在热升华纸，形成所需图文；
5)取烘干的不锈钢基材，将热升华纸上的图文位置相匹配地贴合于该不锈钢基材上；
6)将贴合有热升华纸的不锈钢基材放于密封装置中，通过抽真空(真空度为0.05pa)，密封装置使热升华纸在不锈钢正面和侧面全方位的紧密贴合；
7)将密封装置放入已经加热的烘烤箱中，烘烤温度为240℃，烘烤时间为2分钟；
8)烘烤结束后，自然冷却，将不锈钢件取出，去掉贴合的热升华纸，将已转印好的不锈钢件放入6％醋酸镍封孔剂溶液中，在95℃下浸泡20min进行封孔，然后用水清洗，再在90℃烘箱中，烘烤30分钟，烘干即可得到本公开的金属制品A2。
实施例3
在铝合金表面实现3D装饰图文，包括以下步骤：
1)首先对具有曲面的铝合金素材进行前处理，分别用SP-101型除油剂、RC-800型除锈剂和水对铝合金表面进行油污清洗，以露出光亮的铝合金表面。然后在90℃下烘烤30分钟；
2)对清洗后的铝合金进行微孔处理，微孔处理的具体方法为:将金属基材浸入阳极液中(由160g/L的硫酸组成)，在25摄氏度，控制电流密度为1.3A/dm2处理20分钟。处理后得到的微孔D50为50纳米，深度为5μm；
3)调节烘箱的温度在90℃，烘烤微孔处理后的铝合金基材30分钟；
4)取一张厚度在0.09毫米左右的热升华纸，将热升华油墨打印在热升华纸，形成所需图文；
5)取烘干的铝合金基材，将热升华纸上的图文位置相匹配地贴合于该铝合金基材上；
6)将贴合有热升华纸的铝合金基材放于密封装置中，通过抽真空(真空度为0.05pa)， 密封装置使热升华纸在铝合金件正面和侧面全方位的紧密贴合；
7)将密封装置放入已经加热的烘烤箱中，烘烤温度为80℃，烘烤时间为360分钟；
8)烘烤结束后，自然冷却，将铝合金件取出，去掉贴合的热升华纸，将已转印好的铝合金件放入6％醋酸镍封孔剂溶液中，在95℃下浸泡20min进行封孔，然后用水清洗，再在90℃烘箱中，烘烤30分钟，烘干即可得到本公开的金属制品A3。
实施例4
在铝合金表面实现3D装饰图文，包括以下步骤：
1)首先对具有曲面的铝合金素材进行前处理，分别用SP-101型除油剂、RC-800型除锈剂和水对铝合金表面进行油污清洗，以露出光亮的铝合金表面。然后在90℃下烘烤30分钟；
2)对清洗后的铝合金进行微孔处理，微孔处理的具体方法为：用硫酸溶液对金属基体进行预处理，条件包括硫酸浓度在10％；电压为15V；浸泡时间为20min。形成表面不规则的腐蚀孔金属基体，再将预处理后的金属基体放入碱蚀溶液中进行电化学腐蚀，腐蚀溶液的浓度为5％-10％，浸泡时间为10min，在腐蚀孔的金属基体上形成更细小的孔，处理后得到的微孔D50为10纳米，深度为30μm；
3)调节烘箱的温度在90℃，烘烤微孔处理后的铝合金基材30分钟；
4)取一张厚度在0.09毫米左右的热升华纸，将热升华油墨打印在热升华纸，形成所需图文；
5)取烘干的铝合金基材，将热升华纸上的图文位置相匹配地贴合于该铝合金基材上；
6)将贴合有热升华纸的铝合金基材放于密封装置中，通过抽真空(真空度为0.05pa)，密封装置使热升华纸在铝合金件正面和侧面全方位的紧密贴合；
7)将密封装置放入已经加热的烘烤箱中，烘烤温度为190℃，烘烤时间为30分钟；
8)烘烤结束后，自然冷却，将铝合金件取出，去掉贴合的热升华纸，将已转印好的铝合金件放入6％醋酸镍封孔剂溶液中，在95℃下浸泡20min进行封孔，然后用水清洗，再在90℃烘箱中，烘烤30分钟，烘干即可得到本公开的金属制品A4。
对比例1
在铝合金表面实现平面装饰图文，包括以下步骤：
第一步，在铝合金表面喷涂一层聚氨酯涂层，膜厚在20μm；
第二步，将热升华油墨打印到热升华纸上；
第三步，将打印完成的热升华纸与铝合金上的涂层面接触；
第四步，通过烫画机加热180℃，利用涂层来吸附热升华油墨，以达到图文从热升华纸上转印到金属产品上，得到产品CA1。
对比例2
在铝合金表面实现3D装饰图文，包括以下步骤：
第一步，在铝合金表面喷涂一层聚氨酯涂层，膜厚在20μm；
第二步，将热升华油墨打印到热升华纸上；
第三步，将打印完成的热升华纸与铝合金上的涂层面接触；
第四步，通过烫画机加热180℃，利用涂层来吸附热升华油墨，以达到图文从热升华纸上转印到金属产品上，得到产品CA2。
性能测试
1、盐雾测试
1)、将产品A1-A4及CA1-CA2放置到盐雾箱中，在温度为+35℃条件下连续喷雾2小时(NaCl溶液浓度：5％，PH为6.5-7.2，供给空气压力为10-25psi，喷雾速度为0.75-3c.c./80cm2.hr)；
2)、喷雾结束后，将样品转移到温度为+40℃相对湿度为80％的储存箱内放置96个小时；
3)、将样品取出在室温下恢复两小时后用肉眼进行检查，结果见表1。
2、金属质感
用肉眼观察产品A1-A4及CA1-CA2的表面金属效果，结果见表1。
表1
  盐雾 金属质感
A1 金属基材表面的图文完好 有金属质感
A2 金属基材表面的图文完好 有金属质感
A3 金属基材表面的图文完好 有金属质感
A4 金属基材表面的图文完好 有金属质感
CA1 金属基材表面的图文完好 无金属质感
CA2 金属基材表面的图文不完整 无金属质感
从表1中可以看出，用本公开的方法得到的金属制品表面图文完好，有金属质感，且可以得到3D效果的图文效果。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本公开的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。
尽管已经示出和描述了本公开的实施例，本领域的普通技术人员可以理解：在不脱离本公开的原理和宗旨的情况下可以对这些实施例进行多种变化、修改、替换和变型，本公开的范围由权利要求及其等同物限定。

Claims (14)

  1. 一种具有装饰图文的金属制品，其中所述金属制品包括表面具有微孔的金属基材、填充于部分所述微孔中的热升华油墨和位于所述金属基材表面的封孔层。
  2. 根据权利要求1所述的金属制品，其中所述微孔的D50为1nm-100μm。
  3. 根据权利要求1或2所述的金属制品，其中所述微孔的深度为10nm-100μm。
  4. 根据权利要求1-3中任一项所述的金属制品，其中所述金属基材为铝合金、不锈钢和镁合金中的一种。
  5. 一种具有装饰图文的金属制品的制备方法，其中所述方法包括以下步骤：
    S1、对金属基材进行微孔处理，得到表面具有微孔的所述金属基材；并将热升华油墨按照所需的图文形状印刷到热升华纸上；
    S2、将所述热升华纸上的图文相匹配地贴合于所述金属基材表面；
    S3、加热所述热升华油墨使所述热升华油墨进入所述金属基材表面的微孔中形成装饰图文；
    S4、去掉所述热升华纸并进行封孔即得到具有所述装饰图文的所述金属制品。
  6. 根据权利要求5所述的制备方法，其中在步骤S3之前还包括将贴合有所述热升华纸的所述金属基材放入密封装置中并抽真空。
  7. 根据权利要求5或6所述的制备方法，其中所述微孔处理的方法可以为磷化处理、硅烷化处理、阳极氧化处理和蚀刻处理中的一种或两种的组合处理方法。
  8. 根据权利要求5-7中任一项所述的制备方法，其中所述微孔的D50为1nm-100μm。
  9. 根据权利要求5-8中任一项所述的制备方法，其中所述微孔的深度为10nm-100μm。
  10. 根据权利要求6-9中任一项所述的制备方法，其中步骤S3中将热升华油墨加热的方法是对所述密封装置进行烘烤，烘烤温度为80℃-240℃，烘烤时间为2-360分钟。
  11. 根据权利要求5-10中任一项所述的制备方法，其中所述封孔的方法为水封孔或封孔剂封孔。
  12. 根据权利要求5-11中任一项所述的制备方法，其中所述金属基材在所述微孔处理后还包括烘干步骤，烘干温度为80-100℃。
  13. 根据权利要求5-12中任一项所述的制备方法，其中所述金属基材为铝合金、不锈钢和镁合金中的一种。
  14. 一种由权利要求5-13中任一项所述的制备方法制备得到的具有装饰图文的金属制品。
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