TW202138185A - Coated metal plate - Google Patents

Abstract

The present invention provides a coated metal plate which is provided with: a metal plate; and a hydroxide coating film that is formed on the metal plate and contains nickel. The hydroxide coating film contains, as the states of nickel in the outermost surface of the hydroxide coating film, elemental Ni represented by Nimetal, nickel (II) oxide represented by NiO, and nickel (II) hydroxide represented by Ni(OH)2; and the state ratio of Nimetal to Ni(OH)2 in the nickel in the outermost surface of the hydroxide coating film, namely, the Nimetal: Ni(OH)2 ratio is from 1:1 to 1:62.

Description

Metal plate with coating film

The present invention relates to a metal sheet forming a coating film having excellent adhesion to resin.

In the past, metal was used in various fields such as ball grid array (BGA), integrated circuit components (IC, LSI) and other electronic and electrical parts, or conductive substrates for capacitive touch panels. Joint body of board and resin.

For example, Patent Document 1 discloses a joint body of a metal plate and resin used for electronic and electrical parts, a metal plate having a chromium compound layer with many fine scaly protrusions on the surface, and a joint body of resin. However, in the technology of Patent Document 1, the chromium contained in the chromium compound layer is not required in terms of environmental load, and materials with less environmental load are being sought. Furthermore, a metal plate with good adhesion to resin is being sought. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2000-183235 A

[The problem to be solved by the invention]

The object of the present invention is to provide a metal sheet forming a coating film which is excellent in adhesion to resin. [Means to solve the problem]

The inventors of the present invention have conducted diligent studies to achieve the above-mentioned object and found that a hydroxide coating film containing specific nickel is formed on a metal plate, specifically, by forming the uppermost surface of the hydroxide coating film. The state of nickel is contained in the state _{of Ni elementary substance represented by Ni metal} , the state of nickel oxide (II) represented by NiO, and the state of nickel hydroxide (II) represented by _{Ni(OH) 2, and is contained in the hydroxide} Nickel in the outermost surface of the coating, Ni _metal state Ni (OH) ₂ in a ratio of "Ni _metal: Ni (OH) _2" ratio of 1: 1~1: 62 is the scope of the film hydroxide , The above-mentioned object can be achieved, and the present invention is finally completed.

That is, according to the present invention, there is provided a metal plate for forming a coating film, which is provided with a metal plate, and a metal plate for forming a coating film including a hydroxide coating film of nickel formed on the aforementioned metal plate, and The feature is that the state of the hydroxide coating film as the nickel on the outermost surface of the hydroxide coating film includes the state _{of Ni elementary substance represented by Ni metal} , the state of nickel oxide (II) represented by NiO, and the state of Ni(OH) ) ₂ represents the state of nickel hydroxide (II). In the nickel on the outermost surface of the hydroxide coating film, the state ratio of _{Ni metal} to Ni(OH) _{2 is "Ni metal} : Ni(OH) ₂ " The ratio is 1:1~1:62.

The metal plate forming the coating film of the present invention preferably has a plurality of protruding convex portions on the surface, and when the cut surface of the protruding convex portion is observed with a scanning electron microscope, the The height is defined as H [nm]. From the tip of the aforementioned protruding portion, in the range higher than the height of H/2, the width of the portion displaying the widest width is defined as the maximum width W _max [nm] , In the range below the height of H/2, which is the height of one half of the protruding portion, and the width of the portion displaying the narrowest width is set as the minimum width W _min [nm], the following formula (1) is satisfied And the following formula (2). 20nm≦H≦500nm (1) 20nm≦H×(W _min /W _max )≦500nm (2)

The metal plate for forming the coating film of the present invention preferably further includes a nickel conductive layer containing nickel on the metal plate, and the hydroxide coating film penetrates the nickel conductive layer and is formed on the metal plate. The metal plate for forming a coating film of the present invention is preferably on the metal plate, further comprising a base layer containing zinc, and a nickel conductive layer containing nickel formed on the base layer, and the hydroxide coating film penetrates The base layer and the nickel conductive layer are formed on the metal plate. In the metal plate forming the coating film of the present invention, it is preferable _{that the state ratio of Ni(OH) 2} in the total nickel element on the outermost surface of the hydroxide coating film is 50% or more. In the metal plate forming the coating film of the present invention, it is preferable that the thickness of the hydroxide coating film is 20 to 500 nm. In the metal plate forming the coating film of the present invention, the aforementioned hydroxide coating film can be formed in a predetermined pattern. In the metal plate forming the coating film of the present invention, the aforementioned metal plate is preferably an aluminum plate.

In addition, according to the present invention, there is provided a metal plate for forming a coating film, and an electronic component transportation jig provided with a resin adsorbing portion for adsorbing the electronic component. [Effects of the invention]

According to the present invention, it is possible to provide a metal sheet forming a coating film having excellent adhesion to resin.

FIG. 1 is a cross-sectional view showing the structure of a metal plate 10 on which a coating film is formed according to this embodiment. As shown in FIG. 1, the metal plate 10 on which the coating film is formed in this embodiment is formed on the metal plate 11, and the hydroxide coating film 12 is formed as the outermost layer. In this embodiment, as the metal plate 10 on which the coating film is formed, although the hydroxide coating film 12 is formed on the metal plate 11 through the nickel conductive layer 13 as an example, this is the same. It is not particularly limited, and it may be a form in which the hydroxide coating film 12 is directly formed on the metal plate 11 without penetrating the nickel conductive layer 13. Or, it may be a state in which a hydroxide coating film 12 is formed on the metal plate 11 through a layer different from the nickel conductive layer 13.

Although it does not specifically limit as the metal plate 11, a steel plate, a stainless steel steel plate, a copper plate, an aluminum plate, an aluminum alloy plate, a nickel plate, or the base material which carried out metal plating, etc. are mentioned. Among these, steel plates, aluminum plates, or aluminum alloy plates are preferred because of their low prices. Furthermore, when it is bonded to a resin and used as a resin-metal plate composite material, from the viewpoint that the weight reduction of the obtained resin-metal plate composite material becomes possible, an aluminum plate is more preferable, and an aluminum alloy plate is particularly preferable. Although the thickness of the metal plate 11 is not particularly limited, from the viewpoint of operability when transporting electronic parts, it is preferably 0.025 to 2 mm, more preferably 0.05 to 0.8 mm.

The hydroxide coating film 12 is a coating film formed on the metal plate 11 and constitutes the outermost layer of the metal plate 10 forming the coating film. In this embodiment, the hydroxide coating film 12 is formed on the metal plate 11 through the nickel conductive layer 13.

In this embodiment, the state of the nickel on the outermost surface of the hydroxide coating film 12 includes the state _{of Ni elementary substance represented by Ni metal} , the state of nickel oxide (II) represented by NiO, and the state represented by _{Ni(OH) 2} The state of nickel hydroxide (II). That is, when X-ray photoelectron spectroscopy (XPS) measurement was performed on the outermost surface of the hydroxide coating film 12, _{the peak of Ni elementary substance represented by Ni metal} , the peak of nickel oxide (II) represented by NiO, and Ni (OH) ₂ represents the peak of nickel hydroxide (II). In the present embodiment, the term Ni elementary substance refers to the element nickel that exists in a state that is not oxidized or oxidized.

In addition, the hydroxide coating film 12 is in the nickel on the outermost surface, and the state ratio of _{Ni metal} to Ni(OH) _{2 is "Ni metal} : Ni(OH) ₂ "in a ratio of 1:1 to 1:62. . _Furthermore , the state ratio of Ni metal and Ni(OH) ₂ is measured by X-ray photoelectron spectroscopy (XPS) on the surface of the hydroxide coating film 12, and the integral value of the peak of Ni elemental substance is calculated and the ratio of Ni(OH) ) peak integrated value of _2, and thus like, (OH) ratio was calculated in the whole state of the nickel element in the outermost surface of the simple substance of Ni and Ni is _2, Ni can be determined, the state of Ni (OH) ₂ ratio.

According to this embodiment, the state of the nickel on the outermost surface of the hydroxide coating film 12 includes the state _{of Ni elementary substance represented by Ni metal} , the state of nickel oxide (II) represented by NiO, and Ni(OH) ₂ represents the state of nickel hydroxide (II), and when _{the state ratio of Ni metal} to Ni(OH) ₂ is in the above range, the metal plate 10 forming the coating film can be made to have excellent adhesion to the resin.

The state ratio of Ni _metal to Ni(OH) ₂ is based on the ratio of "Ni _metal : Ni(OH) ₂ "being 1:1~1:62, preferably 1:1.5~1:10, more preferably 1: 1.5~1:4, more preferably 1:1.6~1:3, particularly preferably 1:1.6~1:2.2. Even if the ratio of Ni(OH) _{2 to Ni metal} is too low or too high, the metal plate that forms the coating film will deteriorate the adhesion to the resin.

_{The state ratio of Ni(OH) 2} in the total nickel element on the surface of the hydroxide coating film 12 (that is, relative to Ni elementary substance, oxides such as NiO, and hydroxide such as _{Ni(OH) 2} The total of Ni compounds and Ni compounds other than Ni oxides and hydroxides is the _{ratio of the state of Ni(OH) 2} in terms of nickel element), preferably 50% or more, more preferably 50~93%, and More preferably, it is 53 to 87%. _{By setting the state ratio of Ni(OH) 2} in the total nickel element on the outermost surface to the above range, the metal plate 10 forming the coating film can be more excellent in adhesion to the resin.

_{In addition, the state ratio of Ni metal} (Ni simple substance) in the total nickel element on the outermost surface of the hydroxide coating film 12 (that is, relative to Ni simple substance, oxides such as NiO, and Ni(OH) ₂ The total of the hydroxide, the oxide of Ni and the Ni compound other than the hydroxide is the state ratio of Ni elementary substance in terms of nickel element), preferably 1.5-50%, more preferably 7-34%, More preferably, it is 13 to 34%. The state ratio of NiO in the total nickel element on the surface of the hydroxide coating film 12 (that is, relative to Ni elementary substance, oxides such as NiO, hydroxides such as _{Ni(OH) 2, and Ni} The total amount of Ni compounds other than oxides and hydroxides is the ratio of NiO in terms of nickel element), which may be 0.1 to 13%.

Although the thickness of the hydroxide coating film 12 is not particularly limited, when it is bonded to a resin and becomes a resin-metal plate composite material, it is from the viewpoint that the bonding strength of the obtained resin-metal plate composite material becomes more sufficient In terms of view, it is preferably 20 to 500 nm, more preferably 22 to 500 nm, and still more preferably 50 to 500 nm.

Although the method for forming the hydroxide coating film 12 on the metal plate 11 is not particularly limited, it can be enumerated to form a plating layer containing nickel on the metal plate 11, and for the formed plating layer containing nickel , The method of electrolytic treatment. From the state where the formed hydroxide coating film 12 is the nickel on the outermost surface, it includes the state _{of Ni elementary substance represented by Ni metal} , the state of nickel oxide (II) represented by NiO, and the state of hydrogen represented by _{Ni(OH) 2} From the viewpoint of the state of nickel (II) oxide and _{the state ratio of Ni metal} to Ni(OH) ₂ within the above-mentioned range, a method of electrolytic treatment is preferable.

Still, a plating layer containing nickel is formed, and in the case of forming the hydroxide coating film 12 by electrolytic treatment of the formed plating layer containing nickel, the resultant coating film is formed As shown in FIG. 1, the metal plate 10 is formed by penetrating the nickel conductive layer 13 and forming a hydroxide coating film 12 on the metal plate 11.

The plating layer containing nickel is not particularly limited. Although it may be a plating layer composed of a single substance of nickel or a plating layer composed of a nickel alloy, it can be coated with a hydroxide that can be formed well. From the viewpoint of the film 12, a plating layer made of a nickel alloy is preferable, and a Ni-P alloy plating layer is preferable. Furthermore, in the case of forming a plating layer composed of nickel simple substance, the obtained metal plate 10 forming a coating film serves as the nickel conductive layer 13 and is provided with a nickel plating layer, and the plating layer composed of nickel alloy is formed. In the case of a clad layer, the obtained metal plate 10 on which the coating film is formed serves as the nickel conductive layer 13 and is provided with a nickel alloy plating layer. Although either crystalline or amorphous may be used for the nickel conductive layer 13, it is more preferably amorphous from the viewpoint of good corrosion resistance. In addition, in the case of forming a Ni-P alloy plating layer, the obtained metal plate 10 forming a coating film serves as the nickel conductive layer 13 and is provided with the Ni-P alloy plating layer. Furthermore, the Ni-P alloy plating layer can be formed, for example, by electroless plating using a plating bath containing Ni-P alloy on the metal plate 11. In the Ni-P alloy plating layer, the content of P is preferably 1-13% by weight, more preferably 5-13%.

A plating layer containing nickel is formed, and for the formed plating layer containing nickel, the electrolytic treatment conditions during the electrolytic treatment are not particularly limited, but as an electrolytic treatment bath, nickel sulfate, The method of electrolytic treatment bath containing nickel ions such as nickel chloride and nickel nitrate. In the electrolytic treatment bath used in the electrolytic treatment bath, the nickel ion concentration is preferably 0.03 to 0.4 mol/L, more preferably 0.05 to 0.3 mol/L, and still more preferably 0.1 to 0.2 mol/L.

In addition, the bath temperature of the electrolytic treatment bath during electrolytic treatment is preferably 20 to 80°C, more preferably 25 to 80°C, and still more preferably 50 to 60°C. The current density during electrolytic treatment is higher than best of 0.8~3.5 mA / cm ^2, more preferably 1~3mA / cm ^2, and still more preferably 1.5~2mA / cm ^2, performing the electrolysis treatment time of electrolytic treatment is preferably 30~200 seconds, more preferably It is 60 to 180 seconds, and more preferably 120 to 180 seconds.

Still, a plating layer containing nickel is formed, and in the case of forming the hydroxide coating film 12 by electrolytic treatment of the formed plating layer containing nickel, the nickel conductive layer 13 is formed. However, the thickness of the nickel conductive layer 13 is not particularly limited, and is preferably 1-40 μm, more preferably 1-20 μm, and still more preferably 1-10 μm.

In addition, in this embodiment, when a plating layer containing nickel is formed on the metal plate 11, although the plating layer containing nickel can be directly formed, the plating layer containing nickel is formed well, and the electrolytic treatment From the viewpoint of the formed hydroxide coating film 12, it is preferable to form a base layer containing zinc as a base layer on the metal plate 11 in advance, and then form a base layer containing nickel on the base layer containing the zinc. The plating layer.

Although the method of forming the zinc-containing base layer is not particularly limited, a method of not performing degreasing treatment for the metal plate 11, and then, if necessary, etching or pickling, and then performing zinc substitution plating. Known ones can be used for zinc substitution plating, and monozinate treatment or double zincate treatment can be used. In the case of double zincate treatment, by going through the steps of the first zinc substitution treatment (1st zincate treatment), zinc nitrate stripping treatment (dezincate treatment), and the second zinc substitution treatment (2nd zincate) conduct. In this case, water washing treatment is performed after the treatment in each step.

In addition, the metal plate 10 for forming the coating film of the present embodiment preferably has a plurality of protruding protrusions on the surface, and the plurality of protruding protrusions are preferably observed with a scanning electron microscope on the cut surface of the plurality of protrusions. When the following conditions are met. That is, it is preferable to set the height of the protruding convex portion as H [nm]. In a range higher than the height of one half of the protruding convex portion, that is, the height of H/2, it will be displayed in the widest part of the width. The width is defined as the maximum width W _max [nm]. In the range below the height of H/2, which is the height of one half of the protruding part, the width of the part showing the narrowest width is defined as the minimum width W _min [nm ], if the following formula (1) and the following formula (2) are satisfied, the adhesion to the resin can be achieved by the plural protruding portions satisfying the following formula (1) and the following formula (2) The better one. 20nm≦H≦500nm (1) 20nm≦H×(W _min /W _max )≦500nm (2)

Here, the method of measuring the height H, the maximum width W _max , and the minimum width W _{min of the protruding convex portion will be described.} FIG. 2(A) is a scanning electron microscope photograph (SEM photograph) of a cut surface near the surface of the metal plate 10 on which the coating film is formed according to Example 1. FIG. The SEM photograph of FIG. 2(A) is a cross-sectional SEM photograph showing a range of 1.25 μm in width of the cut surface of the metal plate 10 on which the coating film is formed. The cross-sectional SEM photograph of the protrusion-shaped protrusion passing through the cut surface, the protrusion-shaped protrusion with the highest height, measured the height H, the maximum width W _max , and the minimum width W _min . As the reason, when measuring the cut surface of the metal plate 10 on which the coating film is formed, resin filling, etc., and polishing are performed. Although it is the measurement of the cut surface, the protrusions appearing on the cut surface The shape of the convex portion depends on the cutting position, and there are cases where the correct shape cannot be formed due to the cutting position. On the other hand, if it is the protrusion with the highest height among the plurality of protrusions appearing in the range of 1.25 μm in width (that is, the protrusion shown by the arrow in FIG. 2(A)), Since it can be judged that a cut surface passing through the vicinity of the apex appears, it is important to focus on the protrusion with the highest height (that is, the protrusion shown by the arrow in Figure 2(A)). H. The tester of the maximum width W _max and the minimum width W _min.

The specific measurement method is as follows. First, as shown in FIG. 2(B), the height H of the protruding convex portion is obtained. That is, first, draw a line connecting the valley portions on both sides of the protruding convex portion, and use this as a reference line. In addition, the length from the reference line to the top of the protruding convex portion is defined as the height H [nm] of the protruding convex portion.

Next, as shown in FIG. 3(A), with respect to the height H of the protruding convex portion, the half height position, that is, the position of H/2, is obtained from the reference line. And, as shown in Fig. 3(B), in a range higher than the height of one half of the protruding convex portion, that is, the height of H/2, the portion showing the widest width is obtained, and the width of the widest portion Set as the maximum width W _max [nm]. Furthermore, as shown in FIG. 3(B), in the range below the height of H/2, which is the height of one half of the protruding convex portion, the width of the portion displayed at the narrowest width is obtained, and this is the narrowest The width of the part of is set as the minimum width W _min [nm]. Then, from the measured height H, maximum width W _max , and minimum width W _{min of the} protruding portion, the value of H×(W _min /W _max ) is obtained. However, in this embodiment, such a measurement is performed for 5 fields of view at different positions, and the measurement results of the 5 fields of view are taken as an average.

In addition, FIG. 4(A) is a scanning electron micrograph (SEM photograph) of a cut surface near the surface of the metal plate 10 on which the coating film is formed in Example 12. In FIG. 4(A), the width is 1.25 μm. Among the plurality of protrusions that appear in the range of, the protrusion with the highest height (ie, the protrusion shown by the arrow in FIG. 4(A)) can be clearly understood from FIG. 4(A) , In the range below the height of H/2, which is the height of one half of the protruding convex portion, the structure has branches. In this case, in each branch, the width of the narrowest part is displayed (Figure 4(B), the width W1, the width W2, the width W3, and the width W4 are measured separately), and these are added together Set as the minimum width W _min (that is, set as W _min =W1+W2+W3+W4).

In the present embodiment, the plurality of protruding portions formed on the surface of the metal plate 10 forming the coating film satisfies the above-mentioned formula (1) and the above-mentioned formula (2), although it is preferable that it satisfies the following formula (3) and the following formula (4), and more preferably satisfy the following formula (5) and the following formula (6). 30nm≦H≦360nm (3) 48nm≦H×(W _min /W _max )≦225nm (4) 66nm≦H≦300nm (5) 60nm≦H×(W _min /W _max )≦225nm (6)

In addition, in this embodiment, the method of forming a plurality of protruding portions satisfying the above-mentioned formula (1) and the above-mentioned formula (2) on the surface of the metal plate 10 on which the coating film is formed is not particularly limited, but For example, when the hydroxide coating film 12 is formed on the metal plate 11, a plating layer containing nickel is formed, and the plating layer containing nickel is formed under the above-mentioned electrolytic treatment conditions by electrolytic treatment The method of formation, etc. Furthermore, in this case, the plural protruding portions formed on the surface of the metal plate 10 on which the coating film is formed are substantially formed by the material constituting the hydroxide coating film 12.

Furthermore, in this embodiment, as shown in FIG. 5, it may be a metal plate 10a on which a coating film is formed. That is, the metal plate 10a forming the coating film is also the same as the metal plate 10 forming the coating film shown in FIG. 1 except that the hydroxide coating film 12a is formed in a predetermined pattern. Specifically, the hydroxide coating film 12a of the metal plate 10a forming the coating film is the same as the hydroxide coating film 12 of the metal plate 10 forming the coating film, except that it is formed into a specified pattern. . Still, the metal plate 10a that forms the coating film is used on the metal plate 11 to form a plating layer containing nickel and a mask with a specified pattern. The coating can be manufactured by electrolytic treatment. In particular, according to this embodiment, in accordance with the pattern of the mask used, the hydroxide coating film 12a can be formed well (the hydroxide coating film can be formed in almost the same pattern as the mask used. 12a), which is excellent in pattern formation. Still, it is preferable that the metal plate 10a on which the coating film is formed has a plurality of protruding portions satisfying the above formula (1) and the above formula (2) on the surface of the metal plate 10a on which the coating film is formed, Among the surfaces, the portion where the hydroxide coating film 12a is formed may be provided with a plurality of protruding portions satisfying the above-mentioned formula (1) and the above-mentioned formula (2).

The above-mentioned metal plates 10, 10a of the present embodiment that form the coating film have excellent adhesion to the resin. Although there are no particular limitations on such resins, for example, polydimethylsiloxane ( PDMS) and other silicone resins. As polysiloxane-based resin, in addition to polydimethylsiloxane, it has a silicone bond as the main skeleton and contains any one of a hydroxyl group, an amino group, a methyl group, a carboxyl group, and a ketone group as a function. Base.

Alternatively, in addition to silicone resins, non-silicone resins can also be used. Examples of non-silicone resins include polyether resins, polyester resins, and fluororesins. Among them, suitable Polyether resin. As a polyether resin, it is suitable to have an ether bond as the main skeleton and contain any one of a hydroxyl group, an amino group, a methyl group, a carboxyl group, and a ketone group as a functional group. In addition, as a polyester resin, it is suitable to have an ester bond as the main A skeleton containing any one of a hydroxyl group, an amino group, a methyl group, a carboxyl group, and a ketone group as a functional group. In addition, as the non-polysiloxane resin, urethane resin, polylactic acid resin, fluorine resin, ester resin, and acrylic-styrene resin may also be used. As urethane-based resins, polylactic acid-based resins, fluorine-based resins, ester-based resins, and acrylic-styrene-based resins, for example, urethane bonds, ester bonds, ether bonds, amide bonds, Any one of the acrylic bond is used as the main skeleton, and any one of a hydroxyl group, an amino group, a methyl group, a carboxyl group, a ketone group, and an acrylic group is included as a functional group. Moreover, as a fluororesin, polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), polyvinylidene fluoride (PVDF), etc. are mentioned, for example.

Since the metal plates 10 and 10a forming the coating film of the present embodiment have excellent adhesion to the resin, they can be bonded to the resin to form a resin-metal plate composite material, which can be used in various applications. For such applications, it is suitable to use, for example, ball grid arrays (BGA), integrated circuit components (IC, LSI), etc., which are used in electronic and electrical parts, conductive substrates for capacitive touch panels, and metal parts for transportation of electronic parts. , Gas flow path forming members, chemical resistant members, sliding parts, substrates for forming electronic circuits, etc. Among them, the metal plates 10 and 10a forming the coating film of the present embodiment can be suitably used as a tool for transporting electronic parts, especially as electronic parts for transporting fine electronic parts such as micro LEDs, capacitors, and semiconductor elements. Use of jigs for parts transportation.

For example, as shown in FIG. 6(A), the electronic component transportation jig 40 of this embodiment is attached to the metal plate 10 (10a) for forming the coating film of this embodiment, and is provided with a patterned resin part ( The resin adsorbing part) 20, as shown in FIG. 6(A), the electronic component transportation jig 40 presses a plurality of electronic components 60 placed in the reservoir 50, and is formed into a patterned resin The part (resin adsorption part) 20 adsorbs a plurality of electronic components 60. And, as shown in FIG. 6(B), the electronic component transportation jig 40 transports a plurality of electronic components 60 on the circuit board 70 for mounting this, and then, as shown in FIG. 6(C), by It is pressed on the circuit board 70 in order to mount a plurality of electronic components 60 on the circuit board 70 for use. Especially in the jig 40 for electronic parts transportation, it is found that the resin part (resin adsorption part) 20 is also formed in the shape of a pattern by the electronic parts being transported. From the viewpoint of sufficient bonding of 20, it is suitable to use the metal plate 10a for forming the coating film in which the hydroxide coating film 12a shown in FIG. 5 is formed into a predetermined pattern. [Example]

Although examples are given below to describe the present invention in more detail, the present invention is not limited to these examples. However, the evaluation method of each characteristic is as follows.

<XPS measurement> It is formed on the surface of the metal plate formed with the coating film obtained in the Examples and Comparative Examples (in Comparative Example 1, the plated plate without electrolytic treatment, the following descriptions for each measurement and evaluation are the same) On the surface of the hydroxide coating film, an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, model: VersaProbe II) was used to measure the peaks of Ni2p3/2 and O1s, respectively. Separate the state ratio of Ni elementary substance, the state ratio of NiO, and the state ratio of Ni(OH) ₂ , the peak value of Ni2p3/2 into waveforms corresponding to each chemical state, and the peak area of Ni2p3/2 from the corresponding Ni elementary substance ( The ratio of the peak area of Ni _metal ), the peak area of NiO, or _{the ratio of the peak area of Ni(OH) 2 is calculated.}

<The shape of the protruding part> The cut surface of the metal plate formed with the coating film obtained in the Examples and Comparative Examples was observed with a scanning electron microscope (SEM) to determine the shape of the protruding part Values of height H [nm], maximum width W _max [nm], minimum width W _min [nm], and H×(W _min /W _max ) [nm]. Specifically, through observation with a scanning electron microscope (SEM), for an arbitrary cross-section, under conditions such as a width of 1.25 μm, 5 cross-sectional SEM photos are taken, and the obtained 5 cross-sectional SEM photos are taken by Measure the height H, the maximum width W _max and the minimum width W _min of the protrusion with the highest height, and average the measurement results to obtain the height H, the maximum width W _max and the minimum width W _min and H of the protrusion ×(W _min /W _max ) value. At this time, as shown in FIG. 4(A), the protrusion-shaped protrusion with the highest height is in the range below the height of half of the protrusion-shaped protrusion, that is, the height of H/2 or less, and it has a branch-like structure. Next, measure the width of the part showing the narrowest width in each branch part, and determine the total of these as the minimum width W _min .

＜Measuring thickness of hydroxide coatings＞ Observation with a scanning electron microscope (SEM) was performed on the cut surface of the metal plate forming the coating film obtained in the Examples and Comparative Examples. The contrast of the base material in the SEM image will be different from the point to the protruding convex portion. Measured as the thickness of the hydroxide coating film up to the tip.

<Peel strength of resin layer> The metal plate for forming the coating film provided with the resin layer obtained in the Examples and Comparative Examples was cut out with a cutting knife to a width of 20 mm, and peeled from the end to a length of 20 mm. In the peeling section, tape (manufactured by Nitto Denko CS System Co., Ltd., "Super Cloth Tape No. 757Super") is attached to both sides. Coat baby powder (Siccarol) (manufactured by Asahi Group Food Co., Ltd.) on the resin layer of the unattached part of the tape, and use Tensilon universal material testing machine RTC-1210A (manufactured by Orientec Co., Ltd.) with a weighing feeling of 5kgf The tester measures the peel strength (peel load) of the resin layer in the 180° direction at a speed of 50 mm/min. The higher the value of the display peel strength, the better the adhesion to the metal plate forming the coating film and the resin layer.

＜Pattern formativeness＞ With respect to the metal plates formed with the coating film obtained in the Examples and Comparative Examples, the size of the formed hydroxide coating film was measured and compared with the size of the mask to evaluate the pattern formability. The evaluation of pattern formatting is based on the following criteria. ○: Comparing the size of the formed hydroxide coating film with the size of the mask, it is within ±0.2mm ×: Comparing the size of the formed hydroxide coating film with the size of the mask, it exceeds ±0.2mm

＜Difficult peelability of resin layer＞ For the metal plate forming the coating film with the resin layer obtained in the examples and comparative examples, by stretching at 100 mm/min, the difficulty of peeling (difficult to peel) during the peeling of the resin layer is reduced The benchmark assessment. ◎: No peeling, cracked resin layer ○: Although it can be peeled off, it is not easy to peel off ×: easy to peel off

"Example 1" An aluminum plate (Al#5000) with a thickness of 0.68 mm was prepared. In addition, the prepared aluminum plate for degreasing is carried out in the order of etching, coal dust removal, 1st zincate, dezincate, and 2nd zincate. After washing in each step, use a Ni-P plating bath. (The well-known malic acid-succinic acid electroless Ni-P plating bath), by electroless plating, a Ni-P alloy plating layer with a thickness of 10μm is formed on the substrate (P content: 12.0~12.5 weight %). Next, after degreasing and pickling the aluminum plate on which the Ni-P alloy plating layer is formed, a mask with an opening of 4 cm x 4 cm is used, and electrolysis is performed under the following conditions to obtain hydrogen with a thickness of 57 nm A metal plate made of an oxide coating film to form a coating film. <Electrolysis treatment conditions> The composition of the electrolysis treatment bath: NiSO ₄ 0.2mol/L The temperature of the electrolysis treatment bath: 25℃ The current density: 1.0mA/cm ^{2 The} electrolysis treatment time: 30 seconds

Furthermore, for the obtained metal plate forming the coating film, according to the above-mentioned method, the state ratio of Ni elementary substance, the state ratio of NiO, and the state ratio of Ni(OH) ₂ were calculated from the results of XPS measurement, and the protrusion-like protrusions were performed. Determination of the shape and pattern formation of the shape. The results are shown in Table 1.

Next, on the surface where the hydroxide coating film is formed on the metal plate forming the coating film obtained above, as a resin layer, a layer composed of dimethylsiloxane (DMS) is formed, and the ratio is 85 ℃, 10 minutes of heating, and by hardening the layer composed of dimethylsiloxane (DMS), polydimethylsiloxane (PDMS) with a thickness of 100μm is formed on the hydroxide coating film ) Layer (resin layer). Furthermore, with respect to the metal plate with the PDMS layer forming the coating film, the peel strength and the hard-to-peel property were measured according to the above-mentioned method. The results are shown in Table 1.

"Examples 2 to 11" Except that the electrolytic treatment conditions were changed to the conditions shown in Table 1, the same procedure as in Example 1 was carried out to manufacture electrolytically treated plated plates and metal plates with a PDMS layer to form a coating film, and evaluated in the same way. The results are shown in Table 1.

"Comparative Examples 1 to 3" Except that the electrolytic treatment conditions were changed to the conditions shown in Table 1, the same procedure as in Example 1 was carried out to produce a metal plate for forming a coating film and a metal plate for forming a coating film with a PDMS layer. Evaluate. The results are shown in Table 1.

"Comparative Example 4" Except that the electrolytic treatment was not performed, the same procedure as in Example 1 was carried out to manufacture a plated board, and a plated board provided with a PDMS layer, and the same evaluation was performed. The results are shown in Table 1.

尚，在表1中，「電解處理被覆膜最表面之鎳的狀態比例」，係表示將在鎳元素中，在最表面之全鎳的化學狀態(Ni單質、Ni之氧化物、與Ni之氫氧化物、與Ni之氧化物及氫氧化物以外之Ni化合物)定為100%時，「Ni單質(Ni_metal 」的狀態之鎳、「NiO」的狀態之鎳、「Ni(OH)₂ 」的狀態之鎳所佔有的比例(在表2、表3亦相同)。

Furthermore, in Table 1, "The ratio of the state of nickel on the top surface of the electrolytic treatment coating film" means the chemical state of the total nickel on the top surface of the nickel element (Ni element, Ni oxide, and Ni When the hydroxides, Ni oxides and Ni compounds other than hydroxides) are set to 100%, "Ni element (Ni _metal " state nickel, "NiO" state nickel, "Ni(OH) ₂ "The proportion of nickel in the state (the same in Table 2 and Table 3).

As shown in Table 1, as the state of nickel on the top surface, if it is the state _{of Ni elementary substance represented by Ni metal} , the state of nickel oxide (II) represented by NiO, and the state of nickel hydroxide (II _{) represented by Ni(OH) 2} The state of) includes, and in the nickel on the top surface, _{the state ratio of Ni metal} to Ni(OH) _{2 is} a hydroxide whose ratio of "Ni _metal : Ni(OH) ₂ "is 1:1~1:62 Coating film The metal plate forming the coating film has high peel strength with respect to resin (PDMS), and is also excellent in hard-to-peel properties, and is excellent in adhesion to resin (PDMS) (Examples 1 to 11). Especially with regard to Examples 10 and 11, it is considered that the resin (PDMS) is cracked in the measurement of the peel strength, so it is considered to have more excellent adhesion. Furthermore, for Examples 10 and 11, the peel strength when the resin is broken is shown. Furthermore, FIG. 2(A) shows an SEM photograph of a cut surface in the vicinity of the surface of the metal plate 10 on which the coating film is formed in the first embodiment. On the other hand, when the state ratio of _{Ni metal} to Ni(OH) _{2 in the nickel on the outermost surface is outside the range of "Ni metal} : Ni(OH) ₂ "from 1:1 to 1:62, Relative to resin (PDMS), the peel strength is low, and the hard-to-peel property is also deteriorated, and the adhesion with resin (PDMS) is deteriorated (Comparative Examples 1 to 4).

"Example 12" An aluminum plate (Al#5000) with a thickness of 0.68 mm was prepared. In addition, the prepared aluminum plate for degreasing is carried out in the order of etching, coal dust removal, 1st zincate, dezincate, and 2nd zincate. After washing in each step, use a Ni-P plating bath. (The well-known malic acid-succinic acid electroless Ni-P plating bath), by electroless plating, a Ni-P alloy plating layer with a thickness of 10μm is formed on the substrate (P content: 12.0~12.5 weight %). Next, for the aluminum plate on which the Ni-P alloy plating layer is formed, a mask with an opening of 4 cm x 4 cm is used, and electrolysis is performed under the following conditions to obtain a hydroxide coating film with a thickness of 335 nm. The metal plate that forms the coating film. <Electrolysis treatment conditions> The composition of the electrolysis treatment bath: NiSO ₄ 0.1mol/L The temperature of the electrolysis treatment bath: 25℃ The current density: 1.5mA/cm ^{2 The} electrolysis treatment time: 180 seconds

Furthermore, for the obtained metal plate forming the coating film, according to the above-mentioned method, the state ratio of Ni elementary substance, the state ratio of NiO, and the state ratio of Ni(OH) ₂ were calculated from the results of XPS measurement, and the protrusion-like protrusions were performed. Determination of the shape and pattern formation of the shape. The results are shown in Table 2.

Next, on the surface where the hydroxide coating film is formed on the metal plate forming the coating film obtained above, as a resin layer, a layer composed of a non-polysiloxane resin (polyether resin) is formed , And heated at 110°C for 10 minutes, and by hardening the non-silicone-based resin, a non-silicone-based resin layer with a thickness of 200μm is formed on the metal plate where the coating film is formed. In addition, the peel strength and hard-to-peel properties of the metal plate formed with the coating film provided with the non-silicone-based resin layer were measured according to the above-mentioned method. The results are shown in Table 2.

"Examples 13-20" Except that the electrolytic treatment conditions were changed to the conditions shown in Table 2, the other procedures were the same as in Example 12 to produce a metal plate with a coating film and a coating film with a non-polysiloxane resin layer. Metal plates are also evaluated. The results are shown in Table 2.

"Comparative Examples 5-7" Except that the electrolytic treatment conditions were changed to the conditions shown in Table 2, the other procedures were the same as in Example 12 to produce a metal plate with a coating film and a coating film with a non-polysiloxane resin layer. Metal plates are also evaluated. The results are shown in Table 2.

"Comparative Example 8" Except that the electrolytic treatment was not performed, the same procedure as in Example 12 was carried out to manufacture a plated plate and a plated plate provided with a non-silicone-based resin layer, and the same evaluation was performed. The results are shown in Table 2.

As shown in Table 2, as the state of the nickel on the top surface, if it is the state _{of Ni elementary substance represented by Ni metal} , the state of nickel oxide (II) represented by NiO, and the state of nickel hydroxide (II _{) represented by Ni(OH) 2} The state of) includes, and in the nickel on the top surface, _{the state ratio of Ni metal} to Ni(OH) _{2 is} a hydroxide whose ratio of "Ni _metal : Ni(OH) ₂ "is 1:1~1:62 Coating film The metal plate that forms the coating film has high peeling strength relative to resin (non-silicone resin), and it is also difficult to peel. It is adhesive to resin (non-silicone resin). Excellent ones (Examples 12-20). Especially with regard to Example 19, it is considered that the resin (non-silicone-based resin) was broken in the measurement of the peel strength, so it was considered to have more excellent adhesion. Still, for Example 19, the peel strength when the resin is broken is shown. 4(A) shows an SEM photograph of a cut surface in the vicinity of the surface of the metal plate 10 on which the coating film is formed according to Example 12. On the other hand, when the state ratio of _{Ni metal} to Ni(OH) _{2 in the nickel on the outermost surface is outside the range of "Ni metal} : Ni(OH) ₂ "from 1:1 to 1:62, Compared with resin (non-silicone resin), the peeling strength is low, and the hard-to-peel property is also deteriorated, and the adhesion with resin (non-silicone resin) is deteriorated (Comparative Examples 5-8).

"Example 21" An aluminum plate (Al#5000) with a thickness of 0.68 mm was prepared. In addition, the prepared aluminum plate for degreasing is carried out in the order of etching, coal dust removal, 1st zincate, dezincate, and 2nd zincate. After washing in each step, use a Ni-P plating bath. (The well-known malic acid-succinic acid electroless Ni-P plating bath), by electroless plating, a Ni-P alloy plating layer with a thickness of 10μm is formed on the substrate (P content: 12.0~12.5 weight %). Next, for the aluminum plate on which the Ni-P alloy plating layer is formed, a mask with an opening of 4 cm x 4 cm is used, and electrolysis is performed under the following conditions to obtain a hydroxide coating film with a thickness of 386 nm The metal plate that forms the coating film. <Electrolysis treatment conditions> The composition of the electrolysis treatment bath: NiSO ₄ 0.1mol/L The temperature of the electrolysis treatment bath: 50℃ The current density: 1.5mA/cm ^{2 The} electrolysis treatment time: 180 seconds

Furthermore, for the obtained metal plate forming the coating film, according to the above-mentioned method, the state ratio of Ni elementary substance, the state ratio of NiO, and the state ratio of Ni(OH) ₂ were calculated from the results of XPS measurement, and the protrusion-like protrusions were performed. Determination of the shape and pattern formation of the shape. The results are shown in Table 3.

Next, on the surface where the hydroxide coating film is formed on the metal plate forming the coating film obtained above, as a resin layer, a layer made of polytetrafluoroethylene (PTFE) with a size of 20 mm × 50 mm and a thickness of 500 μm is used. The layer was formed by heating at 360° C. and a load of 1.5 MPa for 10 minutes. Furthermore, with respect to the metal plate formed with a coating film provided with a layer made of polytetrafluoroethylene, the peel strength and the hard-to-peel property were measured according to the above-mentioned method. The results are shown in Table 3.

"Comparative Example 9" Except that the electrolytic treatment was not performed, the same procedure as in Example 21 was carried out to manufacture a plated plate and a plated plate provided with a non-silicone-based resin layer, and the same evaluation was performed. The results are shown in Table 3.

As shown in Table 3, as the state of the nickel on the outermost surface, if it is the state _{of Ni elementary substance represented by Ni metal} , the state of nickel oxide (II) represented by NiO, and the state of nickel hydroxide (II _{) represented by Ni(OH) 2} The state of) includes, and in the nickel on the top surface, _{the state ratio of Ni metal} to Ni(OH) _{2 is} a hydroxide with a ratio of "Ni _metal : Ni(OH) ₂ "of 1:1~1:2 Coating film The metal plate forming the coating film has high peel strength with respect to resin (PTFE), and is also excellent in hard-to-peel properties, and is excellent in adhesion to resin (PTFE) (Example 21). 7 shows an SEM photograph of a cut surface in the vicinity of the surface of the metal plate 10 on which the coating film is formed in the 21st embodiment. 2 out of the range of the case: the other hand, the outermost surface of the nickel, Ni _metal state Ni (OH) ₂ in a ratio of "Ni _metal: Ni (OH) _2" ratio of 1: 1~1 Relative to resin (PTFE), the peel strength is low, and the hard-to-peel property is also deteriorated, and the adhesion to resin (PTFE) is deteriorated (Comparative Example 9).

10: Forming the metal plate of the coated film 11: metal plate 12: Hydroxide coated film 13: Nickel conductive layer

[Fig. 1] Fig. 1 is a cross-sectional view of a metal plate forming a coating film according to this embodiment. [Fig. 2] Fig. 2(A) is a scanning electron microscope photograph (SEM photograph) of a cut surface near the surface of the metal plate 10 on which the coating film is formed of Example 1, and Fig. 2(B) is for A diagram illustrating the method of measuring the shape of the protruding convex portion. [Fig. 3] Fig. 3(A) and Fig. 3(B) are diagrams for explaining a method of measuring the shape of a protruding convex portion. [FIG. 4] FIG. 4(A) is a scanning electron microscope photograph (SEM photograph) of a cut surface near the surface of the metal plate 10 on which the coating film is formed in Example 12, and FIG. 4(B) is for A diagram illustrating the method of measuring the shape of the protruding convex portion. [Fig. 5] Fig. 5 is a cross-sectional view of a metal plate forming a coating film according to another embodiment. [Fig. 6] Fig. 6 is a diagram for explaining the jig for electronic component transportation related to this embodiment. [Fig. 7] Fig. 7 is a scanning electron microscope photograph (SEM photograph) of a cut surface in the vicinity of the surface of the metal plate 10 on which the coating film is formed of Example 21.

Claims (9)

A metal plate for forming a coating film, comprising a metal plate, and a metal plate for forming a coating film formed on the aforementioned metal plate and containing a hydroxide coating film of nickel, characterized by the aforementioned hydroxide coating The state of the nickel on the outermost surface of the above-mentioned hydroxide coating film includes the state _{of Ni elementary substance represented by Ni metal} , the state of nickel oxide (II) represented by NiO, and nickel hydroxide represented by _{Ni(OH) 2 (} In the state of II), in the nickel on the outermost surface of the hydroxide coating film, the state ratio of _{Ni metal} to Ni(OH) _{2 is “Ni metal} : Ni(OH) ₂ ”ratio of 1:1~1 : 62. The metal plate for forming a coating film according to claim 1, wherein the metal plate for forming the coating film is provided with a plurality of protruding protrusions on the surface, and the cut surface of the protruding protrusions is measured by a scanning electron microscope During observation, the height of the aforementioned protruding portion is set as H [nm], and in a range higher than the height of one half of the aforementioned protruding portion, that is, the height of H/2, it will be in the part showing the widest width. The width is defined as the maximum width W _max [nm], and in the range below the height of H/2, which is the height of one half of the above-mentioned protruding portion, the width of the portion displaying the narrowest width is defined as the minimum width W _min [nm ], the following formula (1) and the following formula (2) are satisfied, 20nm≦H≦500nm (1) 20nm≦H×(W _min /W _max )≦500nm (2). For example, the metal plate forming the coating film of claim 1 or 2, which is further provided with a nickel conductive layer containing nickel on the aforementioned metal plate, The hydroxide coating film penetrates the nickel conductive layer and is formed on the metal plate. The metal plate forming the coating film according to claim 3, which is on the aforementioned metal plate, and further includes a base layer containing zinc, and a nickel conductive layer containing nickel formed on the aforementioned base layer, The hydroxide coating film penetrates the base layer and the nickel conductive layer and is formed on the metal plate. The metal plate forming the coating film according to claim 1 or 2, wherein _{the state ratio of Ni(OH) 2} in the total nickel element on the outermost surface of the hydroxide coating film is 50% or more. The metal plate forming a coating film according to claim 1 or 2, wherein the thickness of the hydroxide coating film is 20 to 500 nm. The metal plate forming a coating film according to claim 1 or 2, wherein the hydroxide coating film is formed in a specified pattern. The metal plate forming the coating film according to claim 1 or 2, wherein the metal plate is an aluminum plate. A jig for transporting electronic parts, which is attached to a metal plate forming a coating film as claimed in claim 1 or 2, and is provided with a resin adsorption part for adsorbing electronic parts.

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