Exposure device stage plate and method for producing same

Abstract

The present invention provides: an exposure device stage plate which is for a semiconductor package substrate and a printed substrate, which has both easy peelability and UV resistance, and on which a coating film is formed; and a method for producing the same.　An exposure device stage plate according to the present invention comprises: an aluminum member that has a porous type anodic oxide coating which is formed on the surface of a base material composed of aluminum or aluminum alloy; and a coating film that is formed on the surface of the anodic oxide coating and that has a silicone layer containing a silicone polymer (excluding silicone oil) which does not substantially include a functional group having a fluorine atom. A method for producing an exposure device stage plate according to the present invention comprises: an anodizing step for subjecting the surface of a base material to an anodizing treatment for forming an anodic oxide coating to produce an aluminum member; and a coating film forming step for subjecting the surface of the anodic oxide coating to a coating film forming treatment for forming a silicone layer to form a coating film.

Description

Stage plate for exposure apparatus and method for manufacturing the same

[0001] The present invention relates to a stage plate for an exposure apparatus used in the solder resist process of an exposure apparatus used in the manufacture of semiconductor package substrates and printed circuit boards, and a method for manufacturing the same.

[0002] When manufacturing semiconductor package substrates and printed circuit boards (printed wiring boards), a solder resist film is formed (solder resist process) using an exposure apparatus equipped with a stage plate (also called a stage, plate, cover plate, coating plate, etc.). In the solder resist process, first, solder resist is applied to both sides of a substrate on which a circuit pattern made of copper foil has been formed on a resin substrate or glass substrate. Then, this substrate is placed on a plate (the aforementioned stage plate) provided on the stage of the exposure apparatus. Next, the substrate is attracted to the stage plate by drawing in air through intake holes provided on the stage plate, and the substrate is held (fixed) to the stage plate. Furthermore, the substrate held on the stage plate is exposed to light. Finally, the exposed substrate is removed from the stage plate and sent to the next manufacturing process.

[0003] However, when removing the substrate from the stage plate after exposure, the solder resist applied to the substrate may adhere to the stage plate and peel off from the substrate. Therefore, the stage plate is required to be made of a material that has high peelability against substances adhering to its surface and excellent peelability.

[0004] Here, regarding members with release properties, for example, Patent Document 1 describes a substrate having a coating layer having a surface layer formed from a fluororesin layer containing a crosslinked fluororesin or a fluororesin such as a hexafluoropropylene-tetrafluoroethylene copolymer (FEP), a tetrafluoroethylene-perfluoroalkoxyethylene copolymer (PFA), or polytetrafluoroethylene (PTFE), and the surface layer being roughened. According to the coating layer described in Patent Document 1, in addition to the chemical and mechanical interactions of the fluororesin layer, the non-stick effect on adhesive materials such as adhesive tapes is improved by the geometric shape effect.

[0005] Furthermore, for example, Patent Document 2 describes a mold release treatment method in which a mold having a porous alumina layer on its surface is given a release agent containing a fluorine-based silane coupling agent and a solvent, and the mold is heated under predetermined relative humidity and temperature conditions before and after the application of the release agent. According to the mold release treatment method of Patent Document 2, stable mold release properties can be achieved by the strong bonding of the hydrolyzed fluorine-based silane coupling agent to the surface of the porous alumina layer.

[0006] Furthermore, for example, Patent Document 3 describes a mold for molding fiber-reinforced plastics in which the mold surface to which a liquid release agent is applied is made of aluminum, and an anodic oxide film with numerous dispersed pores is formed on this mold surface, and the release agent is filled into the pores of this anodic oxide film. In the molding mold of Patent Document 3, the release agent is stored in the pores of the anodic oxide film, so that much of it remains on the mold surface, and the release effect of the release agent can be sustained for a longer period of time compared to conventional methods.

[0007] Japanese Patent Publication No. 2007-054749, International Publication No. 2013 / 146656, Japanese Patent Publication No. 63-30211

[0008] However, when a coating film was formed on the surface of the stage plate using a cross-linked fluororesin or a fluororesin containing FEP, PFA, or PTFE as described in Patent Document 1, the ease of peeling was not sufficient.

[0009] Furthermore, when a coating film is formed on the surface of a stage plate using a fluorine-based silane coupling agent as described in Patent Document 2, the ease of peeling may decrease when exposed to i-line (wavelength 365 nm), which is the light source used when exposing solder resist in an exposure apparatus, and the resistance to ultraviolet (UV) light (UV resistance) was insufficient.

[0010] Furthermore, in methods using liquid release agents such as silicone oil, as described in Patent Document 3, there is still a risk that the liquid release agent, such as silicone oil, may migrate to the solder resist, potentially leading to a decrease in release properties and a decline in the quality of the solder resist. In addition, release agents made of silicone oil easily peel off during cleaning, losing their release properties. Moreover, because silicone oil has a low degree of polymerization, the bonding force between molecular chains is weak, and intermolecular delamination occurs easily.

[0011] This invention has been made in view of the prior art concerning mold release properties, and aims to provide a stage plate for exposure apparatus for semiconductor package substrates and printed circuit boards, on which a coating film combining easy peelability and UV resistance is formed. Another object of this invention is to provide a method for manufacturing a stage plate for exposure apparatus for semiconductor package substrates and printed circuit boards.

[0012] The present inventors have conducted extensive research on stage plates for exposure apparatuses for semiconductor package substrates and printed circuit boards, and have found that this can be achieved by providing a coating film on the surface of an aluminum member having a porous anodic oxide film, which has a silicone layer containing a silicone polymer (excluding silicone oil) that substantially does not contain functional groups having fluorine atoms. This led to the completion of the present invention.

[0013] In other words, the gist of the present invention is as follows: (1) A stage plate for use in the solder resist process of an exposure apparatus used in the manufacture of semiconductor package substrates and printed circuit boards, comprising: an aluminum member having a substrate made of aluminum or an aluminum alloy and a porous type anodic oxide film formed on the surface of the substrate; and a coating film having a silicone layer formed on the surface of the anodic oxide film of the aluminum member and containing a silicone polymer (excluding silicone oil) that substantially does not contain functional groups having fluorine atoms. (2) The silicone layer is Si-CH ３ (1) A stage plate for an exposure apparatus, characterized in that the Si-O-Si intensity ratio is 1 or more. (3) The silicone layer has a Si-O-Si wavenumber shift of -5 cm －１ Above, 20cm －１ A stage plate for an exposure apparatus according to (1), characterized in that it is as follows: (4) The silicone layer comprises a methyl silicone elastomer, characterized in that it is as follows: (5) The anodic oxide film is semi-sealed, characterized in that it is as follows: (6) The anodic oxide film satisfies at least one of the following conditions 1 and 2, characterized in that it is as follows: (Condition 1) The impedance is 1.0 × 10 ５(1) The conductivity is less than Ω. (Condition 2) The conductivity is greater than 10 μS. (7) The coating film has a primer layer containing alkyl silicate, and the primer layer is formed between the anodic oxide film and the silicone layer, as described in (1). (8) The anodic oxide film has a film thickness of 0.1 μm or more and less than 15 μm, as described in (1). (9) The silicone layer has a film thickness greater than 0.1 μm and 300 μm or less, as described in (1). (10) The Si intensity of fluorescent X-rays on the surface of the exposure apparatus stage plate is 20 kcps or more, as described in (1). (11) The aluminum exposure rate on the surface of the exposure apparatus stage plate is 50% or less, as described in (1). (12) Integrated irradiation energy of 2,333 kJ / cm with ultraviolet light at a wavelength of 360 nm. ２ A stage plate for an exposure apparatus according to (1), characterized in that the peel strength measured by a tape peel test after exposure to ultraviolet light due to irradiation is 4 N / cm or less.

[0014] A method for manufacturing a stage plate used in a solder resist process of an exposure apparatus used for manufacturing a semiconductor package substrate and a printed circuit board, the method comprising: an aluminum member having a base material made of aluminum or an aluminum alloy and a porous anodic oxide film formed on the surface of the base material; and a coating film having a silicone layer formed on the surface of the anodic oxide film of the aluminum member and containing a silicone polymer (excluding silicone oil) that substantially does not contain a functional group having a fluorine atom. The method further comprises an anodic oxidation step of manufacturing the aluminum member by subjecting the surface of the base material to an anodic oxidation treatment for forming the anodic oxide film, and a film formation step of forming the coating film by subjecting the surface of the anodic oxide film of the aluminum member to a film formation treatment for forming the silicone layer. A method for manufacturing a stage plate for an exposure apparatus, characterized by comprising the above steps.

[0015] According to the present invention, it is possible to obtain a stage plate for an exposure apparatus of a semiconductor package substrate and a printed circuit board, on which a coating film having both easy peelability and UV resistance is formed.

[0016] FIG. 1 is a schematic cross-sectional view for explaining an example of a stage plate for an exposure apparatus. FIG. 2 is a schematic cross-sectional view for explaining an example of a stage plate for an exposure apparatus. FIG. 3 is a flowchart for explaining an example of a method for manufacturing a stage plate for an exposure apparatus. FIG. 4 is a flowchart for explaining an example of a method for manufacturing a stage plate for an exposure apparatus. FIG. 5 is a flowchart for explaining an example of a method for manufacturing a stage plate for an exposure apparatus. FIG. 6 shows a binary image obtained in the evaluation of the exposure rates of Examples 1 to 7 and 10. FIG. 7 is a graph showing the results of the Al exposure rate and the peeling strength (initial tape peeling strength) of the initial peeling evaluation for Examples 1 to 7 and 10.

[0017] The stage plate for an exposure apparatus of a semiconductor package substrate and a printed circuit board according to the present invention (hereinafter, simply referred to as "stage plate for an exposure apparatus") will be described in detail together with its manufacturing method. The components of the present invention described below can be appropriately combined in part or in whole. The dimensional ratios in the drawings may be different from the actual ratios.

[0018] [1. Stage plate for exposure apparatus] As shown in FIG. 1, the stage plate 1 for an exposure apparatus of the present invention includes an aluminum member 10 having a base material 11 made of aluminum or an aluminum alloy and a porous anodic oxide film 12 formed on the surface of the base material 11, and a silicone polymer (excluding silicone oil) formed on the surface of the anodic oxide film 12 of the aluminum member 10 and substantially containing a functional group having a fluorine atom (hereinafter, may be simply referred to as "silicone polymer") And a coating film 20 (20a) having a silicone layer 21. As shown in FIG. 2, the stage plate 2 for an exposure apparatus may further include a primer layer 22 in the coating film 20 (20b), and the primer layer 22 may be formed between the anodic oxide film 12 and the silicone layer 21. In the following description of this specification, the reference numerals will be omitted for explanation.

[0019] [1-1. Aluminum Components] <Base Material> The base material used for aluminum components consists of aluminum or an aluminum alloy. Various types of base materials exist, from 100% pure aluminum to aluminum alloys with different types and amounts of alloying elements. The material is not limited and can be determined based on the application of the exposure apparatus stage plate formed using it, and the various physical properties such as strength, corrosion resistance, and workability required for that application. Processed materials obtained by appropriately processing them into a desired shape, and combined materials obtained by appropriately combining these processed materials, can also be used. Of these, for example, from the viewpoint of excellent strength and corrosion resistance, it is preferable to use 3000 series alloys, 5000 series alloys, or 6000 series alloys. In particular, from the viewpoint of suppressing distortion, it is preferable to use aluminum or aluminum alloys with a 0.2% yield strength of 100 MPa or more. There is no upper limit to the 0.2% yield strength, but it is usually preferable to be 600 MPa or less.

[0020] Furthermore, although not limited by the exposure equipment used, a general guideline for substrate thickness is that a thickness of approximately 0.3 mm to 10 mm can be used.

[0021] <Anodized Coating> The substrate also has a porous type anodic oxide coating formed on its surface. There are two main types of anodic oxide coatings: barrier type coatings that do not have pores and porous type coatings that have countless fine pores. Of these, the porous type anodic oxide coating is required. With the porous type anodic oxide coating, a porous film grows on the barrier layer, so it can be grown to a practical desired thickness, and the silicone polymer contained in the silicone layer described later can be allowed to penetrate the pores, thereby improving the adhesion between the anodic oxide coating and the silicone layer, and improving the ease of peeling by the silicone layer.

[0022] The porous anodic oxide film formed on the surface of the substrate is not limited in shape or the like within the scope of the objectives of the present invention, and as is commonly known, it consists of a structure in which basic units of porous layers (porous layers) (sometimes commonly called cells) are assembled, each having a bottomed hole (sometimes commonly called a hole or pore) that opens to the surface and a wall that rises upright around the hole.

[0023] The thickness of the anodic oxide film should be sufficient to allow the silicone polymer described later to penetrate the pores, preferably 0.1 μm or more, more preferably 1 μm or more, and even more preferably 3 μm or more. On the other hand, from the viewpoint of crack resistance, it is preferably 30 μm or less, more preferably less than 15 μm, even more preferably 10 μm or less, and particularly preferably 5 μm or less. The thickness of the anodic oxide film can be appropriately adjusted depending on the conditions of the anodic oxidation treatment.

[0024] Furthermore, the pore size of the anodic oxide film only needs to be large enough for the silicone polymer described later to penetrate the pores, and is usually preferably several nm to several tens of nm. For example, in the case of sulfuric acid anodic oxidation, which is performed using a sulfuric acid bath, the pore size of the resulting sulfuric acid anodic oxide film is usually 10 to 20 nm.

[0025] In this embodiment, the anodic oxide film is preferably partially sealed to prevent water, foreign matter, and impurities from entering and adsorbing into the numerous pores formed in the film after anodic oxidation. The degree of sealing can be appropriately adjusted within the scope of the objectives of the present invention, but it is more preferable that the pores are partially sealed. Compared to the case where the pores of the anodic oxide film are completely sealed, partial sealing allows the silicone polymer described later to penetrate, improving the adhesion between the anodic oxide film and the silicone layer. Furthermore, compared to the case where the pores of the anodic oxide film are completely sealed, when the silicone polymer described later is heated and cured, the stress generated due to the volume change of the anodic oxide film due to heating is more easily released, making it easier to suppress cracks that occur in the anodic oxide film.

[0026] Here, regarding the degree of semi-sealing of the anodic oxide film, if the effects such as the above-mentioned adhesion and crack suppression can be obtained, the degree can be appropriately adjusted, but it is preferable to satisfy at least one of the following Condition 1 and Condition 2. (Condition 1) The impedance is less than 1.0×10 ５ Ω. (Condition 2) The conductivity is greater than 10 μS.

[0027] That is, the degree of semi-sealing of the anodic oxide film can be defined by measuring the difficulty (ease) of current flow in an AC circuit using electrical measurement, and it can be defined using the measured value of the impedance as in Condition 1 or the conductivity (also referred to as admittance) as in Condition 2. Regarding the measurement methods of these impedance and conductivity, as described in the examples below, JIS H 8683-3 can be referred to.

[0028] Regarding the impedance (difficulty of current flow) of Condition 1, it is usually preferably 1.0×10 ６ Ω or less, more preferably less than 1.0×10 ５ Ω, and even more preferably 5.0×10 ４ Ω or less. On the other hand, the lower limit value of the impedance is not restricted, but it is usually preferably 1.0×10 ３ Ω or more, and more preferably 1.0×10 ４ Ω or more. When the impedance is below the above upper limit value, the pores of the anodic oxide film can be changed from a completely sealed state to a semi-sealed state. Also, when the impedance is above the above lower limit value, the pores of the anodic oxide film can be changed from a state without sealing treatment to a semi-sealed state. Therefore, when the impedance is within the above numerical range, the anodic oxide film becomes semi-sealed, the adhesion between the anodic oxide film and the silicon layer described later is improved, and the peelability due to the silicon layer is improved.

[0029] Furthermore, the conductivity (admittance, ease of current flow) in condition 2 is preferably 1 μS or more, more preferably greater than 10 μS, and even more preferably 20 μS or more. On the other hand, there is no upper limit to the conductivity, but it is preferably 100 μS or less, and more preferably 70 μS or less. By having a conductivity below the above upper limit, the pores of the anodized film can be moved from an unsealed state to a semi-sealed state. Also, by having a conductivity above the above lower limit, the pores of the anodized film can be moved from a completely sealed state to a semi-sealed state. Therefore, by having a conductivity within the above numerical range, the anodized film becomes semi-sealed, improving the adhesion between the anodized film and the silicone layer described later, and improving the ease of peeling by the silicone layer.

[0030] [1-2. Coating Film] <Silicone Layer> The coating film formed on the surface of the anodic oxide film of the aluminum member has a silicone layer containing a silicone polymer (excluding silicone oil) that substantially does not contain functional groups having fluorine atoms. The silicone layer is a solid layer. Silicone is a polymer (silicone polymer) having siloxane bonds, in which silicon and oxygen are alternately bonded, as its main backbone. In this specification, silicone is referred to as silicone polymer in order to distinguish it from silane monomers (silicone monomers).

[0031] Silicone polymers can be classified into three types: silicone oil, silicone elastomer, and silicone resin. The silicone layer contains at least one selected from silicone elastomer and silicone resin. In other words, the silicone layer contains a silicone polymer excluding silicone oil. It should be noted that the silicone polymer contained in the silicone layer only needs to contain at least one selected from silicone elastomer and silicone resin as the main component; this does not exclude the inclusion of silicone oil. The content ratio (mass%) of silicone elastomer and silicone resin in the silicone polymer contained in the silicone layer is preferably 50% by mass or more, more preferably 90% by mass or more, even more preferably 99% by mass or more, particularly preferably 99.9% by mass or more, and most preferably 100% by mass.

[0032] Typically, silicone oil is liquid, while silicone elastomers and silicone resins are solid. Therefore, if the silicone layer is a solid layer, it can be determined that the silicone layer contains silicone polymers excluding silicone oil, i.e., silicone elastomers and / or silicone resins.

[0033] 29 The degree of crosslinking of silicone polymers can be measured using Si-NMR. A low degree of crosslinking indicates the presence of silicone oil, a moderate degree indicates the presence of silicone elastomer, and a high degree indicates the presence of silicone resin.

[0034] As will be described later, using infrared absorption (IR) spectroscopy, the "Si-CH ３ By obtaining the "Si-O-Si strength ratio," the proportion of M units, D units, T units, and Q units contained in the silicone polymer can be evaluated. If M units and D units are present in large quantities, it can be determined that silicone elastomer is present, and if T units and Q units are present in large quantities, it can be determined that silicone resin is present.

[0035] ​Hereafter, unless otherwise noted, the term "silicone polymer" in this specification shall mean a silicone polymer excluding silicone oil, i.e., a silicone elastomer and / or silicone resin. Furthermore, silicone rubber shall be treated as synonymous with silicone elastomer.

[0036] The silicone layer is mainly composed of a silicone polymer. The silicone layer is formed from a cured silicone polymer in a film-like structure. The silicone polymer is preferably present in the silicone layer at a concentration of 50 to 100% by mass. Other known pigments and fillers may be added as needed, but are not limited to these.

[0037] As the silicone polymer used, one that substantially does not contain functional groups having fluorine atoms is used. Here, "substantially" means that the intention is not to exclude the content of functional groups having fluorine atoms or compounds having such functional groups that may be present in a range that does not impair the objectives of the present invention, and as mentioned above, the intention is not to exclude content up to a level that does not impair the peelability and UV resistance that are the issues of the present invention. The fact that the silicone polymer contained in the silicone layer substantially does not contain functional groups having fluorine atoms is determined by the fluorine atom content of the silicone layer. Specifically, it is preferable that the fluorine atom content in the silicone layer be less than 10% by mass, more preferably less than 5% by mass, even more preferably less than 1% by mass, particularly preferably less than 0.1% by mass, and most preferably none (below the detection limit). The fluorine atom content in the silicone layer can be calculated by performing elemental analysis of the silicone layer using X-ray fluorescence analysis and using the fundamental parameter method (FP method) from the X-ray fluorescence intensity values ​​measured for all elements. The FP method is a method of calculating the theoretical intensity using fundamental parameters (physical constants) and determining the composition from the measured intensity.

[0038] The functional group having a fluorine atom is not limited to any commonly known functional group having a fluorine atom, but specifically, perfluoroalkyl groups (-C) ｎ F２ｎ＋１ ) or difluoromethylene group (-CF ２ -) or fluorovinyl group (-CF=CF ２ ) and trifluoromethoxy group (-OCF ３ ) are some examples.

[0039] As for the silicone polymer, as is generally known, it is not limited to any polymer (referred to as polysiloxane, organopolysiloxane, etc.) that has a siloxane bond (Si-O) as its main backbone and organic substituents such as methyl groups or phenyl groups in its side chains, and one or more types can be selected and used within the scope of the object of the present invention.

[0040] Furthermore, such silicone polymers include those having various structures depending on the degree of polymerization, the type of organic substituent, and the number of siloxane bonds with a single Si atom (so-called M units, D units, T units, and Q units), as mentioned above.

[0041] As described above, the silicone polymer of the present invention is preferably formed as a film having a certain film thickness, as described later, that is, as a layer of a coating film, from the viewpoint of improving the easy peelability that is the objective of the present invention. It is preferable that the silicone polymer be a high molecular weight silicone elastomer or silicone resin having a certain degree of polymerization. Although there are no limitations on such high molecular weight silicone elastomers or silicone resins, for example, those with a degree of polymerization of 5000 or more are generally used. Also, silicone resins generally tend to have a higher degree of polymerization than silicone elastomers. The degree of polymerization of silicone oil is lower than that of silicone elastomers and silicone resins. The molecular weight of silicone oil is lower than that of silicone elastomers and silicone resins. From this viewpoint, the silicone polymer (silicone layer) of the present invention is different from liquid mold release agents such as silicone oil described in Patent Document 3.

[0042] Silicone polymers include those with various structures, particularly those with different degrees of polymerization, types of organic substituents, and the number of siloxane bonds with a single Si atom (so-called M units, D units, T units, and Q units), as mentioned above.

[0043] Furthermore, from the viewpoint of improving the ease of peeling, which is an issue of the present invention, it is preferable that the silicone polymer of the present invention has a small surface free energy, which is considered to contribute to the ease of peeling. From this viewpoint, a silicone elastomer mainly containing D units as constituent units is preferred as the silicone polymer. That is, a linear silicone polymer mainly containing D units as constituent units is preferred. Examples of silicone elastomers include methyl-based silicone elastomers, methylalkyl-based silicone elastomers, and methylphenyl-based silicone elastomers. Methyl-based refers to a system in which a methyl group is bonded to the Si in the main chain. Methylalkyl refers to a system in which a methyl group and an alkyl group are bonded to the Si in the main chain. Methylphenyl refers to a system in which a methyl group and a phenyl group are bonded to the Si in the main chain. In order for the surface free energy to be small in a polysiloxane that takes on a characteristic helical structure, it is preferable to use organic substituents that have a functional group that can reduce the surface free energy as the organic substituents facing outward from the helix, and such an organic functional group is preferably a methyl group. For this reason, a methyl-based silicone elastomer is more preferable. Methyl-based silicone elastomers include, for example, polydimethylsiloxane (PDMS). Among these, linear polydimethylsiloxane, in which all side chains consist of methyl groups, is a more preferred embodiment. By using a methyl-based silicone elastomer in this way, the density of methyl groups is maximized, reducing the surface free energy and contributing to improved peelability, especially in the initial state.

[0044] In contrast, a silicone resin mainly containing T units and / or Q units as constituent units can also be used as the silicone polymer. That is, a non-linear silicone polymer mainly containing T units and / or Q units as constituent units can also be used. Alternatively, a silicone resin having a structure in which linear and cyclic parts are mixed can also be used. Examples of silicone resins include methyl-based silicone resins, methylalkyl-based silicone resins, and methylphenyl-based silicone resins. Other examples include polyether-modified silicones in which some of the methyl groups bonded to the Si of the main chain are replaced with siloxane bonds, or in which some of the methyl groups bonded to the Si of the main chain are replaced with ether chains. Examples of methyl-based silicone resins include non-linear polydimethylsiloxane (PDMS).

[0045] Furthermore, such a silicone polymer can be the linear PDMS mentioned above or any other silicone polymer that can improve the peelability, which is the objective of the present invention. Whether or not a silicone polymer is such a polymer can be determined by the following Si-CH ３ It is also possible to select based on the Si-O-Si intensity ratio and the Si-O-Si wavenumber shift.

[0046] In other words, the silicone polymer (silicone layer) of the present invention has a Si-CH ratio relative to the peak intensity of the Si-O-Si bond when the infrared absorption (IR) spectrum is measured. ３ Ratio of bond peak intensity (Si-CH ３ The Si-O-Si intensity ratio is preferably 0.9 or higher, and more preferably 1 or higher. For peak intensity, the height of the peak top is used. When measuring the IR spectrum of linear PDMS, the fingerprint region (800-1300 cm²) is used. －１ ) in the Si-C bond (approximately 1250 cm) －１ ), Si-O-Si bond (approximately 1081 cm －１ ) and Si-CH ３ Combined (approximately 785cm －１Because it has three characteristic peaks, these peaks are used. Furthermore, if the silicone polymer contains many T units and Q units, Si-CH ３ Since the proportion of Si-CH becomes relatively small, ３ The peak intensity will decrease. Conversely, if the silicone polymer contains a large amount of M units and D units, Si-CH ３ Since the proportion of Si-CH is relatively large, ３ The peak intensity of Si-O-Si increases. In other words, the peak intensity of Si-O-Si is not constant depending on the structure adopted by the silicone polymer, therefore, the peak intensity of Si-CH ３ When the "Si-O-Si strength ratio" is within the above range, the silicone polymer tends to contain a large amount of M units and D units, and in doing so, Si-CH ３ As the proportion of becomes relatively larger, the surface free energy decreases, the bonding strength with the silicone layer (coating film) decreases, and peelability improves. Conversely, "Si-CH ３ If the "Si-O-Si strength ratio" is below the above range, the silicone polymer tends to contain a large amount of T units and Q units, resulting in Si-CH ３ As the proportion of becomes relatively smaller, the peelability tends to decrease. In particular, Si-CH ３ The Si-O-Si strength ratio has a significant impact on initial delamination evaluation and repeated delamination evaluation. ３ The Si-O-Si intensity ratio is more preferably 1.1 or higher, and particularly preferably 1.2 or higher. On the other hand, while there is no upper limit, it is preferably 1.5 or lower, more preferably 1.4 or lower, and even more preferably 1.3 or lower.

[0047] Furthermore, the silicone polymer (silicone layer) of the present invention exhibits a Si-O-Si wavenumber shift of -5 cm when its infrared absorption (IR) spectrum is measured. －１ Above, 20cm －１ Preferably, the following: -3 cm －１ Above, 10cm －１The following is more preferable: The "Si-O-Si wavenumber shift" is such that the peak position of Si-O-Si when the IR spectrum of the silicone polymer is measured is the same as the peak position of the linear PDMS (cm －１ This represents the wavenumber shifted from the peak position of linear PDMS when compared to PDMS. A wavenumber shift indicates that a functional group other than a methyl group is attached to the Si atom forming the siloxane bond. When the functional group attached to the Si atom forming the siloxane bond is close to PDMS (methyl group addition), the Si-O-Si wavenumber shift becomes 0. When a phenyl group, vinyl group, or other group other than a methyl group is attached, the Si-O-Si wavenumber takes a value far from 0. Since the surface free energy of the functional group is smallest for the perfluoromethyl group and next smallest for the methyl group, when the Si-O-Si wavenumber shift takes a value far from 0, the surface free energy increases due to the attachment of a group other than a methyl group to Si, and the peelability decreases. In other words, when the Si-O-Si wavenumber shift is within the above numerical range, it tends to indicate that a large proportion of the functional groups attached to the Si atom forming the siloxane bond are methyl groups, resulting in high peelability. The Si-O-Si wavenumber shift is more preferably -2 cm. －１ More than 5cm －１ The following, and particularly preferably -1 cm －１ Above 2 cm －１ The following applies:

[0048] The thickness of the silicone layer is not limited, but is usually preferably 0.1 μm or more, more preferably greater than 0.1 μm, preferably 300 μm or less, and more preferably 30 μm or less. By making the silicone layer above the lower limit, the exposure rate of the anodic oxide film (i.e., the exposure rate of aluminum, a constituent element of the anodic oxide film) is reduced, and the exposure rate of the silicone layer (i.e., the exposure rate of silicon, a constituent element of the silicone layer) is improved, thereby improving the ease of peeling by the silicone layer. On the other hand, by making the silicone layer below the upper limit, it becomes easier to suppress the occurrence of defects in the appearance of the silicone layer (such as cracks).

[0049] <Primer Layer> The silicone layer may be formed directly on the surface of the anodic oxide film, or, from the viewpoint of stabilizing (maintaining performance) the formed silicone layer, a primer layer containing alkyl silicate may be formed between the anodic oxide film and the silicone layer, and the silicone layer may be formed on the anodic oxide film via the primer layer. By having a primer layer, siloxane bonds are formed after dehydration condensation between the hydroxyl groups of the anodic oxide film and the silanol groups constituting the alkyl silicate contained in the primer layer, and siloxane bonds are also formed after dehydration condensation between the silanol groups constituting the alkyl silicate contained in the primer layer and the silanol groups of the silicone polymer contained in the silicone layer. Therefore, the adhesion between the anodic oxide film and the silicone layer can be improved via the primer layer, contributing to the stabilization (maintaining performance) of the silicone layer.

[0050] Such alkyl silicates are not limited, but for example, methyl silicates ((CH) ３ -O-) ３ Alkyl silicate (-Si-OH), ethyl silicate, butyl silicate, propyl silicate, etc. can be used, with ethyl silicate being preferred. That is, a coating film having a silicone layer preferably has a primer layer containing the alkyl silicate in addition to the silicone layer, and it is preferable that the silicone layer is in close contact with the anodic oxide film via the primer layer. In addition to these silicone layers and primer layers, or in place of the primer layer, the coating film may also have other layers.

[0051] <Silicon (Si) content on the surface> On the surface of the coating film having the silicone layer as described above (i.e., the surface of the stage plate for the exposure apparatus), it is preferable that the silicone layer is sufficiently covering the surface, and a high content of Si, an element constituting the silicone layer, is preferable from the viewpoint of performance. Such a high Si content can be confirmed by measuring the intensity of the Si element by fluorescent X-ray analysis of the surface of the coating film (i.e., the surface of the stage plate for the exposure apparatus), and it is preferable that the Si intensity of the fluorescent X-rays is 15 kcps or more, and more preferably 20 kcps or more. There is no upper limit to the Si intensity of the fluorescent X-rays, but it is usually 200 kcps or less.

[0052] <Exposure Rate of Aluminum (Al), Exposure Rate of Si> Furthermore, on the surface of the coating film having the silicone layer (i.e., the surface of the stage plate for the exposure apparatus), it is preferable from the viewpoint of performance that the exposure rate of the underlying anodic oxide film, that is, the exposure rate of Al, a constituent element of the anodic oxide film, is low because it is sufficiently covered by the silicone layer. Such a low exposure rate of Al can be shown by analyzing the surface of the coating film (i.e., the surface of the stage plate for the exposure apparatus) using scanning electron microscope energy-dispersive X-ray spectroscopy (SEM-EDX), mapping the number of signals originating from Al (kcps), and determining the area percentage of the binarized result. The Al exposure rate (area %) shown by this measurement method is preferably 70% or less, more preferably 60% or less, even more preferably 50% or less, and particularly preferably 30% or less.

[0053] On the other hand, in addition to a low Al exposure rate, it is preferable that the Si exposure rate on the surface of the coating film having the silicone layer (i.e., the surface of the stage plate for the exposure apparatus) is high, which is synonymous with a high Si exposure rate. The Si exposure rate can be shown by mapping the signal (kcps) originating from Si using the same method as for measuring the Al exposure rate, and determining the area percentage of the binarized signal. The Si exposure rate (area %) shown by this measurement method is preferably 30% or more, more preferably 40% or more, even more preferably 50% or more, and particularly preferably 70% or more.

[0054] <Easy Peelability and UV Resistance> Furthermore, regarding the ease of peelability and UV resistance of the surface of the exposure apparatus stage plate of the present invention equipped with such a coating film, it is preferable that it is excellent in any or all of the following: initial peel evaluation, repeated peel evaluation (1000 repetitions), and post-UV exposure peel evaluation, as evaluated in the examples, and in all cases, the peel strength is preferably 4 N / cm or less. More preferably 3 N / cm or less, even more preferably 2 N / cm or less, particularly preferably 1 N / cm or less, and most preferably 0.5 N / cm or less. That is, for the initial peel evaluation, it is preferable that the peel strength measured by a tape peel test performed with reference to JIS Z0237 is within the above range. Furthermore, for the repeated peel evaluation (1000 repetitions), it is preferable that the peel strength after repeating the tape application, pressing, and peeling 1000 times in the initial peel evaluation is within the above range. Furthermore, for the post-UV exposure peel evaluation, it is preferable that the cumulative irradiation energy of 2,333 kJ / cm with ultraviolet light at a wavelength of 360 nm is used. ２ It is preferable that the peel strength measured by a tape peel test after exposure to ultraviolet light due to irradiation is within the above range.

[0055] [2. Method for Manufacturing a Stage Plate for an Exposure Apparatus] As shown in Figure 3, the method for manufacturing a stage plate 1 for an exposure apparatus according to the present invention comprises: an aluminum member 10 having a substrate 11 made of aluminum or an aluminum alloy and a porous type anodic oxide film 12 formed on the surface of the substrate 11; and a coating film 20 (20a) having a silicone layer 21 formed on the surface of the anodic oxide film 12 of the aluminum member 10 and containing a silicone polymer (excluding silicone oil) that substantially does not contain functional groups having fluorine atoms. The method comprises an anodizing step S10 (S10a) for manufacturing the aluminum member 10 by performing an anodizing treatment S1 to form an anodic oxide film 12 on the surface of the substrate 11; and a coating formation step S20 (S20a) for forming a coating film 20a by performing a coating formation treatment S2 to form a silicone layer 21 on the surface of the anodic oxide film 12 of the aluminum member 10. As shown in Figure 4, the manufacturing method S1 (S1b) for the exposure apparatus stage plate 1 may, in the anodic oxidation step S10 (S10b), perform an anodic oxidation treatment S1 to form an anodic oxide film 12, followed by a semi-sealing treatment S11 to semi-seal the anodic oxide film 12 of the substrate 11. As shown in Figure 5, the manufacturing method S2 for the exposure apparatus stage plate 2 may, in the film formation step S20 (S20b), perform a primer layer formation treatment S22 to form a primer layer 22 containing alkyl silicate on the anodic oxide film 12 after the anodic oxidation step S10. Furthermore, the film formation treatment S2 may be performed after the primer layer formation treatment S22. In the following description of this specification, reference numerals will be omitted.

[0056] [2-1. Anodizing Process] <Anodizing Treatment> First, in the anodizing process, an anodizing treatment is performed on a substrate made of aluminum or an aluminum alloy to form an anodic oxide film. The method of anodizing treatment is not particularly limited and can be the same as known methods. For example, the surface of the substrate to be treated is anodized in an electrolyte under a constant voltage to form an oxide film. In addition, known pretreatments may be performed prior to the anodizing treatment. As pretreatments, known treatments such as degreasing, etching, and smut removal may be performed. Chemical polishing or chemical texture finishing may also be performed.

[0057] Examples of electrolytes used in anodizing include sulfuric acid, oxalic acid, and phosphoric acid. These electrolytes may be used individually or in combination of two or more. Among these electrolytes, sulfuric acid is preferred from a practical standpoint. The concentration of the electrolyte may be, for example, 1 g / L to 600 g / L.

[0058] Other anodizing conditions are not particularly limited and can be adjusted as appropriate from the standpoint of the substrate condition, achieving the desired porous type, and maintaining the preferred film thickness range mentioned above. The electrolyte temperature may be, for example, 0°C to 30°C. The current density may be, for example, 1 mA / cm². ２ ~50 mA / cm ２ This is also acceptable. The electrolysis time may be, for example, 10 to 50 minutes.

[0059] <Semi-sealing treatment> After forming an anodic oxide film by the anodizing treatment described above, a semi-sealing treatment is performed to partially seal the anodic oxide film. There are no restrictions on the degree of the semi-sealing treatment, but it is preferable to satisfy at least one of the above-mentioned conditions 1 (impedance) and 2 (conductivity).

[0060] The type of semi-sealing treatment can be selected from known sealing treatments, for example, by using high-temperature water, high-temperature steam, nickel acetate aqueous solution, nickel fluoride, silicate, or a combination thereof. The sealing treatment generates aluminum hydrate in the pores. As a typical example, when performing the sealing treatment in a sealing solution consisting of an aqueous solution of nickel acetate, the temperature of the sealing solution is typically set to 90°C or higher, and the sealing treatment is performed by immersion for about 1 to 30 minutes. In this case, the sealing treatment time is preferably such that it satisfies at least one of the above conditions 1 and 2, for example, preferably 1 minute or more and less than 25 minutes, more preferably 1 minute or more and 20 minutes or less, even more preferably 1 minute or more and 15 minutes or less, and particularly preferably 1 minute or more and 10 minutes or less. By keeping the time below the upper limit of the above numerical range, the anodic oxide film can be semi-sealed without being excessively sealed. This makes it easier to improve the adhesion between the anodic oxide film and the silicone layer.

[0061] [2-2. Film Formation Process] Next, in the film formation process, the coating film is formed by applying a film formation treatment to the surface of the anodic oxide film obtained in the anodizing process to form the silicone layer. <Film Formation Treatment> The film formation treatment is not limited as long as it is a treatment that can form a coating film by forming a silicone layer on the surface of the anodic oxide film. For example, a method can be given in which a silicone layer is formed by using a resin composition containing the silicone polymer and coating it onto the surface of the anodic oxide film and curing it. Although there are no limitations on such a resin composition, examples include one in which the silicone polymer is the main component and, if necessary, known solvents, known pigments, fillers, etc. are appropriately blended. For example, silica, mineral spirits, zinc compounds, diisopropoxydi(ethoxyacetoacetyl) titanate, organic titanate, alkoxide, alkoxysiloxane, methyltrimethoxysilane, octamethylcyclotetrasiloxane, isopentyl acetate, etc. can be blended.

[0062] The method of coating the surface of the anodic oxide film with the resin composition is not limited, and known coating methods can be used. Examples include brush coating, roller coating, trowel coating, spatula coating, flow coater coating, spray coating (e.g., air spray coating, airless spray coating, etc.), bar coating, dip coating, spin coating, etc. The amount of coating can be appropriately adjusted according to the desired film thickness after curing.

[0063] Furthermore, there are no limitations on the curing method of the resin composition after painting, and known drying methods can be used, such as natural drying or heat drying. There are also no limitations on the curing temperature or time, and for example, a method of curing at room temperature (25°C) to 200°C in one go or in stages, for example, for about 1 minute to 1180 minutes can be used.

[0064] <Primer Layer Formation Treatment> In the film formation step, a primer layer formation treatment may be applied to the anodic oxide film to form a primer layer containing alkyl silicate. By providing a primer layer, as described above, the adhesion between the anodic oxide film and the silicone layer can be improved, contributing to the stabilization (performance maintenance) of the silicone layer. The method of the primer formation treatment is not limited, but one example is a method of forming a primer layer by coating the surface of the anodic oxide film with a composition for forming a primer layer containing alkyl silicate and, if necessary, other solvents and other components, and curing it. The coating method and curing method are also not limited and can be appropriately adjusted within the same range of conditions as the film formation treatment conditions described above.

[0065] [3. Effects] The exposure apparatus stage plate in the present invention is provided with a coating film on the surface of an aluminum member having a porous anodic oxide film, the coating film having a silicone layer containing a silicone polymer (excluding silicone oil) that substantially does not contain functional groups having fluorine atoms, thereby providing an exposure apparatus stage plate with improved peelability and UV resistance.

[0066] The inventors speculate that the effects of this easy peeling and UV resistance are as follows:

[0067] In other words, for example, a coating film formed using the fluororesin described in Patent Document 1 tends to have poor peelability in its initial state. Peelability is strongly influenced not only by the surface free energy but also by the mechanical properties of the material (especially flexibility and deformability). Specifically, compared to silicone polymers, fluororesins have high main chain rigidity and are less prone to surface deformation, leading to localized stress concentration and inhibiting peelability. Furthermore, compared to silicone polymers, the movement of molecular chains in fluororesins is restricted, making stress relaxation less likely, thus inhibiting peelability. For these reasons, it is thought that fluororesins have poor peelability despite having low surface free energy.

[0068] Furthermore, while coating films formed using fluorinated silane coupling agents, such as those described in Patent Document 2, are considered to have excellent peelability in their initial state, their UV resistance is poor, and therefore, their peelability tends to deteriorate after UV exposure. In fluorinated silane coupling agents, the perfluoromethyl group, which has the lowest surface free energy among the functional groups, is located at the terminal, resulting in excellent peelability. However, general fluorinated silane coupling agents have a C-Si bond in part of the main chain. Since the dissociation wavelength calculated from the bond energy of C-Si is approximately 390 nm, they decompose easily with light at a wavelength of 360 nm, thus reducing UV resistance. It is also thought that UV resistance decreases when a functional group that decomposes with light at a wavelength of 360 nm, such as a C-O-C structure (ether bond), is present in part of the main chain.

[0069] In contrast, the present invention provides a coating film having a silicone layer containing a silicone polymer (excluding silicone oil) that substantially does not contain functional groups having fluorine atoms, thereby exhibiting excellent ease of peeling in the initial state. As mentioned above, silicone polymers contain a main chain made of siloxane bonds (Si-O bonds) and are highly flexible. Furthermore, they can adopt a characteristic helical structure in which the Si-O bonds face inward and the organic functional groups face outward, allowing for easy movement of molecular chains and relaxation of stress at the interface. Thus, the silicone polymer's excellent flexibility and deformability allow it to fully exhibit its ease of peeling without hindering the ease of peeling caused by its low surface free energy, thereby improving ease of peeling in the initial state.

[0070] Furthermore, the present invention maintains its peelability even after UV exposure, demonstrating excellent UV resistance. The energy of the siloxane bond, which is the main chain of the silicone polymer, is very high at approximately 452 kJ / mol. This is greater than the energy of light with a wavelength of 360 nm (approximately 332 kJ / mol), so it does not degrade when exposed to light in the wavelength range of i-line (wavelength 365 nm) or ultraviolet A (UVA) rays, for example, when exposing solder resist in an exposure apparatus.

[0071] Furthermore, since the present invention uses an aluminum member having a porous type anodic oxide film, the coating film including the silicone layer formed on its surface can be formed by allowing it to penetrate the pores of the anodic oxide film. This improves the adhesion between the anodic oxide film and the silicone layer, thereby improving the ease of peeling and UV resistance of the silicone layer.

[0072] Preferred embodiments of the present invention will be specifically described below based on examples and comparative examples, but the present invention shall not be construed as being limited thereto.

[0073] <Examples 1-16> [1. Sample Preparation] [Preparation of Base Material] An aluminum material measuring 3.0 mm x 50 mm x 50 mm was cut from a 3.0 mm thick plate made of aluminum alloy (JIS A5052-H34).

[0074] Next, the cut aluminum material was subjected to the following pretreatment. First, the aluminum material was immersed in a 30 wt% nitric acid aqueous solution at room temperature (20°C) for 3 minutes, then washed with pure water. Next, it was immersed in a 5 wt% sodium hydroxide aqueous solution at 50°C for 3 minutes, then washed with pure water. Finally, it was immersed in a 30 wt% nitric acid aqueous solution at room temperature (20°C) for 3 minutes, then washed with pure water.

[0075] (Surface roughening treatment) (Example 8 only) A portion of the pre-treated aluminum material obtained was subjected to a surface roughening treatment by immersing it in an aqueous solution containing 40 g / L of ammonium hydrogen fluoride at a treatment temperature of 34°C for 3 minutes, followed by washing with pure water.

[0076] [Anodizing Treatment] The pre-treated aluminum material obtained, or the aluminum material that has undergone the roughening treatment described above, was subjected to anodizing treatment using the electrolyte shown below and under the treatment conditions shown below to form an anodic oxide film on the surface of the aluminum material.

[0077] A sulfuric acid aqueous solution with a concentration of 180 g / L (sulfuric acid electrolyte) was used as the electrolyte. The treatment conditions were a bath temperature of 18°C ​​and a current density of 15 mA / cm². ２ Anodizing treatment was performed under constant conditions until the film thickness shown in Table 1 was obtained.

[0078] [Sealing Treatment (Partial Sealing Treatment)] Anodized aluminum material was sealed (partially sealed) with a nickel acetate-based sealing material at a temperature of 90°C for the time shown in Table 1 to obtain an aluminum component.

[0079] [Silicone Coating (Film Formation Treatment)] A portion of the aluminum material that underwent the sealing treatment was sprayed using an air spray gun (ANESTIWATA W-101, manufactured by Iwata) at a draw pressure of 0.2 MPa until the thickness shown in Table 1 was obtained. The silicone polymers used were silicone elastomers (HC 2000, HC 2100), silicone resin (1-2577, Pelgan Z) (all manufactured by Dow-Toray), or silicone resin (KR-300, manufactured by Shin-Etsu Chemical Co., Ltd.), respectively. The spray was then left at room temperature (25°C) for 15 minutes, and then dried at 60°C for 60 minutes to obtain an aluminum member (hereinafter referred to as silicone coated material) with a silicone coating (i.e., a coating film having a silicone layer) as shown in Table 1.

[0080] <Comparative Example 1> [Fluorine-based coupling agent coating] The aluminum material that underwent the sealing treatment in Example 1 was modified as follows. Specifically, a fluorine-based coupling agent (FG-5093) manufactured by Fluorotechnology, as shown in Table 1, was used and sprayed using an air spray gun (ANESTIWATA W-101 manufactured by Iwata) at a draw pressure of 0.2 MPa until the thickness shown in Table 1 was obtained. Then it was left at room temperature (25°C) for 15 minutes, and then dried at 90°C for 60 minutes to obtain an aluminum member coated with the fluorine-based coupling agent shown in Table 1 (hereinafter referred to as fluorine-based coupling agent coated material).

[0081] <Comparative Example 2> [Fluorine Coating] The aluminum material that underwent the sealing treatment in Example 1 was modified as follows. Specifically, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) based paint (Daikin Neoflon AD-2CRER) was used as the fluororesin shown in Table 1, and it was sprayed using an air spray gun (Iwata ANESTIWATA W-101) at a draw pressure of 0.2 MPa until the thickness shown in Table 1 was obtained. Then it was left at room temperature (25°C) for 15 minutes, then dried at 100°C for 15 minutes, and then sintered at 380°C for 15 minutes to obtain the fluorine-coated aluminum material (hereinafter referred to as fluorine-coated material) shown in Table 1.

[0082] [2. Evaluation Method] [Measurement of Anodized Film Thickness] The thickness of the anodized film on the sealed aluminum material was measured using a film thickness gauge (Fischer Instruments ISOSCOPE FMP10). The results are shown in Table 1.

[0083] [Measurement of Conductivity and Impedance] For the sealed aluminum material, the conductivity was measured using a Fischer ANOTEST (YMP30-S) according to the following evaluation procedure and measurement conditions, with reference to JIS H 8683-3. The impedance was calculated from the reciprocal of the measured conductivity value. The results are shown in Table 1. In Table 1, "E+04" is "×10 ４ This indicates that "E+05" is "×10 ５ This indicates ".

[0084] ≪Evaluation Procedure≫ (1) Attach the cell to the sealed aluminum material. (2) Pour the test solution (35 g / L potassium sulfate) into the cell. (3) Leave for 30 minutes until the test solution permeates the sample. (4) Connect the earth plug to the sample. (5) Immerse the electrode probe in the test solution. (6) Measure the conductivity and impedance using a Fischer ANOTEST (YMP30-S). ≪Measurement Conditions≫ ・Measuring cell diameter: φ13 mm ・Measuring area: 133 mm ２ ・Measurement temperature: 24℃ ・Measurement frequency: 1kHz

[0085] [FT-IR Measurement] The IR spectrum of the silicone coating material was measured using the ATR method with a Fourier transform infrared spectrophotometer (Agilent Cary660 FTIR). Furthermore, the obtained IR spectrum and the IR spectrum of the standard sample PDMS were compared using the Si-CH₂ method. ３ The intensity of the peak and the Si-O-Si (siloxane) peak were compared in the aforementioned Si-CH ３ The Si-O-Si intensity ratio was measured. Furthermore, the Si-O-Si wavenumber shift was measured by comparing the peak positions of the Si-O-Si. The results are shown in Table 1.

[0086] [Measurement of Silicone Coating and Fluorine Coating Thickness] The thickness of the coated areas of the silicone coating material and the fluorine coating material was measured using a film thickness gauge (Fischer Instruments ISOSCOPE FMP10). The results are shown in Table 1.

[0087] [Film Thickness Measurement of Fluorine-Based Coupling Agent Coated Materials] For fluorine-based coupling agent coated materials, the film thickness of the coated area was calculated from cross-sectional images taken using a transmission electron microscope (Thermo Fisher Scientific Talos F200X). The results are shown in Table 1.

[0088] [Surface Roughness Measurement] Surface roughness was calculated as Ra using a surface roughness meter (Mitutoyo SUFTEST SJ-210) after various coatings. The results are shown in Table 2.

[0089] [Post-Painting Appearance Assessment] The post-painting appearance assessment involved visually inspecting the appearance after each type of coating. A circle (○) was used if no cracks were present, and a cross (×) was used if cracks were observed. The results are shown in Table 2.

[0090] [Exposure Rate] The exposure rate was calculated from SEM images (backscattered electron images) taken at 100x magnification using a scanning electron microscope (SEM, JEOL JSM-7200F) after various silicone coatings. For SEM image analysis, binarized images were obtained using ImageJ (free image analysis software developed by the National Institutes of Health (NIH)), and the area ratios of each element, Si and Al, were calculated. Specifically, after importing the SEM image file into the software, it was converted to 8-bit, the processing range was selected and cropped, the threshold was set to Auto (Imagination-Adjust-Trehold-Auto push was selected), the measurement conditions were set (Analyze-SetMeasurements selected Area and Limit to threshold), and the area ratio was measured (Analyze-AnalyzeParticles selected Outlines in Show, and Display results, Clear results and Summarize were selected). The results are shown in Table 2. The obtained binarized image is shown in Figure 6. Furthermore, Figure 7 shows a graph showing the results of Al exposure rate and peel strength (initial tape peel strength) for initial peel evaluation.

[0091] [X-ray fluorescence intensity measurement] The X-ray fluorescence intensity was measured after various coatings using an X-ray fluorescence analyzer (Rigaku ZSXPrimus IV) with an analysis diameter of φ10 mm. The X-ray intensity value (counts) (kcps) for Si was obtained by X-ray fluorescence analysis. The content (mass%) of F was calculated from the X-ray fluorescence intensity values ​​measured for all elements using the fundamental parameter method (FP method). The results are shown in Table 2.

[0092] [Initial Peeling Evaluation] After applying each coating, peeling was evaluated using the following procedure (1) to (5), referring to JIS Z 0237. Procedures (1) to (4) were performed on 200 measurement points, and (5) was performed on the measured value at each of the 200 measurement points. The criteria for determining peeling strength are A (≤0.50): excellent, B (0.51 to 2.50): good, C (2.51 to 4.00): fair, D (>4.01): bad. The results are shown in Table 2. <<Evaluation Procedure>> (1) Wipe each coating material vigorously three times with isopropanol (IPA). (2) Attach Scotch filament tape (3M No. 898) to each coating material. (3) The tape is pressed twice in the same direction using a manual crimping device (IMADA APR-97-2K peel test crimping roller (2kg)). (4) The tape is pulled at 300 mm / min using a digital force gauge (IMADA ZTS-5N) to measure the peel strength of the tape. (5) After extracting values ​​of 0N or greater from the peel strength values ​​of the tape at each measurement point, the average value is calculated and this average value is taken as the peel strength value.

[0093] [Repeated Peeling Evaluation] After applying each coating, peeling evaluation was performed according to the following procedures (1) to (9), referring to JIS Z 0237. Procedures (1) to (8) were performed on 200 measurement points, and procedure (9) was performed on the measured values ​​at each of the 200 measurement points. The criteria for determining peeling strength are A (≤0.50): excellent, B (0.51 to 2.50): good, C (2.51 to 4.00): fair, D (>4.01): bad. The results are shown in Table 2. <<Evaluation Procedure>> (1) Wipe each coating material vigorously three times with IPA. (2) Attach Scotch filament tape (3M No. 898) to each coating material. (3) Press twice in the same direction with a manual pressing device (IMADA APR-97-2K peeling test pressing roller (2kg)). (4) Manually peel off the tape. (5) Return to (2) and repeat (2) to (4) 1000 times. (6) Apply Scotch filament tape (3M No. 898) to the various coating materials. (7) Press twice in the same direction with a manual crimping device (2 kg). (8) Measure the peel strength of the tape by pulling the tape at 300 mm / min using a digital force gauge (IMADA ZTS-5N). (9) After extracting values ​​of 0 N or greater from the peel strength values ​​of the tape at each measurement point, calculate the average value and use this average value as the peel strength value.

[0094] [UV Exposure Peeling Evaluation] After applying various coatings, UV irradiation was performed for 3 months using a UV irradiation device (Micro-Square UVA 45x90 (wavelength 360nm)) (cumulative irradiation energy approximately 2,333 kJ / cm²). ２), the peel strength was evaluated using the following procedure (1) to (5). Procedures (1) to (4) were performed for 200 measurement points, and (5) was performed on the measured value at each of the 200 measurement points. The criteria for determining peel strength are A (≤0.50): excellent, B (0.51 to 2.50): good, C (2.51 to 4.00): fair, D (>4.01): bad. The results are shown in Table 2. <<Evaluation Procedure>> (1) Wipe each coating material vigorously three times with IPA. (2) Attach Scotch filament tape (3M No. 898) to each coating material. (3) Press twice in the same direction with a manual pressing device (IMADA APR-97-2K peel test pressing roller (2kg)). (4) The tape was pulled at 300 mm / min using a digital force gauge (IMADA ZTS-5N) to measure the peel strength of the tape. (5) After extracting values ​​of 0N or greater from the peel strength values ​​of the tape at each measurement point, the average value was calculated and this average value was taken as the peel strength value.

[0095]

[0096]

[0097] [3. Discussion] As can be seen from the results above, in Examples 1 to 16, which have a coating film having a porous type anodic oxide film on the substrate surface and a silicone layer containing a silicone polymer that substantially does not contain functional groups having fluorine atoms on the surface of the anodic oxide film, the initial peel evaluation and the peel evaluation after UV exposure were rated C (acceptable) or higher, confirming that they have easy peeling and UV resistance. ３ In Examples 1 to 15, where the Si-O-Si strength ratio was 0.9 or higher, the repeated peeling evaluation was rated C (acceptable) or higher, in addition to the initial peeling evaluation and the peeling evaluation after UV exposure, confirming improved resistance to repeated peeling. Furthermore, a methyl-based silicone elastomer was used as the silicone layer, and Si-CH ３In Examples 1 to 13, where the Si-O-Si strength ratio was 1.0 or higher, the results tended to be excellent in all aspects of the evaluation: initial peeling, repeated peeling, and peeling after UV exposure. In Examples 1 to 9, by setting the silicone layer thickness to 0.6 μm or higher, the Al exposure rate was kept low, resulting in an A (excellent) rating in all aspects of the evaluation: initial peeling, repeated peeling, and peeling after UV exposure. In Examples 1 to 9, setting the sealing time to 20 minutes or less also tended to result in excellent performance in the repeated peeling evaluation. Furthermore, in Examples 1 to 10 and 12 to 16, it was confirmed that the occurrence of cracks after coating was suppressed by setting the anodic oxide film thickness to 12 μm or less. In particular, Examples 1 to 9, in which a methyl-based silicone elastomer was used as the silicone layer and its thickness was adjusted to keep the Al exposure rate relatively low, and the anodic oxide film thickness and sealing treatment (sealing time) were adjusted, all peeling evaluations were A (excellent), showing remarkable excellence. Furthermore, X-ray fluorescence analysis of Examples 1 to 16 revealed that no "F" (fluorine) was detected in the silicone layer, confirming that the silicone layer contains a silicone polymer that substantially does not contain functional groups with fluorine atoms. In addition, as shown in Figure 7, it was confirmed that a low Al exposure rate, or in other words a high Si exposure rate, tends to be superior in initial peel evaluation.

[0098] In contrast, Comparative Example 1, in which a fluorine coating with a fluorine-based coupling agent was used instead of the silicone layer according to the present invention, showed excellent initial peel evaluation but poor peel evaluation after UV exposure. From this, it can be inferred that the fluorine-based coupling agent coating used in Comparative Example 1, as mentioned above, has a C-O-C structure (ether bond) in part of its main chain, and therefore easily decomposes in UV light, preventing it from exhibiting sufficient functionality (easy peelability).

[0099] Furthermore, in Comparative Example 2, where a fluorine coating was used instead of the silicone layer according to the present invention, the peel evaluation was inferior both in the initial peel evaluation and the peel evaluation after UV exposure. From this, it is presumed that the fluorine coating used in Comparative Example 2, compared to the silicone polymer, has higher rigidity of the main chain due to the fluororesin, making surface deformation less likely, which leads to localized stress concentration and inhibits easy peeling. It is also presumed that compared to the silicone polymer, the movement of molecular chains in the fluororesin is restricted, making stress relaxation less likely, thus inhibiting easy peeling.

[0100] 1, 2… Exposure stage plate 10… Aluminum component 11… Substrate 12… Anodized coating 20, 20a, 20b… Coating film 21… Silicone layer 22… Primer layer

Claims

1. A stage plate for use in the solder resist process of an exposure apparatus used in the manufacture of semiconductor package substrates and printed circuit boards, comprising: an aluminum member having a substrate made of aluminum or an aluminum alloy and a porous type anodic oxide film formed on the surface of the substrate; and a coating film having a silicone layer formed on the surface of the anodic oxide film of the aluminum member and containing a silicone polymer (excluding silicone oil) that substantially does not contain functional groups having fluorine atoms.

2. The silicone layer is Si-CH ３ The stage plate for an exposure apparatus according to claim 1, characterized in that the Si-O-Si intensity ratio is 1 or more.

3. The silicone layer has a Si-O-Si wavenumber shift of -5 cm. －１ Above, 20cm －１ The stage plate for an exposure apparatus according to claim 1, characterized in that it is as follows:

4. The stage plate for an exposure apparatus according to claim 1, characterized in that the silicone layer comprises a methyl-based silicone elastomer.

5. The stage plate for exposure apparatus according to claim 1, characterized in that the anodic oxide film is semi-sealed.

6. The stage plate for exposure apparatus according to claim 1, characterized in that the anodic oxide film satisfies at least one of the following conditions 1 and 2: (Condition 1) Impedance is 1.0 × 10 ５ (Condition 2) The conductivity must be less than Ω. (Condition 2) The conductivity must be greater than 10 μS.

7. The stage plate for an exposure apparatus according to claim 1, characterized in that the coating film has a primer layer containing an alkyl silicate, and the primer layer is formed between the anodic oxide film and the silicone layer.

8. The stage plate for an exposure apparatus according to claim 1, characterized in that the anodic oxide film has a thickness of 0.1 μm or more and less than 15 μm.

9. The stage plate for an exposure apparatus according to claim 1, characterized in that the silicone layer has a film thickness greater than 0.1 μm and 300 μm or less.

10. The exposure apparatus stage plate according to claim 1, characterized in that the Si intensity of fluorescent X-rays on the surface of the exposure apparatus stage plate is 20 kcps or more.

11. The stage plate for exposure apparatus according to claim 1, characterized in that the aluminum exposure rate on the surface of the stage plate for exposure apparatus is 50% or less.

12. Integrated irradiation energy of 2,333 kJ / cm² using ultraviolet light with a wavelength of 360 nm. ２ The stage plate for an exposure apparatus according to claim 1, characterized in that the peel strength measured by a tape peel test after exposure to ultraviolet light due to irradiation is 4 N / cm or less.

13. A method for manufacturing a stage plate used in the solder resist process of an exposure apparatus used in the manufacture of semiconductor package substrates and printed circuit boards, comprising: an aluminum member having a substrate made of aluminum or an aluminum alloy and a porous type anodic oxide film formed on the surface of the substrate; and a coating film having a silicone layer formed on the surface of the anodic oxide film of the aluminum member and containing a silicone polymer (excluding silicone oil) that substantially does not contain functional groups having fluorine atoms, comprising: an anodizing step of manufacturing the aluminum member by performing an anodizing treatment to form the anodic oxide film on the surface of the substrate; and a film forming step of forming the coating film by performing a film forming treatment to form the silicone layer on the surface of the anodic oxide film of the aluminum member.

14. The method for manufacturing a stage plate for an exposure apparatus according to claim 13, characterized in that, after forming the anodic oxide film in the anodic oxidation step, a semi-sealing treatment is performed to semi-seal the anodic oxide film on the substrate.

15. The method for manufacturing a stage plate for an exposure apparatus according to claim 13, characterized in that, in the film formation step, a primer layer formation treatment is performed on the anodic oxide film to form a primer layer containing an alkyl silicate.

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