JP5578513B2 - Method for producing metal microstructure and method for producing resin molding - Google Patents

Description

  The present invention relates to a metal microstructure used for a wiring board having a fine wiring pattern, a plasmon sensor, a manufacturing method thereof, and a manufacturing method of a resin molded product.

Conventionally, a metal microstructure having a fine wiring pattern on the order of μm or nm that can be used for a wiring board, a plasmon sensor, or the like is expected, but has not yet been realized.
As one method for forming a fine wiring pattern made of a metal of μm order or nm order on a substrate such as glass or resin, transfer is performed using a mold (original) corresponding to the fine pattern to be formed. There is a way. For example, a conductive film is formed on a glass substrate, a predetermined pattern is formed on the conductive film with a photoresist, a plating film is formed on a portion where the conductive film is exposed, and a base film is further formed on the plating film. A method of transferring the plating film by bonding the films is disclosed (see Patent Document 1).
However, with such a method, it is difficult to produce a wiring board having a fine pattern on the order of μm or nm.

Japanese Patent Laid-Open No. 2004-63694

  The present invention forms a metal film having no cracks on the concavo-convex pattern of the matrix, suppresses damage to the concavo-convex pattern of the matrix, and transfers the metal film reflecting the concavo-convex pattern to a support member to form a metal microstructure. The main objective is to provide a method that can be manufactured.

In order to achieve the above object, the following invention is provided.
<1> height of the convex portions using a mold having an uneven pattern formed thereon is less than 1μm to the surface, the uneven pattern is formed the surface of the mother mold, represented by the following general formula (I) Forming a film of a silane coupling agent;
Forming a metal film on the silane coupling agent film;
Integrating the metal film and a support member for supporting the metal film;
A metal microstructure having the metal film reflecting the concave-convex pattern of the mother mold by peeling the metal film together with the support member, and the support member integrated with the metal film. And obtaining
The manufacturing method of the metal microstructure characterized by including.


(In the formula (I), n represents an integer of 8, 10, 12, or 14, m represents an integer of 3 or 4, and X, Y, and Z each independently represent a methoxy group, an ethoxy group, It is a hydrolyzable group representing a propoxy group, an isopropoxy group, or a halogen atom.)
<2> The method for producing a metal microstructure according to <1>, wherein in the step of forming the metal film, the metal film is formed by a vapor deposition method.
<3> The metal according to <1>, wherein in the step of forming the metal film, the metal film is formed by applying a metal ink on the silane coupling agent film and then heating. A manufacturing method of a fine structure.
<4> In the step of integrating the metal film and the support member, a resin film is used as the support member, and the metal film is heated and bonded in a state where the resin film is pressed against the metal film. The method for producing a metal microstructure according to any one of <1> to <3>, wherein the support member and the support member are integrated.
<5> In the step of integrating said supporting member and said metal film, after forming the resin layer of uncured by applying a thermosetting resin or a photocurable resin to said metal film, heating or UV irradiation The method for producing a metal microstructure according to any one of <1> to <3>, wherein the support member is formed by curing the resin layer.
<6> In the step of integrating said supporting member and the metal film, the metal film is imparted a thermosetting resin or a photocurable resin is provided a resin layer of uncured, resin film to the resin layer <1> to <3>, wherein the support member including the cured resin layer and the resin film is obtained by curing the resin layer by heating or ultraviolet irradiation. The manufacturing method of the metal microstructure in any one of.
<7> In the step of forming a film of the silane coupling agent, a matrix whose convex portions of the concavo-convex pattern correspond to a wiring pattern is used as the matrix.
In the step of integrating the metal film and the support member, a sheet member having an adhesive layer on one side is used as the support member, and the adhesive layer of the sheet member is brought into pressure contact with the metal film, whereby the uneven pattern Adhering a part of the metal film corresponding to the convex portion of the adhesive layer,
<1> to <3>, wherein in the step of obtaining the metal microstructure, a wiring substrate is manufactured as the metal microstructure by peeling a part of the metal film together with the sheet member. The manufacturing method of the metal microstructure in any one.
<8> The method according to <1> to <7>, further including a step of preparing a matrix having the uneven pattern formed on a surface as a pre-step of the step of forming the silane coupling agent film. The manufacturing method of the metal microstructure in any one.
<9> In the step of forming a film of the silane coupling agent, after the liquid containing the silane coupling agent is applied to the surface of the mother mold on which the concave / convex pattern is formed, heat treatment is performed, and the heat treatment is performed. The method for producing a metal microstructure according to any one of <1> to <8>, wherein the surface of the matrix to which the liquid containing the silane coupling agent is applied is rinsed before or after the step .
<10> the method for producing a aspect ratio of the convex portion of the concavo-convex pattern of the matrix is characterized der Rukoto more <1> to the metal microstructure according to any one of <9>.
< 11 >< 1 > to < 10 > The metal microstructure manufactured by the method for manufacturing a metal microstructure according to any one of the above is used as a mold, and the general formula is applied to the metal film of the metal microstructure. Forming a film of the silane coupling agent represented by (I);
After applying a thermosetting resin or a photocurable resin on the silane coupling agent film, heating or irradiating with ultraviolet rays to cure the applied resin;
A step of obtaining a resin molding having a concavo-convex pattern by peeling the cured resin from the metal film;
The manufacturing method of the resin molding characterized by including.

  According to the present invention, a metal film having no cracks is formed on the concavo-convex pattern of the matrix, and the metal film reflecting the concavo-convex pattern is transferred to the support member while suppressing the breakage of the concavo-convex pattern of the matrix. A method for producing a body, a metal microstructure, and a method for producing a resin molded product are provided.

It is a figure which shows an example of the process of manufacturing a metal microstructure by this invention. It is a schematic block diagram which shows an example of the ECR type ion beam processing apparatus used for preparation of the mother die which has a fine concavo-convex pattern. It is the SEM image which observed the surface which changed the processing time for the glassy carbon substrate by ECR. It is a NMR spectrum of 10F2P3S3M. It is IR spectrum of 10F2P3S3M. It is a mass spectrum of 10F2P3S3M. It is a graph which shows the relationship between the heating temperature and contact angle of each silane coupling agent. 2 is an SEM image showing the surface of an Au film formed by vacuum deposition in Example 1. FIG. 2 is an SEM image showing an Au film transferred to a PET substrate in Example 1. FIG. It is a SEM image which observed Au vapor deposition film in Example 2, (A) shows Au film on a mold before transfer, and (B) shows Au film on a PET substrate after transfer. It is a SEM image which observed the transfer state of the pattern of Au film in Example 2, (A) shows the state which transferred Au film to the PET substrate, and (B) shows the mold which provided Au vapor deposition film on the uneven pattern. . It is a SEM image which observed Au vapor deposition film in comparative example 1, (A) shows Au film on a mold before transfer, and (B) shows Au film on a PET substrate after transfer. It is a SEM image which observed the transfer state of the pattern of Au film in comparative example 1, (A) shows the state which transferred the Au film to the PET substrate, and (B) shows the mold which provided the Au vapor deposition film on the uneven pattern. . 6 is an SEM image showing a concavo-convex pattern formed on a glassy carbon substrate in Example 3. FIG. 10 is a SEM image showing an Au film transferred to the surface of a PET substrate in Example 3. FIG. 16 is an SEM image showing a resin layer in which the pattern of the Au film in FIG. 6 is an SEM image showing the surface of an Au film formed by vacuum deposition in Comparative Example 2.

Hereinafter, the present invention will be specifically described with reference to the accompanying drawings.
According to the verification results of the present inventors, when a fine concavo-convex pattern having a height of several μm or less, particularly in the order of nm, and having a high aspect ratio is densely formed on the master mold, the master pattern transfer pattern It was confirmed that various problems occur even when a metal film is formed by vapor deposition after a release agent is applied to the surface in advance, and then peeling is attempted. Specifically, the existing mold release agent has low heat resistance and decomposes at a high temperature when the metal film is vacuum-deposited. Therefore, the metal film cannot be formed, and the metal film cannot be transferred to another member. Even if the metal film is transferred to another member, the concave / convex pattern of the mother mold is not faithfully reflected (that is, the resolution is poor), cracks occur in the metal film, or if the metal film is forcibly removed, There arises a problem that the uneven pattern is destroyed and cannot be used repeatedly.

  The present inventors have previously used glassy carbon as a base material, and when subjected to ion beam processing by ECR (electron cycloton resonance), needles, cones, pyramids, etc. An anti-reflection structure comprising a fine projection group having a shape with a diameter reduced toward the surface and having a fine concavo-convex pattern with a reflectance of 1% or less was developed, and a patent application was filed first (JP 2008- 233850 publication and WO2008 / 018570 A1 publication). And using the structure in which the concavo-convex pattern is formed as a matrix, the concavo-convex pattern is transferred to another general-purpose transferable material such as a resin or metal, with the aim of giving a good antireflection effect. The research on the transfer technology of fine structure was repeated.

  However, the transfer pattern of the mother die is a pattern in which fine irregularities having a height of less than 1 μm on the order of nm and an aspect ratio of 2 or more are densely formed (in this specification, formed on the mother die). The unevenness to be transferred is also referred to as “unevenness pattern” or “transfer pattern” as appropriate.) When the material to be transferred is a metal film, the unevenness pattern of the matrix is the antireflection layer. Even if it is formed with high accuracy like a structure, it has been difficult to find a method of accurately transferring the pattern and reflecting the unevenness. As a reason for this, an attempt was made to form a release agent film on the concavo-convex pattern, and then to form a metal film by a vacuum deposition method. For example, an optool (known as a general release agent) Since conventional commercial products such as Daikin Kogyo Co., Ltd. and Durasurf 1101Z (Harves Co., Ltd.) do not have characteristics (high temperature heat resistance) that can withstand high temperatures during vacuum deposition, the present inventors Recognized that the above problem could not be solved.

  On the other hand, the present inventors have developed a silane coupling agent represented by the following general formula (I) as a release agent capable of solving the above-mentioned problems, and conducted repeated experiments. As a result, since the silane coupling agent is heat resistant at high temperature, a metal film can be formed by vacuum deposition, and since the water repellency (peelability) is high, the metal film and the matrix can be formed without destroying the concavo-convex pattern. It can be easily peeled off and transferred, and the desired metal microstructure with a metal film that accurately reflects the uneven pattern of the matrix can be produced. It was found that it can be maintained over a period of time.

  In the above formula (I), n represents an integer of 8, 10, 12, or 14, m represents an integer of 3 or 4, and X, Y, and Z each independently represent a methoxy group, an ethoxy group, It is a hydrolyzable group representing a propoxy group, an isopropoxy group, or a halogen atom. X, Y and Z are preferably all the same, and X, Y and Z are preferably a methoxy group or a chlorine atom in terms of high reactivity with the matrix base material, and surface reaction Chlorine atoms are particularly preferred from the standpoint of reactivity to the substrate surface, except that hydrochloric acid is sometimes generated.

FIG. 7 shows that in formula (I), X, Y and Z are all methoxy groups, and the perfluoroalkyl chain (F (CF ₂ ) _n ) is F (CF ₂ ) ₁₀ (10F2P3S3M), F (CF ₂ ) The relationship between temperature and contact angle verified by the present inventors for ₈ (8F2P3S3M) and F (CF ₂ ) ₆ (6F2P3S3M) is shown. The heating time at each temperature is 120 minutes. In this specification, a compound represented by the general formula (I), for example may be referred to as "10F2P3S3M" is "10F" is the n of F _{(CF 2) n} 10, "2P" biphenylene The group “3S” means a compound in which _m of (CH ₂ ) _m Si is 3, and “3M” means three methoxy groups, that is, X, Y and Z are all methoxy groups.

  As can be seen from FIG. 7, according to the verification results of the present inventors, those having n of 6 in the general formula (I) show a contact angle of about 100 degrees at 200 ° C., but higher temperatures. Then, the contact angle decreases rapidly, and the heat resistance is not sufficient. In addition, when n is 4 or less, the contact angle and the heat resistance are further reduced. Therefore, when n is 6 or less, it is not sufficient for application to transfer of a concavo-convex pattern in the case of having a high temperature process. Was confirmed.

On the other hand, the silane coupling agent represented by the general formula (I) used in the present invention and having n of 8 or more has low surface energy, exhibits a contact angle of 100 degrees or more with respect to water, and is about 300 ° C. Or a silane coupling agent having n or more and 10 or more heat resistance is characterized by having extremely high heat resistance even at a high temperature of about 400 ° C.
In the present invention, it was possible to produce a metal microstructure by transferring a metal film at a high resolution because the present inventors made it possible to produce a matrix having a concavo-convex pattern and high-temperature heat resistance. This is because the silane coupling agent was developed.

Although the reason why the silane coupling agent used in the present invention is extremely effective for transferring a fine uneven pattern is not theoretically clear, the following may be considered.
In the transfer of fine concavo-convex patterns, if the space between the fine projections is filled with a release agent, the subsequent transfer becomes impossible, so it is as thin as possible and the same thickness as possible on the transfer pattern It is considered essential to form a release agent layer. Since the silane coupling agent used in the present invention is presumed to easily form a monomolecular layer having a thickness of about 0.25 nm between the base material constituting the base (the surface of the concave and convex pattern of the base). Since the above conditions are satisfied and the surface free energy is small, it is effective for transferring the concavo-convex pattern that it has high releasability, is thermally stable and has little damage to various physical stimuli. it is conceivable that.

The silane coupling agent used in the present invention has high water resistance because it has a water- and oil-repellent fluorine chain, and forms a stable bond with the base material of the matrix. In addition to the bonding, the release agent may cause the silane molecules to come close to each other due to the interaction of the biphenyl ring and the film of the silane coupling agent becomes dense, and the CF ₃ on the outermost surface thereby becomes dense. It is guessed that it will be a factor that brings high performance as.

FIG. 1 is a diagram showing an example of steps of a method for producing a metal microstructure according to the present invention.
The method for producing a metal microstructure according to the present invention includes:
A step of forming a film of a silane coupling agent represented by the following general formula (I) on the surface of the master mold on which the concave / convex pattern is formed, using a master block having a concave / convex pattern formed on the surface;
Forming a metal film on the silane coupling agent film;
Integrating the metal film and a support member for supporting the metal film;
A metal microstructure having the metal film reflecting the concave-convex pattern of the mother mold by peeling the metal film together with the support member, and the support member integrated with the metal film. And obtaining
including.

  In the formula (I), n represents an integer of 8, 10, 12, or 14, m represents an integer of 3 or 4, and X, Y, and Z each independently represent a methoxy group, an ethoxy group, or a propoxy group. A hydrolyzable group representing a group, an isopropoxy group or a halogen atom.

  In the step of forming a film of the silane coupling agent, heat treatment may be performed after applying a liquid containing the silane coupling agent to the surface of the matrix on which the uneven pattern (transfer pattern) is formed. The heat treatment may not be performed. Moreover, it is preferable to perform the rinse before or after the heat treatment as necessary.

The purpose of the heat treatment is to promote the siloxane bond and the bond of the silane coupling agent to the substrate surface, and to bring the fluorine chain into a stable state. In the general formula (I), the case where X, Y, and Z are all methoxy groups will be described as an example. When the silane coupling agent is applied to the substrate surface in the air, the moisture in the air acts to cause the methoxy groups. Becomes an OH group, methanol is released, and when it becomes an OH group, it reacts with a methoxy group of another molecule to form a siloxane bond. Moreover, it reacts with the OH group or adsorbed water on the surface of the substrate to produce a relatively weak bond due to a hydrogen bond. In order to promote the condensation of OH groups and change the bond of Si—O—Si or Si—O— substrate to a strong covalent bond by aging by heat for such various bond formations. A strong bond is formed on the surface. In addition, these objects can also be achieved by putting a time after application without performing heat treatment.
When the siloxane bond is completed, it is considered that the intermolecular distance becomes small and the surface of the base material is covered with the fluorine-based silane coupling agent so that the release property is improved.

  The main purpose of the heat treatment after the release agent is applied is to change the hydrogen bond to a covalent bond to remove water or methanol. In the case of a general mold release agent, the heat treatment is performed at 130 to 150 ° C. According to the experiments by the present inventors, in the case of the silane coupling agent represented by the general formula (I), preferably 130 ° C. Hereinafter, it is more preferable that the heat treatment is performed at 80 to 100 ° C. or the heat treatment is not performed.

On the other hand, the purpose of rinsing is simply physical adsorption on the outside of the silane coupling agent that is firmly bonded to the substrate surface by covalent bond, the bonding direction is disjoint, and the fluorine chain is not necessarily directed to the air side, the surface free energy It is to wash away an extra silane coupling agent that hinders the decrease in the temperature.
As the rinsing liquid, an organic solvent, water, or the like can be used. For example, a fluorine-based solvent such as HFE-7100 (manufactured by Sumitomo 3M) can be used. After rinsing with a fluorine solvent, the coupling effect can be improved by further rinsing with water and changing the methoxy group to an OH group.
Hereinafter, each process and member will be described more specifically.

<Matrix>
A mother die 10 having a concavo-convex pattern formed on the surface is prepared.
The material, shape, size, and concavo-convex pattern 14 of the base material 12 serving as the main body of the mother die 10 are not particularly limited, and may be selected according to the material to be transferred, the use, and the like.
Examples of the material (mold material) of the base material 12 include glassy carbon (glassy carbon) from the viewpoints of formability of the concave / convex pattern 14, mechanical strength as the mother die 10, heat resistance, and film formability of a metal film. ), Silicon, SOG, quartz, ceramics, or nickel, especially nickel plates produced by plating, metals such as tantalum, or oxides of metals such as chromium, nickel, alumina, titania, etc. An inflexible material is preferably used.
Further, the shape of the base material is usually a sheet-like flat plate shape, but it can also be used in a roll shape, and further, a thin film flat plate shape provided with an uneven pattern is wound around a roll, It can also be used for a toe roll transfer system.

The uneven pattern 14 on the surface of the substrate 12 may be formed according to the purpose. For example, the desired uneven pattern 14 may be formed on the surface of the substrate 12 by lithography, electron beam processing, ion beam processing, or the like.
For example, a desired wiring pattern can be formed on the surface (one surface) of the base material 12 such as a silicon substrate by lithography (photolithography, electron beam lithography, etc.) and etching. Further, after baking SOG (Spin on Glass) on a flat substrate such as a silicon substrate, it can be formed into a predetermined uneven pattern.

  In addition, when a fine projection group of nm order is formed on the surface of the base material 12 to impart an antireflection effect to the metal film 18 or to increase the surface area of the metal film 18, for example, glassy carbon or the like A fine projection group on the order of nm may be formed on the surface (processed surface) of the base material 12 by subjecting the base material 12 to ion beam processing. For example, if ion beam processing by ECR (electron cycloton resonance) is performed on a glassy carbon substrate, the height is less than 1 μm and the aspect ratio is 2 or more, such as needles, cones, pyramids, etc. It is possible to form a pattern including a group of fine protrusions having a shape that decreases in diameter. If the transfer pattern is made up of a projection group having a shape whose diameter is reduced from the root toward the tip (for example, a shape having a sharp tip), the transfer pattern is made of a projection group having a substantially constant diameter such as a columnar shape. This is advantageous in that transfer (peeling) is easy. In ECR processing, the height and pitch P of the protrusions formed on the surface of the substrate can be controlled to some extent by adjusting the processing time, acceleration voltage, and gas flow rate (Japanese Patent Laid-Open No. 2008-233850). reference).

  FIG. 2 schematically shows an example of the configuration of an ECR (Electron Cycloton Resonance) type ion beam processing apparatus (plasma etching apparatus) that can be used for manufacturing a matrix according to the present invention. The ion beam processing apparatus 50 includes a holder 66 for holding the substrate 52, a gas introduction tube 54, a plasma generation chamber 56, an extractor 58, an electromagnet 60, an ion beam extraction electrode 62, a Faraday cup 64, and the like. For example, since the current density decreases at a low acceleration voltage of 500 V or less, the extractor 58 is a grid for extracting ions on the plasma side from the extraction electrode 62 in order to increase the current density. If the extractor 58 is used, even if the acceleration voltage is low, the current density increases and the machining speed can be increased.

  In order to manufacture a matrix using such an ECR type ion beam processing apparatus 50, first, a base material 52 made of glassy carbon (glassy carbon) as a raw material is prepared, and this is set in a holder 66. . The glassy carbon substrate to be used may be plate-like or may have a curved surface on which ion beam processing is performed. Note that the surface to be subjected to ion beam processing is preferably polished. If it is a polished surface, it is a smooth surface before etching, and it is easy to form fine protrusions uniformly by processing.

After the glassy carbon substrate is installed in the apparatus 50, a reactive gas is introduced and a predetermined acceleration voltage is applied to the surface of the substrate 52 to perform ion beam processing.
As the reaction gas, a gas containing oxygen is used, and only oxygen may be used, or a gas in which a CF-based gas such as CF ₄ is mixed with oxygen may be used.

  In this way, by performing ion beam processing on the surface of the base material 52 using the ECR type ion beam processing apparatus 50, a minute projection group (microstructure) having a shape that decreases in diameter toward the tip is formed. Can do. The shape and pitch of the protrusions formed on the surface of the glassy carbon substrate 52 are greatly influenced by the acceleration voltage, processing time, and gas flow rate during ion beam processing. Therefore, the shape and pitch of the protrusions formed on the surface of the substrate can be controlled by controlling at least one of the acceleration voltage, the processing time, and the gas flow rate. In addition, by adjusting the acceleration voltage, processing time, gas flow rate, etc., for example, the shape of the protrusion is not only a needle shape but also a conical shape, a polygonal pyramid shape as a shape having a diameter decreasing toward the tip It is also possible to form fine projection groups such as a truncated cone shape, a polygonal truncated cone shape, and a parabolic shape.

  Further, if the ECR type ion beam processing apparatus 50 is used, even a relatively large surface can be processed in a lump. And according to such a method, the glass-like carbon base material can be surface-processed easily, and the mother die which can exhibit the antireflection effect near non-reflection can be manufactured.

According to the researches of the present inventors, in particular, by applying ECR processing to a glassy carbon substrate with an acceleration voltage of 300 V or more and a processing time of 18 minutes or more, a needle-like shape having a reduced diameter from the root portion to the tip portion or A conical protrusion can be reliably formed, and the reflectance can be reduced to 20% or less. If the acceleration voltage is excessively increased, the protrusions become thin and easily break during transfer. If the processing time is increased, the productivity may be reduced. Therefore, the acceleration voltage is 1000 V or less and the processing time is 30 minutes or less. It is preferable.
In the glassy carbon base material, the surface on which the fine protrusion group having a shape that decreases in diameter toward the tip as described above is reflected by the incident light compared to the case where the protrusion of the columnar body is formed. It is difficult to achieve a higher antireflection effect.

  The fine protrusions 14 having a diameter reduced toward the tip formed on the surface of the mother die 10 according to the present invention have an average height (H) of 200 nm to 3000 nm, more preferably 720 nm to 1370 nm. 14 root diameter, that is, the average maximum diameter is in the range of 50 nm to 300 nm, more preferably 80 nm to 220 nm, and 50 nm to 300 nm, more preferably 120 nm to 220 nm. It was found that a high antireflection effect was exhibited. In particular, if the height of the protrusion is 200 nm or more and is formed with a pitch of 140 nm or less, a non-reflective structure can be obtained.

Furthermore, the present inventors have investigated the relationship between the angle of the protrusion tip and the reflectance. When the protrusions 14 that are tapered from the root portion to the tip portion are formed with a predetermined pitch, the angle (vertical angle) of the tip portion of the protrusion 14 is 2θ and the radius of the root portion (D / 2) Where r is the height and h is the height, tan θ = r / h, so θ = tan ⁻¹ (r / h).
In order to achieve a non-reflective structure, theoretically, the pitch (P) <137 nm and the height (h)> 200 nm of the protrusions are required. Thus, a non-reflective structure is obtained when 2θ <37.8 °. Therefore, when the angle of the tip portion of the protrusion 14 satisfies the above relationship, it is considered that non-reflection or a reflectance close thereto can be achieved. However, if the angle of the tip of the protrusion is too small, it is considered that the protrusion is likely to be broken during transfer, and the reflectivity increases as it approaches a columnar shape with a uniform diameter. Therefore, when the protrusion 14 is needle-shaped or conical, the angle of the tip is preferably 3 ° or more, more preferably 10 ° or more, and particularly preferably 15 ° or more.

  A matrix having a fine projection group having a shape that shrinks toward the tip, such as a needle shape, on the surface of such a glassy carbon substrate has a transfer pattern with an antireflection structure that is nearly nonreflective. It becomes. And since the matrix made from such glassy carbon has extremely high heat resistance and high mechanical strength unlike carbon materials such as graphite, for example, not only resin materials but also quartz glass and metal Such a member having a high melting point can be repeatedly transferred.

  Alternatively, the mother die may be manufactured by plating or vapor-depositing a processed surface of glassy carbon with a metal such as nickel or gold. The mold produced in this manner reflects the uneven pattern formed on the processed surface of the glassy carbon. Therefore, if this matrix is used, the antireflection structure can be indirectly transferred to a member having a relatively low melting point (softening point) such as a film made of a resin material, and an antireflection function close to non-reflection is achieved. The resin film etc. which have can be manufactured.

  Furthermore, the matrix according to the present invention has a shape that has a width and height that is five times or more of the fine protrusions that constitute the antireflection structure on the surface of the glassy carbon substrate, and that is reduced in diameter toward the tip. It is good also as what has the large protrusion which has. In order to form such large protrusions, for example, ion beam processing may be performed in a state where a mask material for forming large protrusions is scattered on the surface of a glassy carbon substrate. As a result, portions other than the mask portion are processed, and the masked portion remains as a large protrusion. As the mask material, for example, a siloxane polymer or the like can be used, and the mask can be scattered at predetermined positions on the glassy carbon substrate by photolithography, electron beam lithography, or the like.

Then, using a matrix having an antireflection structure pattern in which large protrusions are scattered together with fine protrusions such as needles on the surface of the glassy carbon base material, an optical substrate such as quartz glass is used. Can be processed into a surface structure having a micro-order notch (referred to as a microprism array or the like) together with a group of fine nano-order protrusions. If the glass has such a surface structure, an optical member having a higher antireflection effect can be obtained.
As described above, the case where glassy carbon (glassy carbon) is used as the material (mold material) of the base material 12 constituting the mother die 10 has been mainly described. However, the material is not limited to glassy carbon. In this way, silicon, SOG, quartz, ceramics, nickel, particularly metals such as nickel or tantalum produced by plating, and the like can also be used.

<Release agent>
In the present invention, as a release agent, a silane coupling agent having a perfluorobiphenylalkyl chain represented by the following general formula (I) (hereinafter referred to as “silane coupling agent” or “release agent” as appropriate). ) Is used to form the silane coupling agent film 16 on the surface of the mother die 10 on which the concave / convex pattern 14 is formed (FIG. 1A).

(In the formula (I), n represents an integer of 8, 10, 12, or 14, m represents an integer of 3 or 4, and X, Y, and Z each independently represent a methoxy group, an ethoxy group, It is a hydrolyzable group representing a propoxy group, an isopropoxy group, or a halogen atom.)

  The silane coupling agent has a low surface energy, exhibits a contact angle of 100 ° or more with water, and has a heat resistance of about 300 ° C. or more. In particular, a silane coupling agent having n of 10 or more can maintain the value of the contact angle even when exposed to an atmosphere of 350 ° C. or more for 4 hours or more, or 400 ° C. for 10 hours. In other words, this silane coupling agent has excellent heat resistance so that the contact angle of the modified surface is not lowered by the silane coupling agent, and is also excellent in durability, releasability and antifouling property. ing.

  The silane coupling agent represented by the general formula (I) can be produced, for example, by the following method.

4,4′-dibromobiphenyl represented by the following general formula (2)

In a perfluoroalkyl iodide represented by the following general formula (3) and a polar solvent, the reaction is carried out using a copper bronze powder catalyst,
F (CF ₂ ) _n I (3)
(In the formula, n is a positive number of 8 to 14.)
4-perfluoroalkyl-4′-bromobiphenyl represented by the following general formula (4) is synthesized.

Next, the 4-perfluoroalkyl-4′-bromobiphenyl is reacted with an unsaturated alkyl bromide represented by the following general formula (5) in a polar solvent using a CuI catalyst,
_{CH 2 = CH (CH 2)} p -Br (5)
(In the formula, p is a positive number of 1 to 4.)
4-perfluoroalkyl-4′-vinylalkylbiphenyl represented by the following general formula (6) is synthesized.

  Thereafter, the 4-perfluoroalkyl-4′-vinylalkylbiphenyl is reacted with one selected from the following silanes in an organic solvent using a chloroplatinic acid catalyst, and represented by the general formula (I). A silane coupling agent can be produced.

  Silanes: trimethoxysilane, triethoxysilane, tripropylsilane, triisopropylsilane, methyldimethoxysilane, methyldiethoxysilane, methyldipropoxysilane, methyldiisopropoxysilane, trichlorosilane, methyldichlorosilane

  The method for applying the silane coupling agent to the transfer pattern surface of the matrix is not particularly limited. However, in the case of a nano-sized uneven pattern, the pattern is buried if the applied silane coupling agent film is too thick. On the other hand, if the application of the silane coupling agent is insufficient, the release agent may not be sufficiently distributed to the bottom (concave portion) of the uneven pattern (especially one having a high aspect ratio). In order to prevent these problems from occurring, it can be selected from known coating methods such as spray coating, spin coating, dipping, their overcoating, roll coating, screen printing, and vapor deposition.

For example, when the transfer pattern has a fine structure in which the height of the protrusion (convex portion) is less than 1 μm and the aspect ratio is on the order of 2 nm or more, when the silane coupling agent is coated, In order to prevent breakage and apply the pattern surface as uniformly as possible, the silane coupling agent is preferably dissolved in a solvent and applied by spin coating. In the case of a large mold, dipping is preferable. Furthermore, in order to reach the silane coupling agent to the bottom (concave portion) of the mold, it is effective to apply convection or ultrasonic vibration.
The release agent layer may be formed on the entire concavo-convex pattern. Depending on the size and density of the concavo-convex pattern, the use of the transferred pattern, the material of the transferred member, etc. You may form only in a convex part.

Examples of the solvent for dissolving the silane coupling agent include benzene, toluene, xylene, and fluorine-based solvents (for example, HFE-7100, HFE-7200 [(CF ₃ ) ₂ CFCF ₂ —O—CH ₂ CH, manufactured by Sumitomo 3M). ₃ ], fluoropolyether solvents, alternative chlorofluorocarbons, etc.), diethyl ether, tetrahydrofuran, ethyl acetate and the like. It is preferable to use a silane coupling agent at a concentration (wt%) of 0.01 to 10%, and further 0.1 to 1.0% in a solvent selected from these.

  Further, if the film 16 of the silane coupling agent formed on the transfer pattern surface of the mother die 10 is too large, the release agent 16 is filled between the fine irregularities of the pattern 14 to transfer the material to be transferred (metal ) 18 becomes difficult to be embedded deeply, so that there is a possibility that the transfer pattern 14 of the master mold is not sufficiently reflected in the metal film 18. Therefore, the film thickness of the release agent 16 formed on the transfer pattern surface of the mother die is preferably a monomolecular layer to 50 nm, and more preferably a monomolecular layer to 10 nm.

  The film thickness of the silane coupling agent can be adjusted by, for example, the concentration of the silane coupling agent in the solution used when applying to the transfer pattern surface, and a solution containing the silane coupling agent is applied to the transfer pattern surface. Then, the film can be thinned by rinsing with a solvent.

Next, the mother die 10 on which the silane coupling agent film 16 is formed is baked by heat treatment as necessary. Further, after the liquid containing the silane coupling agent is applied to the surface of the mother mold 10 on which the uneven pattern 14 is formed, the liquid containing the silane coupling agent (release agent) is applied before or after the heat treatment. It is preferable to rinse the surface of the formed matrix. In particular, rinsing is preferably performed after the heat treatment. The heat treatment conditions are not limited. For example, the heat treatment may be performed in an oven at 130 ° C. for 30 minutes, 150 ° C. for 20 to 30 minutes, or 120 to 160 ° C. for 15 to 35 minutes.
Since the silane coupling agent used in the present invention has a perfluoroalkyl group and a biphenylalkyl group, the release agent film 16 becomes a monolayer (a molecular layer), and a two-dimensional or three-dimensional network siloxane bond is formed by heat treatment. It is presumed that the siloxane network that forms the film is effective in transferring the concavo-convex pattern 14.

<Metal film>
Next, a metal film 18 is formed on the film 16 of the silane coupling agent (FIG. 1B).
The method of applying the metal film 18 to the surface of the matrix 10 on which the silane coupling agent film 16 is formed is not limited, but a vacuum deposition method, a plating method, or a method of heating after applying a metal ink is preferably used. And can be selected according to the purpose of use of the metal microstructure to be manufactured or the material of the mother die 10.
In particular, since the silane coupling agent used in the present invention has high heat resistance, a temperature condition of usually 200 ° C. to 400 ° C. is provided on the concave / convex pattern 14 of the matrix 10 on which the film 16 of the silane coupling agent is formed. The metal film 18 can be formed by using the vacuum evaporation method performed in the above.
Moreover, also in the said method using a metal ink, the high heat resistance of a silane coupling agent can be utilized. After the metal ink dispersion is applied to the surface of the mother die 10 on which the concave / convex pattern 14 is formed, materials other than metal, such as a binder, contained in the dispersion are sublimated and removed by heating. In this way, when a material such as a binder is sublimated and removed by heating, a film mainly composed of metal can be formed without causing decomposition or the like of the silane coupling agent previously applied to the matrix.

The metal film 18 is usually formed on the entire surface on which the matrix pattern 14 is formed, but it may be formed only on the convex portion.
When the metal microstructure to be manufactured is, for example, a catalyst or a plasmon sensor (SPR), a metal film 18 is formed on the entire surface of the mother die 10 on which the concavo-convex pattern 14 is formed, and then the entire metal film is formed. Integrate with the support member 20.

On the other hand, when a wiring board is manufactured as a metal microstructure, a part of the metal film formed on the matrix may be integrated with the support member. For example, the following method can be applied. .
A matrix whose convex portions of the concave / convex pattern correspond to wiring patterns is prepared, and a metal film is formed on the surface on which the concave / convex pattern is formed. Next, a sheet member having an adhesive layer on one side is used as a support member, and preferably the metal corresponding to the convex portion of the concavo-convex pattern is formed by pressing the adhesive layer of the sheet member against the metal film while applying tension to the sheet member. A part of the film is adhered to the adhesive layer. Thereafter, a part of the metal film is peeled off together with the sheet member, whereby a wiring board having a part of the metal film corresponding to the convex pattern of the matrix as a wiring can be manufactured.

Moreover, after forming a metal film only on the convex part of the concavo-convex pattern of the mother die, the wiring board can be produced by integrating the support member with the metal film and peeling it from the mother die.
A wiring board manufactured using a thin and flexible support member such as an adhesive sheet is used for, for example, a narrow internal bent portion of a mobile phone.
The thickness of the metal film is affected by the depth of the concave / convex pattern of the matrix, but if the thickness of the metal film is too thin, it tends to cause high resistance and disconnection of the wiring, and if it is too thick, it takes time to form the film. This increases the manufacturing cost. From these viewpoints, the thickness of the metal film is preferably about 20 to 1000 nm.
What is necessary is just to select as a metal material which comprises a metal film according to the use of the metal microstructure which should be manufactured, the objective, etc., for example, AU, Ag, Cu, Al, Co, Ni, W, Pt etc. are used. be able to.

<Supporting member>
Next, the support member 20 integrated with the metal film 18 will be described.
The support member 20 may be selected according to the metal microstructure to be manufactured, and glass, ceramic, plastic, or the like may be used. For example, a resin film such as PET may be used. For example, when a thermoplastic resin film is heated while pressed against the metal film 18, the resin film softens and adheres to the metal film 18, and then is cooled and cured again as necessary (FIG. 1 (C )). Thereby, the metal film 18 and the support member 20 adhere.
Thus, the metal fine structure 30 can be obtained by peeling from the film | membrane 16 of a silane coupling agent the unification thing which adhered the resin film 20 to the metal film 18, and was integrated (FIG.1 (D)). .

The material and thickness of the resin film used as the support member are not limited, but if the thickness is too thin, the strength as the support becomes insufficient, and if it is too thick, the flexibility is lowered. Although depending on the material of the resin film, the use of the metal microstructure, etc., a resin film having a thickness of about 10 to 200 μm can be used, for example.
Further, as described above, a resin film having an adhesive layer provided on one side, such as an adhesive tape, is used as the support member 20 and adhered to the metal film 18 formed on the convex portion of the concavo-convex pattern, and then peeled off. By doing so, a wiring board can also be manufactured.

Alternatively, a thermosetting resin or a photocurable resin may be applied to the metal film 18 to provide an uncured resin layer, and then the resin layer may be cured by heating or ultraviolet irradiation to form a support member. The support member obtained by curing the resin layer is integrated with the metal film, and the resulting combined product is peeled from the matrix to produce a metal microstructure. A method for applying a thermosetting resin or a photocurable resin to the metal film 18 is not particularly limited, but a solution containing a resin material of an ultraviolet curable resin or a thermosetting resin is used for spray coating, spin coating, roll coating, etc. A method of applying by a known coating method is suitable.
In addition, when a support member is obtained using a thermosetting resin, the whole including the mother mold is heated. However, since the silane coupling agent used in the present invention has high heat resistance, it is particularly problematic even when heated. Absent.

Further, an uncured resin layer is provided by applying a thermosetting resin or a photocurable resin to the metal film 18, and after placing the resin film on the resin layer, the resin layer is cured by heating or ultraviolet irradiation. By making it, it can also be set as the support member containing the hardened | cured resin layer and resin film. For example, a curable resin is applied to the metal film 18 to form a coating film, and then cured while pressing the resin film against the coating film. As a result, the metal film is bonded to the cured film, and a support member composed of the cured resin film and the resin film is obtained.
In addition, when using an ultraviolet curable resin, it is preferable to use the resin film which permeate | transmits an ultraviolet-ray, and to cure by irradiating an ultraviolet-ray from the resin film side.

The mother die 10 in which the concavo-convex pattern 14 is provided with the silane coupling agent film 16 represented by the general formula (I) is a combination of the support member 20 and the metal film 18 as described above (metal microstructure). ) Can be used advantageously for repeated preparation.
Further, in order to improve the bonding strength with the metal film 18, the surface of the support member 20, particularly the resin film, may be roughened. For example, the surface of the support member 20 is roughened by a method of attaching fine particles to the surface of the support member 20, a method of spraying fine particles at a high pressure (blasting), or the like, whereby irregularities are formed and the material to be transferred (metal film) 18. It is possible to improve the bonding strength.

<Release>
The metal film 18 reflecting the concave / convex pattern 14 of the mother die 12 by separating the metal film 18 from the mother die 12 together with the support member 20, and the support member integrated with the metal film 18 20 is obtained (FIG. 1D).
What is necessary is just to hold | maintain the supporting member 20 integrated with the metal film 18, and to pull away from the mother die 10. FIG. Thereby, the film 16 of the silane coupling agent and the metal film 18 are peeled off, and the metal microstructure 30 having the metal film 18 and the support member 20 in which the fine pattern 14 of the mother die 10 is accurately reflected is obtained. . In the present invention, since the silane coupling agent represented by the general formula (I) is used as a mold release agent, the metal film 18 (transfer member) reflecting the concave / convex pattern 14 of the mother die 10 is used as a mother die. 10 can be easily peeled off, and destruction of the fine pattern 14 of the mother die 10 can be effectively suppressed.

  Although the silane coupling agent film 16 depends on the material of the mother die 10, for example, when glassy carbon is used as the mother die 10, it is firmly bonded to the transfer pattern surface even after the metal film 18 is peeled off. Therefore, after peeling, without applying the silane coupling agent again, formation of the metal film 18 (FIG. 1B), integration of the metal film 18 and the support member 20 (FIG. 1C), support The metal film 18 integrated with the member 20 can be repeatedly peeled off (FIG. 1D). Therefore, if the present invention is applied, for example, a metal microstructure having an antireflection function close to non-reflection and a support member such as a resin film or a glass substrate can be mass-produced at a low cost. Is possible.

  In particular, if ion beam processing by ECR is performed on a glassy carbon substrate, the diameter is reduced from the root to the tip, such as a needle shape, cone shape, pyramid shape, etc., with a height of less than 1 μm and an aspect ratio of 2 or more. Since a pattern composed of a group of fine protrusions having a shape can be formed, if the manufacturing method of the present invention is applied using this as a mother mold, the height is less than 1 μm and the aspect ratio is 2 or more. A metal microstructure comprising a metal film having a pattern including a group of protrusions and a support member can be manufactured.

In addition, by using the metal microstructure manufactured according to the present invention as a mold and repeatedly transferring the pattern of the metal film reflecting the uneven pattern of the matrix to other members, a large number of copies having the uneven pattern Can be produced repeatedly.
For example, after forming a film of a silane coupling agent represented by the general formula (I) on a metal film having a concavo-convex pattern of a metal microstructure, a resin film or thermosetting is performed by the method described above. The concavo-convex pattern is re-transferred to a curable resin made of a curable resin or an ultraviolet curable resin. For example, after a thermosetting resin or a photocurable resin is applied on the silane coupling agent film, the applied resin is cured by heating or ultraviolet irradiation, and the cured resin is peeled from the metal film. Thereby, a resin composition having an uneven pattern is obtained. By repeating this, it is possible to produce a large amount of resin moldings having an uneven pattern.

  As described above, according to the present invention, the metal film can be formed on the concave-convex pattern of the matrix, and can be easily peeled off together with the support member integrated with the metal film. Breakage of the uneven pattern of the matrix is suppressed. The metal film transferred to the support member in this manner reflects the matrix pattern faithfully, that is, the resolution is good, and the metal film transferred to the support member does not easily crack. Further, the mother die can be used repeatedly, and the durability of the mother die can be maintained over a long period of time.

  Hereinafter, examples will be described, but the present invention is not limited to the following examples.

-Surface treatment of substrate-
A glassy carbon (made by Tokai Carbon Co., Ltd.) substrate with a polished surface (thickness: 1 mm, length and width: 10 mm × 10 mm), an ECR (electron cycloton resonance) type ion beam having a structure as shown in FIG. The surface was subjected to ion beam processing using a processing apparatus (trade name: EIS-200ER, manufactured by Elionix Co., Ltd.).
The ion beam processing apparatus 50 includes a holder 66 for holding the substrate 52, a gas introduction tube 54, a plasma generation chamber 56, an extractor 58, an electromagnet 60, an ion beam extraction electrode 62, a Faraday cup 64, and the like. For example, since the current density decreases at a low acceleration voltage of 500 V or less, the extractor 58 is a grid for extracting ions on the plasma side from the extraction electrode 62 in order to increase the current density. If the extractor 58 is used, even if the acceleration voltage is low, the current density increases and the machining speed can be increased.

The glassy carbon substrate 52 was set in a holder 66, oxygen was introduced as a reaction gas, and a predetermined acceleration voltage was applied to the surface of the glassy carbon substrate 52 to perform ion beam processing. The processing conditions are as follows.
Beam irradiation angle: perpendicular to the processing surface (90 ° to the transfer pattern surface of the substrate)
Reaction gas: Oxygen Gas flow rate: 3.0 SCCM
Microwave: 100W
Acceleration voltage: 500V
Processing time: 45 minutes Vacuum degree: 1.3 × 10 ⁻² Pa

  FIG. 3 is an SEM image showing the surface state of the glassy carbon substrate processed by changing the processing time. As can be seen in FIG. 3, the surface (processed surface) of the glassy carbon substrate is formed with a pattern consisting of minute protrusions having a shape that decreases in diameter toward the tip, and the height and pitch of the protrusions according to the processing time. Changed.

-Manufacture of mold release agent-
In the general formula (I), X, Y and Z are all methoxy groups and (1) R is F (CF ₂ ) ₈ (8F2P3S3M), (2) F (CF ₂ ) ₁₀ by the following steps. (10F2P3S3M) and (3) F (CF ₂ ) ₁₂ (12F2P3S3M) were respectively synthesized.

(1) F (CF ₂ ) ₈ (C ₆ H ₄ ) ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ [8F2P3S3M] was synthesized through the following steps (1-1) to (1-3). .

(1-1) Synthesis of F (CF ₂ ) ₈ (C ₆ H ₄ ) ₂ Br [8F2PB]

A 500 ml eggplant type flask equipped with a reflux condenser and a dropping funnel was replaced with a nitrogen atmosphere, copper bronze powder 23.0 g (362 mmol), 4,4′-dibromobiphenyl 25.0 g (80.1 mmol), and DMSO as a solvent. After adding 120 ml, the mixture was heated and stirred at 120 ° C. Two hours later, 23.6 ml (80.5 mmol) of perfluorooctyl iodide was slowly added dropwise, followed by heating and stirring at 120 ° C. for 24 hours. After the refluxing, the solution was cooled to room temperature, and excess copper powder and white solid were separated by filtration using a Kiriyama funnel. From the obtained mixture of copper powder and white solid, Soxhlet extraction was performed using ethyl acetate as a solvent. CuBr ₂ and CuI present in the extract were removed by washing with saturated NaCl water, the extract was dehydrated with magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by vacuum distillation to obtain a distillate.
The obtained distillate was analyzed by each spectrum of ¹ H-NMR, FT-IR, and Mass. The obtained distillate was identified as 8F2PB from each spectrum of ¹ H-NMR, FT-IR, and Mass (m / z 651).
Yield 22.9 g (35.2 mmol)
Yield 44%
Boiling point 134-135 ° C / 30Pa
The property was a white solid.

(1-2) Synthesis of F (CF ₂ ) ₈ (C ₆ H ₄ ) ₂ CH ₂ CH═CH ₂ [8F2PA]

A 200 ml eggplant type flask equipped with a dropping funnel was replaced with a nitrogen atmosphere and cooled with a dry ice / methanol refrigerant (−78 ° C.), and then 6.79 ml (18.1 mmol) of a 2.66 M n-butyllithium / hexane solution. Then, 11.9 ml (9.04 mmol) of a 0.76 M isopropylmagnesium bromide / THF solution was added and stirred for 1 hour. Thereafter, 4.80 g (7.40 mmol) of 8F2PB dissolved in 50 ml of diethyl ether was slowly added dropwise and stirred at -78 ° C for 1 hour.
After adding 0.42 g (22.2 mmol) of catalyst CuI to the solution that has turned yellowish brown, 3.82 ml (45.18 mmol) of allyl bromide is added dropwise, and after stirring for 2 hours, no saturated NH ₄ Cl aqueous solution precipitates. Until the reaction was stopped. After extraction with ethyl acetate, dehydration was performed with magnesium sulfate, and ethyl acetate was removed under reduced pressure. The residue was purified by distillation under reduced pressure to obtain a distillate.
The obtained distillate was analyzed by each spectrum of ¹ H-NMR, FT-IR, and Mass. The obtained distillate was identified as 8F2PA by ¹ H-NMR, FT-IR, and Mass (m / z 612) spectra.
Yield 1.86 g (3.04 mmol)
Yield 41%
Boiling point 164-167 ° C / 80Pa
The property was a white solid.

(1-3) Synthesis of F (CF ₂ ) ₈ (C ₆ H ₄ ) ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ [8F2P3S3M]

A 200 ml eggplant type flask equipped with a reflux condenser was replaced with a nitrogen atmosphere, THF 10 ml, 8F2PA 1.86 g (3.04 mmol), trimethoxysilane 0.77 g (6.08 mmol), 0.1 MH ₂ PtCl as a catalyst ₆ / THF solution (0.1 ml, 0.01 mmol) was collected and stirred at 50 ° C. for 48 hours. After standing to cool, THF and trimethoxysilane were distilled off under reduced pressure. The residue was purified by distillation under reduced pressure to obtain a distillate.
The obtained distillate was analyzed by each spectrum of ¹ H-NMR, FT-IR, and Mass. The obtained distillate was identified as 8F2P3S3M by ¹ H-NMR, FT-IR, and Mass spectra.
Yield 1.50 g (2.04 mmol)
Yield 67%
Boiling point 160-165 ° C / 30Pa
The property was a white solid.

_{(2) F (CF 2)} 10 (C 6 H 4) 2 CH 2 CH 2 CH 2 Si (OCH 3) 3 (10F2P3S3M) is synthesized through the following steps (2-1) to (2-3) did.

(2-1) Synthesis of F (CF ₂ ) ₁₀ (C ₆ H ₄ ) ₂ Br [10F2PB]

A 500 ml eggplant type flask equipped with a reflux condenser and a dropping funnel was replaced with a nitrogen atmosphere, 20.0 g (315 mmol) of copper bronze powder, 20.0 g (64.1 mmol) of 4,4′-dibromobiphenyl, and DMSO as a solvent. After adding 120 ml, the mixture was heated and stirred at 120 ° C. After 2 hours, 42.6 g (66 mmol) of perfluorodecyl iodide was slowly added dropwise, followed by heating and stirring at 120 ° C. for 24 hours. After completion of the reflux, the solution was cooled to room temperature, and excess copper powder and white solid were separated by filtration using a Kiriyama funnel. From the obtained mixture of copper powder and white solid, Soxhlet extraction was performed using ethyl acetate as a solvent. CuBr ₂ and CuI present in the extract were removed by washing with saturated NaCl water, the extract was dehydrated with magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain a distillate. The obtained distillate was identified as 10F2PB from the analysis result of Mass spectrum, m / z (molecular weight) 751.
Yield 28.2 g (37.5 mmol)
Yield 59%
Boiling point 139-143 ° C / 32Pa
The property was a white solid.

(2-2) Synthesis of F (CF ₂ ) ₁₀ (C ₆ H ₄ ) ₂ CH ₂ CH═CH ₂ [10F2PA]

A 200 ml eggplant type flask equipped with a dropping funnel was replaced with a nitrogen atmosphere and cooled with a dry ice / methanol refrigerant (−78 ° C.), and then 7.2 ml (19.2 mmol) of a 2.66 M n-butyllithium / hexane solution. Subsequently, 0.73 M isopropylmagnesium bromide / THF solution (12.3 ml, 9.3 mmol) was added, and the mixture was stirred for 1 hour. Thereafter, 5.27 g (7.40 mmol) of 10F2PB dissolved in 50 ml of diethyl ether was slowly added dropwise and stirred at -78 ° C for 1 hour. After adding 0.5 g (1.6 mmol) of catalyst CuI ₂ to the solution that has turned yellowish brown, 5.4 g (45 mmol) of allyl bromide is added dropwise, and after stirring for 2 hours, no saturated NH ₄ Cl aqueous solution precipitates. Until the reaction was stopped. After extraction with ethyl acetate, dehydration was performed with magnesium sulfate, and ethyl acetate was removed under reduced pressure. The residue was distilled under reduced pressure to obtain a distillate.
The obtained distillate was identified to be 10F2PA by the analysis result of Mass spectrum, m / z (molecular weight) 712.
Yield 2.16 g (3.04 mmol)
Yield 41%
Boiling point 169-173 ° C / 77Pa
The property was a white solid.

(2-3) Synthesis of F (CF ₂ ) ₁₀ (C ₆ H ₄ ) ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ [10F2P3S3M]

A 200 ml eggplant type flask equipped with a reflux condenser was replaced with a nitrogen atmosphere, 10 ml of THF, 2.16 g (3.04 mmol) of 10F2PA, 1.0 g (8.2 mmol) of trimethoxysilane, and 0.1 MH ₂ PtCl ₆ as a catalyst. / THF solution 0.1 ml (0.01 mmol) was collected and stirred at 50 ° C. for 48 hours. After standing to cool, THF and trimethoxysilane were distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain a distillate.
The obtained distillate was analyzed for each spectrum of NMR, FT-IR, and Mass. Each spectrum of FT-IR and Mass is shown in FIG. 4, FIG. 5, and FIG.
As a result of analysis of each spectrum, the obtained distillate was identified as 10F2P3S3M. HRMS = 834.0108 (calculated value: 834.5323).
Yield 1.65 g (1.98 mmol)
Yield 65%
Boiling point 164-167 ° C / 28Pa
The property was a white solid.

(3) Synthesis of F (CF ₂ ) ₁₂ (C ₆ H ₄ ) ₂ CH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ [12F2P3S3M]

A 200 ml eggplant type flask equipped with a reflux condenser was replaced with a nitrogen atmosphere, THF 10 ml, 12F2PA 2.50 g (3.07 mmol), trimethoxysilane 1.0 g (8.2 mmol), 0.1 MH ₂ PtCl ₆ as a catalyst. / THF solution 0.1 ml (0.01 mmol) was collected and stirred at 50 ° C. for 48 hours. After standing to cool, THF and trimethoxysilane were distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain a distillate.
As a result of analyzing a mass spectrum about the obtained distillate, it was identified as 12F2P3S3M by m / z (molecular weight) 934.
Yield 1.96 g (2.09 mmol)
Yield 65%
Boiling point 172-174 ° C./26 Pa
The property was a white solid.

-Surface modification of glass-
A slide glass (manufactured by Matsunami S-7214) was immersed in a 1N aqueous potassium hydroxide solution (pH> 9) for 2 hours and then taken out and washed thoroughly with distilled water. Thereafter, the slide glass was dried in a desiccator and used for the next surface modification.
Various silane coupling agents having perfluoroalkyl chains were prepared in a iso-C ₄ F ₉ OCH ₃ (3M HFE-7100) solvent to a concentration of 15 mmol / l and used for glass surface modification.

  The glass slide that had been washed by the above method was placed in a 200 ml wide-mouth receiver, and nitrogen substitution was performed. On the other hand, the modified solution prepared above was added to the wide-mouth receiver, and the slide glass was completely immersed in the modified solution, and heated and refluxed for 2 hours. After cooling, the removed glass was washed with a modifying solvent and then with distilled water to change the methoxy group to an OH group. Then, heat treatment is performed in an oven at 150 ° C. for 30 minutes for the purpose of constructing a siloxane network that forms a two-dimensional or three-dimensional network siloxane bond by condensation reaction with OH groups between adjacent silane coupling agents. It was. After the heat treatment, the glass was cooled to room temperature in a desiccator to obtain a modified glass.

-Measurement of contact angle of modified glass-
The contact angle of water with the modified glass was measured. The contact angle was measured by using a droplet method in which a contact angle was measured by dropping 0.9 μl of water droplets onto a horizontal glass plate using a CA-X type contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd.

-Heat resistance test of modified glass using 8F2P3S3M-
The characteristic test result is shown about the case where 8F2P3S3M is used as a silane coupling agent.
A modified glass sample was prepared by the method for modifying the surface of the glass.
Next, this modified glass was heat-treated in an oven at a predetermined temperature (200, 250, 300, 350, 370, 400 ° C.) for 2 hours. After the heat treatment, it was cooled to room temperature in a desiccator, and the contact angle of water with the modified glass was measured. The contact angle was measured by the method described above. The results are shown in Table 1.

  From this result, it can be seen that the glass surface modified with the silane coupling agent 8F2P3S3M shows a high contact angle even after 2 hours at a temperature of 350 ° C.

-Durability test of modified glass using 8F2P3S3M-
In the same manner as described above, with respect to the modified glass produced using the 8F2P3S3M solution, the contact angle (water) change of the modified glass surface with respect to the heat exposure time of 350 ° C. was examined, and the heat resistance durability was examined. The results are shown in Table 2.

  From this result, it can be seen that the modified glass using the silane coupling agent 8F2P3S3M solution maintains a high contact angle at 350 ° C. even after 8 hours.

-Heat resistance due to difference in structure of silane coupling agent-
For comparison, the modified glass prepared using each modified solution prepared using 8F2P3S3M, 8F2P2S3M, and 8F2S3M as the silane coupling agent was subjected to a heat exposure time of 350 ° C. in the same manner as described above. About the contact angle (water) on the surface of the modified glass, the contact angle after each time elapsed was measured. The results are shown in Table 3.

  From this result, it can be seen that the silane coupling agent 8F2P3S3M has higher heat resistance than 8F2P2S3M.

-Heat resistance test of modified glass using 10F2P3S3M-
The characteristic test result is shown about the case where 10F2P3S3M is used as a silane coupling agent.
A modified glass sample was prepared by the method for modifying the surface of the glass.
Next, this modified glass was heat-treated in an oven at a predetermined temperature (250, 300, 350, 400, 450 ° C.) for 2 hours. After the heat treatment, it was cooled to room temperature in a desiccator, and the contact angle of water with the modified glass was measured. The contact angle was measured by the method described above. Table 4 shows the results compared with the case of using 8F2P3S3M.

  From this result, it can be seen that the glass surface modified with the silane coupling agent 10F2P3S3M shows a high contact angle even after 2 hours at a temperature of 400 ° C.

-Durability test of modified glass using 10F2P3S3M-
In the same manner as described above, with respect to the modified glass produced using the 10F2P3S3M solution, the change in the contact angle (water) of the modified glass surface with respect to the heat exposure time of 400 ° C. was examined, and the heat resistance durability was examined. The results are shown in Table 5.

  From this result, it can be seen that the modified glass using the silane coupling agent 10F2P3S3M solution maintains a high contact angle at 400 ° C. even after 10 hours.

  The high contact angle with water shown in the above data indicates that the surface free energy is low, indicating that the releasability and antifouling properties are high.

<Example 1>
A mold having a concavo-convex pattern with a height of 180 nm and a space width of 270 nm was produced on a Si substrate by SOG (Acuglass 512B manufactured by Honeywell) under the following conditions.
EB exposure conditions
Acceleration voltage: 10 KV Beam current: 10 pA Dose amount: 800 μC / cm ²
Development condition-Developer: BHF-Development time: 1 minute A mold having this concavo-convex pattern for 24 hours with a 0.1% solution containing 8F2P3S3M silane coupling agent (solvent: "HFE-7100" manufactured by Sumitomo 3M) The liquid phase treatment was performed, followed by rinsing with hydrofluoroether (Sumitomo 3M, HFE-7100) for 1 minute, followed by heating at 100 ° C. for 30 minutes.
Next, an Au film having a film thickness of about 330 nm was formed on the heat-treated silane coupling agent layer by vacuum deposition using an apparatus of VPC-260F (manufactured by ULVAC KIKO). When this surface was observed with an SEM, an Au film without cracks was formed on the surface as shown in FIG.
Next, the PET substrate was pressed onto the Au film and heated at 90 ° C. for 10 minutes, and then the PET substrate was peeled off to produce a metal microstructure comprising the Au film and the PET substrate.
When the metal microstructure was observed with an SEM, as shown in FIG. 9, an Au film reflecting the unevenness of the mold was transferred to the surface of the PET substrate.

<Example 2>
In the same manner as in Example 1, a mold having a concavo-convex pattern on a Si substrate was produced.
The mold having the concavo-convex pattern was ultrasonically cleaned first with acetone and then with ethanol for 15 minutes, respectively, and then cleaned with ozone for about 1 hour. Next, the mold was subjected to a liquid phase treatment in a 0.1% solution containing 10F2P3S3M silane coupling agent (solvent: “HFE-7100” manufactured by Sumitomo 3M Limited) by dipping for about 30 minutes, and then hydrofluoroether ( Rinsing was performed for about 45 minutes with a rinsing solution in which HFE-7100 (manufactured by Sumitomo 3M Ltd.) and tetrahydrofuran were mixed at a ratio of 8: 1.
On the silane coupling agent layer of the mold thus treated, an Au film having a thickness of about 330 nm was formed by vacuum deposition in the same manner as in Example 1.
Next, the PET substrate was pressed onto the Au film and heated at 90 ° C. for 10 minutes, and then the PET substrate was peeled off to produce a metal microstructure comprising the Au film and the PET substrate.

FIG. 10 is an SEM photograph observing the surface of the Au film. (A) shows the Au film on the mold before transfer, and (B) shows the Au film on the PET substrate after transfer. It can be seen that there are no cracks on the surface.
FIG. 11 is an SEM image obtained by observing the pattern transfer state. (A) is a mold itself provided with a pattern, and (B) is an SEM image in which Au is deposited on the entire concavo-convex portion of the pattern and then transferred to a PET substrate. It can be confirmed that the original pattern lines are transferred even after the Au film is transferred onto the PET substrate.

<Comparative Example 1>
The experiment was performed in the same manner as in Example 2 except that an optool was used as a release agent.
FIG. 12 is an SEM image obtained by observing the surface of the Au film. (A) shows the Au film on the mold before transfer, and (B) shows the Au film on the PET substrate after transfer. It can be seen that both have cracks on the surface.
FIG. 13 is an SEM image in which the pattern transfer state is observed. (A) is the mold itself provided with the pattern, and (B) is an SEM image of observing the state in which Au is deposited on the entire concavo-convex portion of the pattern and then transferred to the PET substrate. It can be confirmed that the pattern lines are not transferred after the Au film is transferred onto the PET substrate.

<Example 3>
Using the apparatus having the configuration shown in FIG. 2, the surface of the glassy carbon substrate (GC substrate) was finely processed under the following conditions.
Beam irradiation angle: perpendicular to the processing surface (90 ° to the transfer pattern surface of the substrate)
Reaction gas: Oxygen Gas flow rate: 3.0 SCCM
Microwave: 100W
Acceleration voltage: 500V
Time: 30 minutes Degree of vacuum: 1.3 × 10 ⁻² Pa
This finely processed surface is shown in FIG. A fine structure pattern composed of a group of conical fine protrusions (pitch: 62 nm, height: 540 nm) is formed.

Next, a Cr film having a thickness of 30 nm was formed on the concavo-convex pattern using a vacuum deposition apparatus VPC-260F (manufactured by ULVAC KIKO), and an Au film having a thickness of 340 nm was further formed on the Cr film.
Further, after pressing the PET substrate onto the Au film and heating at 90 ° C. for 30 minutes, the PET substrate was peeled off and observed with an SEM. As shown in FIG. As a result, an Au film having a height of 550 nm and a pitch of 122 nm was transferred.

Next, a metal microstructure comprising the Au film reflecting the mold irregularities and the PET substrate thus produced was used as a mold, and this mold was used as a 0.1% solution (solvent containing 8F2P3S3M silane coupling agent. : "HFE-7100" manufactured by Sumitomo 3M Co., Ltd.) for 24 hours, followed by rinsing and heat treatment in the same manner as in Example 1 to form a layer of silane coupling agent on the metal film having irregularities. Formed.
After applying a photocurable resin (PAK-01, manufactured by Toyo Gosei Co., Ltd.) on the heat-treated silane coupling agent layer, the resin was cured by irradiating with ultraviolet rays at 5 J / cm ² , It peeled and the resin molding which has an uneven | corrugated pattern on the surface was produced.
As shown in FIG. 16, the surface of the resin molding reflects the uneven shape of the mold formed on the first glassy carbon substrate, and the average height of the protrusions was 217 nm and the average pitch was 91 nm. .

<Comparative example 2>
In the same manner as in Example 3, the surface of the GC substrate was finely processed to form a Cr film. Next, when an optool was used as a release agent and a release agent layer was provided on the surface of the Cr film, an Au film was formed by vacuum deposition. As a result, many cracks were formed on the surface of the Au film as shown in FIG. It was. It is inferred that cracks occurred in the release agent due to heat during vapor deposition, and cracks also occurred in the Au film.

10 ... Mother 12 ... Base 14 ... Uneven pattern (transfer pattern)
16 ... Silane coupling agent (release agent)
DESCRIPTION OF SYMBOLS 18 ... Metal film 20 ... Support member 30 ... Metal microstructure 50 ... ECR type ion beam processing apparatus P ... Pitch

Claims (11)

A silane coupling represented by the following general formula (I) is used on the surface of the mother mold on which the concavo-convex pattern is formed, using a matrix on which the concavo-convex pattern having a convex portion height of less than 1 μm is formed. Forming a film of the agent;
Forming a metal film on the silane coupling agent film;
Integrating the metal film and a support member for supporting the metal film;
A metal microstructure having the metal film reflecting the concave-convex pattern of the mother mold by peeling the metal film together with the support member, and the support member integrated with the metal film. And obtaining
The manufacturing method of the metal microstructure characterized by including.


(In the formula (I), n represents an integer of 8, 10, 12, or 14, m represents an integer of 3 or 4, and X, Y, and Z each independently represent a methoxy group, an ethoxy group, It is a hydrolyzable group representing a propoxy group, an isopropoxy group, or a halogen atom.)   The method for producing a metal microstructure according to claim 1, wherein in the step of forming the metal film, the metal film is formed by a vapor deposition method.   2. The metal microstructure according to claim 1, wherein in the step of forming the metal film, the metal film is formed by applying a metal ink on the film of the silane coupling agent and then heating. Manufacturing method.   In the step of integrating the metal film and the support member, a resin film is used as the support member, and the resin film is heated and bonded in a state of pressing the resin film against the metal film. The method for producing a metal microstructure according to any one of claims 1 to 3, wherein the member is integrated. In the step of integrating said metal film and the supporting member, after providing the metal layer in a thermosetting resin or a photocurable resin layer of the resin applied to uncured, and heat or ultraviolet radiation the The method for producing a metal microstructure according to any one of claims 1 to 3, wherein the support member is formed by curing a resin layer. In the step of integrating said supporting member and the metal film, the metal film is imparted a thermosetting resin or a photocurable resin is provided a resin layer of uncured, it was placed a resin film to the resin layer 4. The support member including the cured resin layer and the resin film is obtained by curing the resin layer by heating or ultraviolet irradiation. 2. A method for producing a metal microstructure according to item 1. In the step of forming a film of the silane coupling agent, a matrix whose convex portions of the concavo-convex pattern correspond to a wiring pattern is used as the matrix.
In the step of integrating the metal film and the support member, a sheet member having an adhesive layer on one side is used as the support member, and the adhesive layer of the sheet member is brought into pressure contact with the metal film, whereby the uneven pattern Adhering a part of the metal film corresponding to the convex portion of the adhesive layer,
The process of obtaining the said metal fine structure WHEREIN: A wiring board is manufactured as the said metal fine structure by peeling a part of said metal film with the said sheet | seat member. The manufacturing method of the metal microstructure of any one of Claims 1.   8. The method according to claim 1, further comprising a step of preparing a mother die having the concavo-convex pattern formed on a surface as a pre-step of the step of forming the silane coupling agent film. The manufacturing method of the metal microstructure according to the item.   In the step of forming a film of the silane coupling agent, after the liquid containing the silane coupling agent is applied to the surface of the base pattern on which the concave / convex pattern is formed, heat treatment is performed before the heat treatment or The method for producing a metal microstructure according to any one of claims 1 to 8, wherein the surface of the matrix to which the liquid containing the silane coupling agent is applied is rinsed later. Method for producing a metal microstructure according to any one of claims 1 to 9, the aspect ratio of the convex portion of the concavo-convex pattern of the mother die is characterized in der Rukoto 2 or more. Using metal fine structure manufactured by the manufacturing method of the metal microstructure according to any one of claims 1 to 10 as a mold, the general formula to the metal layer of the metal fine structure ( Forming a film of the silane coupling agent represented by I);
After applying a thermosetting resin or a photocurable resin on the silane coupling agent film, heating or irradiating with ultraviolet rays to cure the applied resin;
A step of obtaining a resin molding having a concavo-convex pattern by peeling the cured resin from the metal film;
The manufacturing method of the resin molding characterized by including.