JP2013028006A - Resin mold for spin coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin mold for spin coating exhibiting excellent release properties from a resin material, exhibiting good adhesion to a substrate, and capable of making a film by a spin coating method.SOLUTION: The resin mold (1) for spin coating includes: an inorganic material substrate (11); and a resin layer (12) mounted on a main surface of the inorganic material substrate (11), and having a fine concavo-convex structure (12a) on a surface of the resin layer (12). Regarding the resin layer (12), the fluorine element concentration (Es) in a resin mold surface portion on which the fine concavo-convex structure (12a) is formed is higher than the average fluorine element concentration (Eb) in the resin layer (12).

Description

  The present invention relates to a resin mold used for manufacturing a resin molded body, and particularly to a resin mold for spin coating used for film formation of a resin material by a spin coating method.

  In recent years, in optical elements and biomaterials, precise processing control in the nano / micrometer size region is required in order to realize desired physical properties. In the development of optical elements and biomaterials, high-viscosity resin materials are used as raw materials, and a technique for accurately forming a molded body having a fine uneven structure on the surface from a high-viscosity resin material is required. .

  In general, in order to produce a molded body having a fine concavo-convex structure on the surface, a high viscosity resin material is formed on the surface of the original mold having the fine concavo-convex structure by a cast method or a spin coat method. . Then, by peeling the formed resin material from the original mold, a molded body of the resin material in which the fine uneven structure of the original mold is transferred to the surface is manufactured.

  The fine uneven structure of the original mold is formed by a fine processing technique. Known microfabrication techniques include, for example, a direct microfabrication method using an electron beam, and a method of collectively drawing a fine concavo-convex structure having a large area by interference exposure. Recently, fine pattern processing by a step & repeat method using a stepper device in semiconductor technology is also known. However, all of them require a plurality of processing steps and require high capital investment, so it is difficult to say that the technology is good in terms of throughput and cost. Furthermore, when producing an original mold using a stepper device, it is necessary to use an immersion method in which the space between the projection lens and the original mold is filled with a liquid in order to cope with the recent miniaturization of the fine uneven structure. There is a problem that an environmental load is generated depending on the type of liquid used. Thus, since the original mold is manufactured by a manufacturing method with a high environmental load, it is desirable to manufacture a molded body of a resin material from a resin mold manufactured by a method with a low environmental load from the original mold.

  Further, in the manufacturing process of the molded body of the resin material, a peeling process for peeling the molded body of the resin material from the original mold having the fine uneven structure on the surface is required. In the peeling process, when the peeling force for peeling the molded body of the resin material from the original mold is large, the fine uneven structure on the surface of the molded body of the resin material accompanying the peeling or the molded body of the resin material itself is broken. In order to solve such problems, in the manufacturing process of the molded body of the resin material, a mold release treatment process for applying a mold release treatment agent for reducing the peeling force is introduced to the surface of the fine uneven structure of the original mold. The However, the mold release treatment agent contains fluorine and has low durability, and it is necessary to perform a mold release treatment step periodically every time transfer is performed from the original mold to the resin material a plurality of times. For this reason, a technique that does not require mold release treatment is desired from the viewpoint of environmental performance and productivity. In order to eliminate the need for a mold release treatment, a resin mold using a fluororesin polymer that improves the mold release from the original mold has been proposed (see, for example, Patent Document 1).

JP 2006-198883 A

  By the way, in the manufacturing process of the molded body of the resin material, it is desirable to use the spin coat method for forming the resin material on the mold for manufacturing the molded body of the resin material in consideration of throughput and cost. In the spin coating method, it is necessary to apply the resin material in a state where the mold for producing a molded body of the resin material is rotated at a high speed by a spin coater.

  However, since the resin mold described in Patent Document 1 (mold for producing a molded body of resin material) is made of a fluororesin polymer and has flexibility, the resin material can be applied in a state of being rotated at high speed by a spin coater. There is a problem that becomes difficult. Moreover, even if it is a case where the resin mold of patent document 1 is provided on a smooth base material and it is a case where it uses as a casting_mold | template for resin body molding, it contains the fluororesin polymer which is excellent in releasability. There is a problem that the adhesion between the substrate and the resin mold is not always sufficiently obtained, and there is a problem that film formation by a spin coating method becomes difficult.

  The present invention has been made in view of the above points, and has excellent releasability with a resin material, good adhesion to a substrate, and can be formed by a spin coating method. An object is to provide a resin mold.

  The resin mold for spin coating of the present invention comprises an inorganic base material, and a resin layer provided on the main surface of the inorganic base material and having a fine concavo-convex structure on the surface. The fluorine element concentration (Es) in the surface portion of the surface where the structure is formed is higher than the average fluorine element concentration (Eb) in the resin layer.

  According to this configuration, since the fluorine element concentration (Es) on the fine concavo-convex structure forming surface side in the resin layer is relatively higher than the average fluorine element concentration (Eb) in the resin layer, the resin from the resin mold The mold releasability of the molded body of the material is improved, and the adhesion between the inorganic base material and the resin layer is improved.

  The resin mold for spin coating of the present invention preferably has an adhesive layer provided between the inorganic base material and the resin layer.

In the resin mold for spin coating of the present invention, the resin layer has a ratio of the fluorine element concentration (Es) in the surface portion to the average fluorine element concentration (Eb) in the resin layer expressed by the following formula (1). ) Is preferably satisfied.
20 ≦ Es / Eb ≦ 200 Formula (1)

  The laminate of the present invention comprises the resin mold for spin coating and a thin film provided on the surface of the resin layer on which the fine concavo-convex structure is formed.

  The self-supporting thin film of the present invention is a self-supporting thin film manufactured through a process of isolating the thin film from the laminate, and has a fine concavo-convex structure on one main surface of a pair of opposing main surfaces. .

  The method for producing a self-supporting thin film of the present invention includes a coating step of coating a resin material on the fine concavo-convex structure of the resin layer of the resin mold for spin coating, and a peeling step of peeling the thin film from the resin layer. It is characterized by having.

  ADVANTAGE OF THE INVENTION According to this invention, while being excellent in the mold release property with a resin material, the adhesiveness with a base material is favorable, and also the spin-coat resin mold which can be formed into a film by a spin coat method is realizable.

It is a cross-sectional schematic diagram which shows an example of the resin mold for spin coating which concerns on this Embodiment. It is a cross-sectional schematic diagram which shows the example of the laminated body which concerns on this Embodiment. It is a cross-sectional schematic diagram of the self-supporting thin film which concerns on this Embodiment. It is a schematic diagram which shows the fine concavo-convex structure pattern of the resin mold for spin coating according to the present embodiment. It is the schematic of the manufacturing method of the resin mold for spin coats concerning this Embodiment.

Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
1A and 1B are schematic cross-sectional views showing an example of a resin mold for spin coating according to the present embodiment. As shown in FIG. 1A, a spin-coat resin mold 1 according to the present embodiment is provided on an inorganic base material 11 and a main surface of the inorganic base material 11, and a fine concavo-convex structure 12a is formed on the surface. And a resin layer 12. As the fine uneven structure 12a of the resin layer 12, for example, the surface of the resin layer 12 may be used as a reference surface, and a plurality of convex portions protruding upward from the reference surface may be provided. A plurality of recessed portions may be provided. In the resin mold 1 for spin coating according to the present embodiment, the fine concavo-convex structure 12a on the surface of the resin layer 12 is transferred to the resin material to produce a molded body of the resin material.

  In the resin mold 1 for spin coating according to the present embodiment, the resin layer 12 has a surface portion (hereinafter simply referred to as a “fine concavo-convex structure forming surface”) on which the fine concavo-convex structure 12a is formed (hereinafter referred to as “surface portion”). The fluorine element concentration (Es) is also higher than the average fluorine element concentration (Eb) in the resin layer 12. Thereby, since the fluorine element concentration (Es) in the surface part of the resin layer 12 becomes relatively higher than the average fluorine element concentration (Eb) in the resin layer 12, the free energy of the fine uneven structure forming surface of the resin layer 12 is increased. Decreases. As a result, the releasability between the resin layer 12 and the resin material (hereinafter also referred to as “transfer material resin”) applied to the surface of the resin layer 12 and transferred with the fine concavo-convex structure 12a is improved, and the nanometer size Resin / resin transfer can be performed repeatedly on fine uneven structures. Furthermore, since the fluorine element concentration on the surface of the resin layer 12 on the inorganic substrate 11 side is relatively low, the free energy on the surface of the resin layer 12 on the inorganic substrate 11 side is kept high, and the inorganic substrate 11 And the resin layer 12 are improved in adhesion.

  Thus, in the resin mold 1 for spin coating according to the present embodiment, the fluorine element concentration (Es) in the surface portion of the resin layer 12 on the fine concavo-convex structure forming surface side is the average fluorine concentration in the resin layer 12 ( Eb), by providing a concentration gradient from the surface portion on the inorganic base material 11 side toward the surface portion on the fine concavo-convex structure forming surface side, that is, the resin layer 12 and the base material 11 The release property of the transfer material resin provided on the fine concavo-convex structure 12a of the resin layer 12 is improved while maintaining the adhesiveness between the two. The concentration gradient of the resin layer 12 is a range in which the fluorine element concentration (Es) of the resin layer 12 on the fine concavo-convex structure forming surface side is relatively larger than the fluorine element concentration (Eb) in the resin layer 12. Anything can be used. For example, the concentration gradient may be continuously stepless from the surface portion on the inorganic base material 11 side of the resin layer 12 toward the surface portion on the fine concavo-convex structure forming surface side. It may change in stages. Further, in the thickness direction from the surface portion of the resin layer 12 on the inorganic base material 11 side to the fine concavo-convex structure forming surface side, a concentration gradient from the surface portion on the inorganic base material 11 side to the center portion of the resin layer 12, and the resin layer The concentration gradient from the center of 12 to the surface portion on the fine concavo-convex structure forming surface side may be the same, or may have a different concentration gradient.

As the resin layer 12, the ratio of the fluorine element concentration (Es) in the surface portion of the resin layer 12 and the average fluorine element concentration (Eb) in the resin layer 12 preferably satisfies the following formula (1). Thereby, the releasability of the transfer material resin from the resin layer 12 and the adhesion between the resin layer 12 and the inorganic base material 11 are further improved.
Formula (1)
1 <Es / Eb ≦ 1500

  Further, the resin layer 12 has a fluorine element concentration (Es) in the surface portion of the resin layer 12 on the fine concavo-convex structure forming surface within a range of 20 ≦ Es / Eb ≦ 200 within the range of the above formula (1). ) Is sufficiently higher than the average fluorine element concentration (Eb) in the resin layer 12. Thereby, since the free energy of the fine concavo-convex structure forming surface of the resin layer 12 is further reduced, the releasability from the transfer material resin is improved. Further, since the average fluorine element concentration (Eb) in the resin layer 12 is relatively lower than the fluorine element concentration (Es) in the surface portion of the resin layer 12, the strength of the resin layer 12 itself is improved, On the surface of the resin layer 12 on the inorganic base material 11 side, the free energy can be kept high. Thereby, the adhesiveness between the inorganic base material 11 and the resin layer 12, the release property of the transfer material resin from the resin layer 12, and the repetitive transfer property are further improved. Further, the range of 26 ≦ Es / Eb ≦ 189 is preferable because the free energy of the surface of the resin layer 12 on which the fine concavo-convex structure is formed becomes lower, so that the repetitive transferability becomes particularly good. Further, the resin layer 12 preferably satisfies 30 ≦ Es / Eb ≦ 160, more preferably 31 ≦ Es / Eb ≦ 155, and 46 ≦ Es / Eb ≦ 155 within the range of the above formula (1). It is particularly preferable because the above effect can be further exhibited.

  Further, as shown in FIG. 1B, the spin-coat resin mold 1 has an adhesive layer 13 for bonding the inorganic base material 11 and the resin layer 12 between the inorganic base material 11 and the resin layer 12. May be. By providing the adhesive layer 13 between the inorganic base material 11 and the resin layer 12, the adhesion between the inorganic base material 11 and the resin layer 12 is further improved.

  In the present specification, the “surface portion of the resin layer 12” refers to the surface portion of the fine concavo-convex structure 12 a of the resin layer 12, and from the surface side of the resin layer 12 in the thickness direction orthogonal to the surface of the resin layer 12. It means a portion in the range of about 1% to 10% or a portion in the range of 2 nm to 20 nm. The “surface portion of the resin layer 12” includes a range in which a specific region having a relatively high average fluorine concentration exists with respect to the average fluorine concentration (Eb) of the entire resin layer 12. For this reason, it is not always necessary that the specific region having a high average fluorine concentration (Es) be present over the entire surface of the resin layer 12 on which the fine concavo-convex structure is formed. Moreover, in this invention, the value calculated | required by XPS method mentioned later is employ | adopted for the fluorine element concentration (Es) of the resin layer 12 surface part. In the present invention, the fluorine element concentration (Es) is a measured value at a depth of several nm, which is the X-ray penetration length in the XPS method.

  On the other hand, in this specification, the “average fluorine element concentration (Eb) in the resin layer 12” is a value calculated from the charged amount, a value analyzed from a gas chromatograph mass spectrometer (GC / MS), or an ion chromatograph. The value analyzed from the analysis is adopted. That is, it means the fluorine element concentration contained in the entire resin layer 12. For example, a section of a resin mold composed of a cured product of a photopolymerizable mixture formed into a film and having a resin part physically peeled off is decomposed by a flask combustion method and subsequently subjected to ion chromatography analysis. Thus, the average fluorine element concentration (Eb) in the resin can be identified.

  Next, the laminate according to the present embodiment will be described. 2A and 2B are schematic cross-sectional views of the laminate 2 according to the present embodiment. As shown in FIG. 2A, the laminate 2 includes a thin film 14 provided on the resin mold 1 for spin coating shown in FIG. That is, the laminate 2 was provided on the inorganic base material 11, the resin layer 12 provided on the inorganic base material 11 and having the fine uneven structure 12 a formed on the surface thereof, and the fine uneven structure 12 a of the resin layer 12. A thin film 14. Moreover, as the laminated body 2, you may have the contact bonding layer 13 which adhere | attaches the inorganic base material 11 and the resin layer 12 between the inorganic base material 11 and the resin layer 12 (refer FIG. 2B). The laminate 2 according to the present embodiment is an intermediate for producing a self-supporting thin film (hereinafter, the thin film 14 is also referred to as a self-supporting thin film 14) having a fine concavo-convex structure 12a described later from the resin mold 1 for spin coating. is there.

  Next, the self-supporting thin film 14 according to the present embodiment will be described. FIG. 3 is a schematic cross-sectional view of the self-supporting thin film 14 according to the present embodiment. The self-supporting thin film 14 according to the present embodiment is manufactured using the above-described resin mold 1 for spin coating. In the self-supporting thin film 14 according to the present embodiment, for example, a thin film 14 is provided by applying a resin material on the fine concavo-convex structure 12a of the resin layer 12 of the resin mold 1 for spin coating using a spin coater or a die coater (application process). ), The thin film 14 to which the fine concavo-convex structure 12a is transferred is separated from the resin layer 12 to be isolated (peeling step). In this case, as shown in FIG. 3, a free-standing thin film 14 having a fine concavo-convex structure 14a on one main surface of a pair of opposed main surfaces is obtained.

<Fine uneven structure shape>
Next, the fine uneven structure 12a of the resin layer 12 will be described in detail. The shape of the fine concavo-convex structure 12a of the resin layer 12 is not particularly limited, but is preferably a pillar shape including a plurality of convex portions having a conical shape, a pyramid shape, or an elliptical cone shape, or a line-and-space structure. It is more preferable to have a pillar shape including a plurality of convex portions having a pyramid shape or an elliptical cone shape. As the pillar shape, the pillars may be adjacent to each other through a smooth recess. Furthermore, a pillar shape may be formed on the large uneven structure. Alternatively, a hole shape including a plurality of conical, pyramidal, or elliptical concavities is preferable. Here, the “pillar shape” is a “shape in which a plurality of columnar bodies (conical states) are arranged”, and the “hole shape” is a “shape in which a plurality of columnar (conical) holes are formed”. is there.

  In FIG. 4, an example of the arrangement | sequence of the fine uneven structure 12a of the resin layer 12 is shown. In addition, in FIG. 4, the top view of the resin layer 12 surface is shown typically, and the direction orthogonal to each other in the resin layer 12 surface is shown as the first direction and the second direction.

  In the example shown in FIG. 4, the fine concavo-convex structure 12 a includes a plurality of convex part rows (or concave part rows) in which a plurality of convex parts (or concave parts) are arranged at a pitch P in the first direction. Each convex part row | line | column (or recessed part row | line | column) is mutually spaced apart and arranged with the pitch S in the 2nd direction. Moreover, each convex part row | line | column (or recessed part row | line | column) is arranged so that each convex part (or each recessed part) which belongs to the mutually adjacent convex part row | line | column produces the positional difference (alpha) mutually in a 1st direction. Here, the positional difference α is the number of convex portions (or concave portions) belonging to the adjacent convex portion rows (or concave portion rows) between the closest convex portion central portions (or concave portion central portions). The distance in one direction. For example, as shown in FIG. 4, a line segment in the second direction passing through the center of each convex portion (or each concave portion) belonging to the (N) -th convex portion row (or concave portion row), and the (N) th It means the distance between the line segment in the second direction passing through the center of each convex portion (or concave portion) belonging to the (N + 1) -th convex portion row (or concave portion row) adjacent to the row. In addition, each convex part row | line | column may arrange | position periodically the positional difference (alpha) in a 1st direction between each convex part row | line | column adjacent in a 2nd direction, and may be arranged aperiodically. Moreover, as an arrangement | sequence of the fine concavo-convex structure 12a other than the example shown in FIG. 4, arrangement | sequences, such as a square lattice and a hexagonal close-packing, are mentioned. Note that the pitch P and the pitch S can be appropriately designed according to the assumed application.

  For example, when the fine uneven structure 14a is formed on the surface of the free-standing thin film 14 and the self-supporting thin film 14 is added with an antireflection function, a function of increasing the transmittance and a function of decreasing the incident angle dependency of incident light, the light is irradiated from the light source. It is necessary to determine factors such as the pitches P and S and the height (or depth) of the fine concavo-convex structure 14a in consideration of all of the wavelength distribution of light. In particular, in order to further exhibit the optical performance of the free-standing thin film 14, it is preferable to design the fine concavo-convex structure 14a on the basis of the light having the shortest wavelength among the light irradiated from the light source. Hereinafter, the shortest wavelength of light emitted from the light source is referred to as a reference wavelength. For example, the i-line has a wavelength distribution of 365 nm ± 10 nm, so the reference wavelength is 355 nm, and the g-line has a wavelength distribution of 436 nm ± 5 nm, so the reference wavelength is 431 nm. Therefore, the fine concavo-convex structure 14a is designed based on the reference wavelength 355 nm if the light emitted from the light source is i-line, and is designed based on the reference wavelength 431 nm if the light emitted from the light source is g-line. It is preferable to do. An example of the self-supporting thin film 14 in which such a design is desirable is a pellicle film.

  When the pitches P and S, which are the distances between adjacent convex portions (or concave portions) of the fine concavo-convex structure 12a, are 0.7 times or less with respect to the reference wavelength, the above-described transmittance improvement and incident angle dependency It is preferable because a decrease in the above can be realized. A lower limit value of the pitches P and S is preferably 50 nm because the peelability of the thin film 14 (pellicle film) becomes good and productivity can be maintained. As the height (or depth) of the fine concavo-convex structure 12a, the aspect ratio [height of convex part (or depth of concave part) / length L1 of convex part top part (or length L2 of concave part bottom part: FIG. If it is 2.5 or less, the peelability of the thin film 14 (pellicle film) is good, and it is more preferably 2 or less. A lower limit of 30 nm or more is preferable because the optical performance can be exhibited. Moreover, in order to exhibit the said optical performance more, it is preferable that the occupation rate (occupation area of the recessed part or convex part in the fine concavo-convex structure formation surface) of the fine concavo-convex structure 12a is 70% or more, and 85% or more. It is more preferable that it is 95% or more.

(Inorganic substrate)
It does not specifically limit as the inorganic base material 11, What is necessary is just to select according to the characteristics (for example, heat | fever, UV tolerance, etc.) calculated | required by a use application. For example, as the material of the inorganic base material 11, inorganic materials such as quartz typified by synthetic quartz and fused quartz, non-alkali glass, low alkali glass, glass typified by soda lime glass, silicon wafer, nickel plate, sapphire, diamond, etc. Examples include materials, SiC substrates, mica substrates, and the like. Among these, it is particularly preferable to use an inorganic material selected from quartz such as synthetic quartz and fused quartz, glass such as alkali-free glass, low alkali glass and soda lime glass, and silicon wafer. In addition, depending on the intended use, heat resistance is required. In this case, it is preferable to use an inorganic base material having a small thermal expansion coefficient in consideration of suppressing cracking of the inorganic base material due to temperature spots in the inorganic base material. In particular, the linear expansion coefficient at 0 ° C. to 300 ° C. is preferably 50 × 10 ⁻⁷ m / ° C. or less. In particular, glass and silicon wafers are preferable from the viewpoint of surface smoothness.

(Resin layer)
The resin layer 12 is formed by curing a resin material by photopolymerization or thermal polymerization. The resin material constituting the resin layer 12 is not particularly limited as long as it is a cured product by photopolymerization or thermal polymerization, and various resin materials can be used. As the resin material constituting the resin layer 12, a resin material containing a photopolymerizable mixture is preferable.

  The photopolymerizable mixture used for the resin layer 12 is preferably one containing non-fluorine-containing (meth) acrylate, fluorine-containing (meth) acrylate, and a photopolymerization initiator. When this photopolymerizable mixture is cured in contact with a hydrophobic interface having a low surface free energy, the fluorine element concentration (Es) in the surface portion of the resin layer 12 is changed to the average fluorine element concentration (Eb) in the resin layer 12. As described above, the average fluorine element concentration (Eb) in the resin layer 12 can be arbitrarily adjusted to be smaller. By making the fluorine element concentration (Es) in the surface portion of the resin layer 12 larger than the average fluorine element concentration (Eb) in the resin layer 12, the free energy on the surface of the resin layer 12 on which the fine concavo-convex structure is formed is reduced. The releasability between the layer 12 and the transfer material resin is improved. Further, the free energy is kept high in the vicinity of the inorganic base material 11 in the resin layer 12, and the adhesion between the resin layer 12 and the inorganic base material 11 is improved. As a result, it is possible to realize a spin coat resin mold 1 in which nanometer-sized concavo-convex structures can be repeatedly transferred to the resin / resin and the adhesiveness between the inorganic base material 11 and the resin layer 12 is good.

  In the resin mold 1 for spin coating according to the present embodiment, the photopolymerizable mixture was brought into contact with an interface having a low surface free energy while the average fluorine element concentration (Eb) in the resin layer 12 was kept low. It is desirable to cure in the state. As a result, the fluorine-containing (meth) acrylate is effectively segregated to the interface having a low surface free energy so as to reduce the energy of the entire system, and thus the Es / Eb becomes larger, and the resin having good repeatability and transferability. A mold can be made.

  Moreover, as a photopolymerizable mixture, 0.1 weight part-50 weight part of fluorine-containing (meth) acrylate, and 0.01 weight of photoinitiators are with respect to 100 weight part of non-fluorine-containing (meth) acrylate. Those containing from 10 to 10 parts by weight are preferred. If the fluorine-containing (meth) acrylate is 0.1 parts by weight or more, the releasability of the transfer material resin from the resin layer 12 is improved, and if it is 50 parts by weight or less, the resin layer 12 and the inorganic base material 11 It is preferable because the adhesion between the two is improved. In particular, when the fluorine-containing (meth) acrylate is 5 to 10 parts by weight, the surface segregation of the fluorine-containing (meth) acrylate is excellent. If the fluorine-containing (meth) acrylate is 0.8 parts by weight or more in the above range, the fluorine element concentration (Es) in the surface portion of the resin layer 12 can be increased, and the transfer material resin from the resin layer 12 can be increased. It is preferable because the releasability is improved and the repetitive transfer property is improved. If the fluorine-containing (meth) acrylate is 6 parts by weight or less, the average fluorine element concentration (Eb) in the resin layer 12 can be lowered, the bulk strength of the resin layer 12, the resin layer 12, the inorganic base material 11, and It is more preferable because the adhesion between the two can be increased.

  In addition, the photopolymerization initiator is excellent in polymerizability if it is 0.01 part by weight or more with respect to 100 parts by weight of (meth) acrylate, particularly non-fluorine-containing (meth) acrylate, and 10 parts by weight or less. For example, bleed-out to the resin surface of the unreacted initiator or decomposition product after curing can be reduced. The photopolymerization initiator is more preferably 0.5 parts by weight or more, and still more preferably 1 part by weight or more. Below, the component of the photopolymerizable mixture used for the resin layer 12 is demonstrated in detail.

(A) (Meth) acrylate The (meth) acrylate is not limited as long as it is a polymerizable monomer other than the (B) fluorine-containing (meth) acrylate described later, but a monomer having an acryloyl group or a methacryloyl group, a vinyl group. And a monomer having an allyl group are preferred, and a monomer having an acryloyl group or a methacryloyl group is more preferred. And it is preferable that they are non-fluorine containing monomers.

  The polymerizable monomer is preferably a polyfunctional monomer having a plurality of polymerizable groups, and the number of polymerizable groups is preferably an integer of 1 to 4 because of excellent polymerizability. Moreover, when mixing and using 2 or more types of polymerizable monomers, the average number of polymeric groups has 1-3. When using a single monomer, the number of polymerizable groups may be 3 or more in order to increase the crosslinking point after the polymerization reaction and to obtain physical stability (strength, heat resistance, etc.) of the cured product. preferable. In the case of a monomer having 1 or 2 polymerizable groups, it is preferably used in combination with monomers having different polymerizable numbers.

  Specific examples of the (meth) acrylate monomer include the following compounds. Examples of the monomer having an acryloyl group or a methacryloyl group include (meth) acrylic acid, aromatic (meth) acrylate [phenoxyethyl acrylate, benzyl acrylate, etc.], hydrocarbon (meth) acrylate [stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaaerythritol triacrylate, dipentaerythritol Hexaacrylate, etc.], hydrocarbon-based (meth) acrylates containing etheric oxygen atoms [ethoxyethyl acrylate, methoxyethyl acrylate, Diyl acrylate, tetrahydrofurfryl acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate, tripropylene glycol diacrylate, etc.], hydrocarbon-based (meth) acrylates containing functional groups [2-hydroxy Ethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl vinyl ether, N, N-diethylaminoethyl acrylate, N, N-dimethylaminoethyl acrylate, N-vinylpyrrolidone, dimethylaminoethyl methacrylate, etc.], silicone-based acrylates, and the like. Others include EO-modified glycerol tri (meth) acrylate, ECH-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, trimethylolpropane tri (meth) Acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, EO-modified trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meta) ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate Alkyl modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, alkyl modified dipentaerythritol tri (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, penta Erythritol tetra (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, ECH-modified 1,6-hexanediol di (Meth) acrylate, allyloxypolyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate , EO-modified bisphenol F di (meth) acrylate, ECH-modified hexahydrophthalic acid diacrylate, neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, EO-modified neopentyl glycol diacrylate, PO Modified neopentyl glycol diacrylate, caprolactone modified hydroxypivalate ester neopentyl glycol, stearic acid modified pentaerythritol di (meth) Acrylate, ECH-modified propylene glycol di (meth) acrylate, ECH-modified phthalic acid di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) Acrylate, polypropylene glycol di (meth) acrylate, silicone di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyester (di) acrylate, polyethylene glycol di (meth) acrylate, di Methylol tricyclodecane di (meth) acrylate, neopentyl glycol modified trimethylol propane di (meth) acrylate, dipropylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, divinylethyleneurea, divinylpropyleneurea, 2-ethyl-2-butylpropanediol acrylate 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acrylic acid dimer, benzyl (meth) acrylate, butanedio Rumono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, cetyl (meth) acrylate, EO-modified cresol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, dipropylene glycol (Meth) acrylate, isoamyl (meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyloxyethyl (Meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxypolyethylene Lenglycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, methoxytripropylene glycol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonyl Phenoxy polypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, ECH modified phenoxy acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol ( (Meth) acrylate, phenoxyethyl (meth) acrylate, polyethyleneglycol (Meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, stearyl (meth) acrylate, EO-modified succinic acid (meth) acrylate, tert-butyl (meth) acrylate, tribromophenyl ( Examples include meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, isocyanuric acid EO-modified di- and triacrylate, ε-caprolactone-modified tris (acryloxyethyl) isocyanurate, and ditrimethylolpropane tetraacrylate. It is done. Examples of the monomer having an allyl group include p-isopropenylphenol, and examples of the monomer having a vinyl group include styrene, α-methylstyrene, acrylonitrile, and vinylcarbazole. Here, EO modification means ethylene oxide modification, ECH modification means epichlorohydrin modification, and PO modification means propylene oxide modification.

(B) Fluorine-containing (meth) acrylate The fluorine-containing (meth) acrylate preferably has a polyfluoroalkylene chain and / or perfluoro (polyoxyalkylene) chain and a polymerizable group, and is a linear perfluoroalkylene group. Or a perfluorooxyalkylene group having an etheric oxygen atom inserted between carbon atoms and a carbon atom and having a trifluoromethyl group in the side chain. Moreover, a linear polyfluoroalkylene chain having a trifluoromethyl group at the molecular side chain or molecular structure terminal and / or a linear perfluoro (polyoxyalkylene) chain is particularly preferred.

  The polyfluoroalkylene chain is preferably a polyfluoroalkylene group having 2 to 24 carbon atoms. Moreover, the polyfluoroalkylene group may have a functional group.

The perfluoro (polyoxyalkylene) chain is a group consisting of (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, (CF ₂ CF ₂ CF ₂ O) units and (CF ₂ O) units. It is preferably composed of one or more perfluoro (oxyalkylene) units selected from: (CF ₂ CF ₂ O) units, (CF ₂ CF (CF ₃ ) O) units, or (CF ₂ CF ₂ CF ₂ O). ) Units. The perfluoro (polyoxyalkylene) chain is particularly preferably composed of (CF ₂ CF ₂ O) units since the physical properties (heat resistance, acid resistance, etc.) of the fluoropolymer are excellent. The number of perfluoro (oxyalkylene) units is preferably an integer of 2 to 200, more preferably an integer of 2 to 50, because the release property and hardness of the fluoropolymer are high.

The polymerizable group is represented by a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an epoxy group, a diquitacene group, a cyano group, an isocyanate group, or a formula — (CH ₂ ) aSi (M1) _3-b (M2) _b. A hydrolyzable silyl group is preferable, and an acryloyl group or a methacryloyl group is more preferable. Here, M1 is a substituent which is converted into a hydroxyl group by a hydrolysis reaction. Examples of such a substituent include a halogen atom, an alkoxy group, and an acyloxy group. As the halogen atom, a chlorine atom is preferable. As an alkoxy group, a methoxy group or an ethoxy group is preferable, and a methoxy group is more preferable. As M1, an alkoxy group is preferable, and a methoxy group is more preferable. M2 is a monovalent hydrocarbon group. Examples of M2 include an alkyl group, an alkyl group substituted with one or more aryl groups, an alkenyl group, an alkynyl group, a cycloalkyl group, and an aryl group, and an alkyl group or an alkenyl group is preferable. When M2 is an alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable. When M2 is an alkenyl group, an alkenyl group having 2 to 4 carbon atoms is preferable, and a vinyl group or an allyl group is more preferable. a is an integer of 1 to 3, and 3 is preferable. b is 0 or an integer of 1 to 3, and 0 is preferable. Examples of the hydrolyzable silyl group include (CH ₃ O) ₃ SiCH ₂ —, (CH ₃ CH ₂ O) ₃ SiCH ₂ —, (CH ₃ O) ₃ Si (CH ₂ ) ₃ — or (CH ₃ CH ₂ O ) ₃ Si (CH ₂ ) ₃ — is preferred.

  The number of polymerizable groups is preferably an integer of 1 to 4 and more preferably an integer of 1 to 3 because of excellent polymerizability. When using 2 or more types of compounds, as for the average number of polymeric groups, 1-3 are preferable.

  When the fluorine-containing (meth) acrylate has a functional group, it has excellent adhesion to the transparent substrate. Examples of the functional group include a carboxyl group, a sulfonic acid group, a functional group having an ester bond, a functional group having an amide bond, a hydroxyl group, an amino group, a cyano group, a urethane group, an isocyanate group, and a functional group having an isocyanuric acid derivative. It is done. In particular, it preferably contains at least one functional group having a carboxyl group, a urethane group, or an isocyanuric acid derivative. The isocyanuric acid derivatives include those having an isocyanuric acid skeleton in which at least one hydrogen atom bonded to a nitrogen atom is substituted with another group. As the fluorine-containing (meth) acrylate, fluoro (meth) acrylate, fluorodiene, or the like can be used. Specific examples of the fluorine-containing (meth) acrylate include the following compounds.

The fluoro (meth) _{acrylate, CH 2 = CHCOO (CH 2} ) 2 (CF 2) 10 F, CH 2 = CHCOO (CH 2) 2 (CF 2) 8 F, CH 2 = CHCOO (CH 2) 2 ( CF ₂ ) ₆ F, CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₁₀ F, CH ₂ ═C (CH ₃ ) COO (CH ₂ ) ₂ (CF ₂ ) ₈ F, CH _{2 = C (CH 3) COO (} CH 2) 2 (CF 2) 6 F, CH 2 = CHCOOCH 2 (CF 2) 6 F, CH 2 = C (CH 3) COOCH 2 (CF 2) 6 F, CH 2 = CHCOOCH ₂ (CF ₂ ) ₇ F, CH ₂ = C (CH ₃ ) COOCH ₂ (CF ₂ ) ₇ F, CH ₂ = CHCOOCH ₂ CF ₂ CF ₂ H, CH ₂ = CHCOOCH ₂ (CF _{2 CF 2) 2 H, CH 2} = CHCOOCH 2 (CF 2 CF 2) 4 H, CH 2 = C (CH 3) COOCH 2 (CF 2 CF 2) H, CH 2 = C (CH 3) COOCH 2 (CF _{2 CF 2) 2 H, CH} 2 = C (CH 3) COOCH 2 (CF 2 CF 2) 4 H, CH 2 = CHCOOCH 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 = CHCOOCH 2 CF 2 O (CF _{2 CF 2 O) 3 CF 3} , CH 2 = C (CH 3) COOCH 2 CF 2 OCF 2 CF 2 OCF 3, CH 2 = C (CH 3) COOCH 2 CF 2 O (CF 2 CF 2 O) 3 CF _{3, CH 2 = CHCOOCH 2 CF} (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F, CH 2 = CHCOOCH 2 CF (CF 3) O _{CF 2 CF (CF 3) O} ) 2 (CF 2) 3 F, CH 2 = C (CH 3) COOCH 2 CF (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F, CH 2 = _{C (CH 3) COOCH 2 CF} (CF 3) O (CF 2 CF (CF 3) O) 2 (CF 2) 3 F, CH 2 = CFCOOCH 2 CH (OH) CH 2 (CF 2) 6 CF (CF _{3) 2, CH 2 = CFCOOCH} 2 CH (CH 2 OH) CH 2 (CF 2) 6 CF (CF 3) 2, CH 2 = CFCOOCH 2 CH (OH) CH 2 (CF 2) 10 F, CH 2 = _{CFCOOCH 2 CH (OH) CH 2} (CF 2) 10 F, CH 2 = CHCOOCH 2 CH 2 (CF 2 CF 2) 3 CH 2 CH 2 OCOCH = CH 2, CH 2 = C (CH 3 _{COOCH 2 CH 2 (CF 2 CF} 2) 3 CH 2 CH 2 OCOC (CH 3) = CH 2, CH 2 = CHCOOCH 2 CyFCH 2 OCOCH = CH 2, CH 2 = C (CH 3) COOCH 2 CyFCH 2 OCOC ( CH ₃₎ = fluoro, such as CH ₂ (meth) acrylate (where, CYF perfluoro (1,4-cyclohexylene-xylene group),. ).

The _{fluorodiene, CF 2 = CFCF 2 CF =} CF 2, CF 2 = CFOCF 2 CF = CF 2, CF 2 = CFOCF 2 CF 2 CF = CF 2, CF 2 = CFOCF (CF 3) CF 2 CF = CF ₂ , CF ₂ = CFOCF ₂ CF (CF ₃ ) CF = CF ₂ , CF ₂ = CFOCF ₂ OCF = CF ₂ , CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF = CF ₂ , CF ₂ = CFCF ₂ C _{(OH) (CF 3) CH} 2 CH = CH 2, CF 2 = CFCF 2 C (OH) (CF 3) CH = CH 2, CF 2 = CFCF 2 C (CF 3) (OCH 2 OCH 3) CH 2 Fluorodienes such as CH═CH ₂ , CF ₂ ═CFCH ₂ C (C (CF ₃ ) ₂ OH) (CF ₃ ) CH ₂ CH═CH _2, etc. may be mentioned.

  The fluorine-containing (meth) acrylate is a fluorine-containing urethane (meth) acrylate represented by the following chemical formula (1) and / or a fluorine-containing (meth) acrylate represented by the following chemical formula (2). Since the surface free energy of the fine concavo-convex structure forming surface of the resin layer 12 can be further reduced, the adhesion between the resin layer 12 and the inorganic base material 11 is improved. Moreover, since the average fluorine element density | concentration (Eb) in the resin layer 12 can be reduced and the intensity | strength of the resin layer 12 can be maintained, since repeat transferability improves more, it is preferable. As such urethane (meth) acrylate, for example, “OPTOOL DAC” manufactured by Daikin Industries, Ltd. can be used.

（化学式（１）中、Ｒ１は、下記化学式（３）を表し、Ｒ２は、下記化学式（４）を表す。）

(In the chemical formula (1), R1 represents the following chemical formula (3), and R2 represents the following chemical formula (4).)

（化学式（３）中、ｎは、１以上６以下の整数である。）

(In chemical formula (3), n is an integer of 1-6.)

（化学式（４）中、Ｒは、Ｈ又はＣＨ_３である。）

(In the chemical formula (4), R is H or CH _3. )

  As a fluorine-containing (meth) acrylate, 1 type may be used independently and 2 or more types may be used together. Further, it can be used in combination with surface modifiers such as abrasion resistance, scratch resistance, fingerprint adhesion prevention, antifouling property, leveling property and water / oil repellency. For example, “Factent” manufactured by Neos Co., Ltd. (for example, M series: Futgent 251, Futgent 215M, Futgent 250, FTX-245M, FTX-290M; S series: FTX-207S, FTX-211S, FTX-220S, FTX-230S; F Series: FTX-209F, FTX-213F, Footage 222F, FTX-233F, Footage 245F; G Series: Footent 208G, FTX-218G, FTX-230G, FTS-240G; Oligomer Series: Footer Gent 730FM, tergent 730LM; tergent P series: tergent 710FL, FTX-710HL, etc.), DIC's "Megafuck" (for example, F-114, F-410, F-4) 3, F-494, F-443, F-444, F-445, F-470, F-471, F-474, F-475, F-477, F-479, F-480SF, F-482, F-483, F-489, F-172D, F-178K, F-178RM, MCF-350SF, etc., Daikin's "OPTOOL (registered trademark)" (eg, DSX, DAC, AES), "Eftone (registered) Trademark) ”(for example, AT-100),“ Zeffle (registered trademark) ”(for example, GH-701),“ Unidyne (registered trademark) ”,“ Daifree (registered trademark) ”,“ Optoace (registered trademark) ” ”,“ Novec EGC-1720 ”manufactured by Sumitomo 3M Co.,“ Fluorosurf (registered trademark) ”manufactured by Fluoro Technology, Inc., and the like.

  As the fluorine-containing (meth) acrylate, the weight average molecular weight Mw is preferably 50 to 50,000, and from the viewpoint of compatibility, the weight average molecular weight Mw is preferably 50 to 5000, and the weight average molecular weight Mw is 100 to 5000. It is more preferable that When using a high molecular weight having low compatibility, a diluting solvent may be used. As a dilution solvent, the solvent whose boiling point of a single solvent is 40 to 180 degreeC is preferable, 60 to 180 degreeC is more preferable, and 60 to 140 degreeC is further more preferable. Two or more kinds of diluents may be used.

(C) Photopolymerization initiator The photopolymerization initiator causes a radical reaction or an ionic reaction by light, and a photopolymerization initiator that causes a radical reaction is preferable. Examples of the photopolymerization initiator include the following photopolymerization initiators.

  As acetophenone-based photopolymerization initiators, acetophenone, p-tert-butyltrichloroacetophenone, chloroacetophenone, 2,2-diethoxyacetophenone, hydroxyacetophenone, 2,2-dimethoxy-2′-phenylacetophenone, 2-aminoacetophenone And dialkylaminoacetophenone.

  Benzoin-based photopolymerization initiators include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2 -Methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal and the like.

  Benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone, acrylic benzophenone, 4,4′-bis ( Dimethylamino) benzophenone, perfluorobenzophenone and the like.

  Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, and dimethylthioxanthone.

  Examples of the anthraquinone-based photopolymerization initiator include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and the like. Examples of ketal photopolymerization initiators include acetophenone dimethyl ketal and benzyl dimethyl ketal.

  Other photopolymerization initiators include α-acyl oxime ester, benzyl- (o-ethoxycarbonyl) -α-monooxime, acyl phosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetra Examples thereof include methyl thiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate and the like. Examples of the photopolymerization initiator having a fluorine atom include perfluoro tert-butyl peroxide and perfluorobenzoyl peroxide. Moreover, you may use these well-known and usual photoinitiators individually or in combination of 2 or more types.

  The photopolymerizable mixture may contain a photosensitizer. Specific examples of the photosensitizer include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzisothiuronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate. , Triethylenetetramine, 4,4′-bis (dialkylamino) benzophenone, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, tri It can be used in combination with one or more known and commonly used photosensitizers such as amines such as ethanolamine.

  Examples of commercially available photopolymerization initiators include “IRGACURE” manufactured by Ciba (for example, IRGACURE 651, 184, 500, 2959, 127, 754, 907, 369, 379, 379EG, 819, 1800, 784, OXE01). , OXE02) and “DAROCUR” (for example, DAROCUR1173, MBF, TPO, 4265).

  A photoinitiator may be used individually by 1 type, or may use 2 or more types together. When two or more types are used in combination, it may be selected from the viewpoint of the dispersibility of the fluorine-containing (meth) acrylate, and the surface portion on the fine concavo-convex structure forming surface side and the internal curability of the photopolymerizable mixture. For example, the combined use of an α-hydroxyketone photopolymerization initiator and an α-aminoketone photopolymerization initiator can be mentioned. Moreover, as a combination in the case of using two types together, for example, “IRGACURE” manufactured by Ciba, “IRGACURE” and “DAROCUR” are combined, DAROCUR1173 and IRGACURE819, IRGACURE379 and IRGACURE127, IRGACURE819 and IRGACURE127, IRGACURE127 IRGACURE184 and IRGACURE369, IRGACURE184 and IRGACURE379EG, IRGACURE184 and IRGACURE907, IRGACURE127 and IRGACURE379EG, IRGACURE819 and IRGACURE184, DAROCURPO4 and IRGACUREPO4

(Adhesive layer)
Examples of the adhesive layer 13 include an epoxy resin adhesive, a polyurethane adhesive, and a silane coupling agent. In particular, a silane coupling agent is preferable. Silane coupling agents include functional groups such as acryloyl group, methacryloyl group, acryloxy group, methacryloxy group, acrylic group, methacryl group, vinyl group, epoxy group, glycidyl group, allyl group, oxetanyl group, etc. Is preferable. In particular, when it is any one of (meth) acrylic group, (meth) acryloyl group, (meth) acryloxy group, epoxy group, glycidyl group, and oxetane group, adhesion to inorganic base material 11 and resin layer 12 Since adhesiveness becomes more favorable, it is preferable. As these silane coupling agents, for example, KBM-1003 (made by Shin-Etsu Silicone) which is vinyltrimethoxysilane, KBE-1003 (made by Shin-Etsu Silicone) which is vinyltriethoxysilane, SZ which is vinyltrimethoxysilane. -6300 (made by Toray Dow Corning), SZ-6075 (made by Toray Dow Corning) which is vinyltriacetoxysilane, TSL8310 (made by GE Toshiba Silicone) which is vinyltrimethoxysilane, TSL8311 (made by GE Toshiba Silicone) GE Toshiba Silicone), KMB-502 (made by Shin-Etsu Silicone) which is 3-methacryloxypropylmethyldimethoxysilane, KMB-503 (made by Shin-Etsu Silicone) which is 3-methacryloxypropyltrimethoxysilane, 3-Methacryl KME-502 (made by Shin-Etsu Silicone) which is loxypropylmethyldiethoxysilane, KBM-503 (made by Shin-Etsu Silicone) which is 3-methacryloxypropyltriethoxysilane, SZ- which is γ-methacryloxypropyltrimethoxysilane 6030 (manufactured by GE Toshiba Silicone), TSL8370 (manufactured by GE Toshiba Silicone) which is γ-methacryloxypropyltrimethoxysilane, TSL8375 (manufactured by GE Toshiba Silicone) which is γ-methacryloxypropylmethyldimethoxysilane, 3-acrylic KBI-5103 (made by Shin-Etsu Silicone) which is loxypropyltrimethoxysilane, KBM-303 (made by Shin-Etsu Silicone) which is 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyl KBM-402 (made by Shin-Etsu Silicone) which is dimethoxysilane, KBM-403 (made by Shin-Etsu Silicone) which is 3-glycidoxypropyltrimethoxysilane, KBE-402 which is 3-glycidoxypropylmethyldiethoxysilane (Shin-Etsu Silicone), 3-glycidoxypropyltriethoxysilane KBE-403 (Shin-Etsu Silicone), p-styryltrimethoxysilane KBM-1403 (Shin-Etsu Silicone), and the like. .

  In addition, as the adhesive layer 13, a photopolymerization initiator can be included in the adhesive layer 13. The photopolymerization initiator causes a radical reaction or an ionic reaction by light. As the photopolymerization initiator, a photopolymerization initiator that causes a radical reaction is preferable. As a photoinitiator, the thing similar to the photoinitiator of the resin layer 12 mentioned above can be used.

  When the thickness of the adhesive layer 13 is 1 μm from the monomolecular layer, the adhesiveness is good, and when it is 500 nm from the monomolecular layer, the thickness uniformity of the adhesive layer 13 is also better, which is preferable.

  It does not specifically limit as a resin material which comprises the self-supporting thin film 14, What is necessary is just to select a material suitably according to a use. For example, when a self-supporting thin film is used as an antireflection film, a material in which the refractive index of the substrate to which the self-supporting thin film is bonded and the refractive index of the self-supporting thin film are approximately equal may be selected. When the self-supporting thin film 14 is used as a pellicle film, it is preferable that the light transmittance is high at the exposure wavelength at which the pellicle film is used. Examples of the material constituting the pellicle membrane include cellulose derivatives (nitrocellulose, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, etc., or a mixture of two or more thereof), cycloolefin resin (norbornene polymer or For example, Apel (registered trademark: manufactured by Mitsui Chemicals), Topas (registered trademark: manufactured by Polyplastics Co., Ltd.), Zeonex (registered trademark: Nippon Zeon Co., Ltd.). ), ZEONOR (registered trademark: manufactured by ZEON CORPORATION), ARTON (registered trademark: manufactured by JSR), etc., fluorine-based resins (tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene terpolymer, perfluoroalkyl ether ring) Fluorine resin with structure That Teflon AF (registered trademark, manufactured by Du Pont Co., Ltd.), Sai top (trade name: manufactured by Asahi Glass Co., Ltd.), Argo freon (trade name: Ausimont Co., Ltd.) and the like) and the resin material, such as is. Among these resin materials, in particular, when a fluororesin having a perfluoroalkyl ether ring structure, cellulose acetate propionate or cycloolefin resin is used as the main component of the pellicle membrane material, the peelability from the mold of the pellicle membrane is good. Therefore, it is preferable.

  For the production of the pellicle film, it is preferable to use a polymer solution in which the pellicle film material is dissolved in an organic solvent. As the solvent, those which have very little volatilization at ambient temperature and whose boiling point is not too high are preferable. In view of the above, the solvent preferably has a boiling point of 100 to 200 ° C.

  Examples of such a solvent include aliphatic hydrocarbon compounds, aromatic compounds, halogenated hydrocarbons such as chlorinated hydrocarbons, ester compounds, and ketone compounds. Of these, organic solvents such as saturated aliphatic hydrocarbon compounds such as alicyclic hydrocarbons, aromatic compounds, and halogenated hydrocarbons can be suitably used for cycloolefin resins, and chlorine derivatives can be used for cellulose derivatives. Soluble in single or mixed organic solvents such as hydrocarbons, ketones, esters, alkoxy alcohols, benzene, alcohols. Examples of these organic solvents include organic solvents such as chlorinated hydrocarbons, ester compounds, and ketone compounds. As the chlorinated hydrocarbon, methylene chloride, ethylene chloride, propylene chloride and the like are preferably used, and as the ketone compound organic solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone and the like are preferably used. As the ester compound organic solvent, acetate esters (methyl acetate, ethyl acetate, butyl acetate, etc.) and lactate esters (ethyl lactate, butyl lactate, etc.) are preferably used. In addition, benzene, ethanol, methanol, cellosolve acetate, carbitol and the like can be used as a single or mixed solvent. The polymer solution in which the pellicle film material is dissolved preferably has an absorbance of 0.05 or less in order to increase the light transmittance of the pellicle film and reduce foreign substances in the pellicle film.

  Next, an example of a method for producing a resin mold for spin coating according to the present embodiment will be described with reference to FIG. FIG. 5 is a schematic view of a method for producing a resin mold for spin coating according to the present embodiment.

  As shown in FIG. 5, in the method for manufacturing a resin mold for spin coating according to the present embodiment, a resin layer 12 is formed on the main surface of the inorganic substrate 11 (resin layer 12 forming step), and the formed resin The fine uneven structure of the resin mold 21 is transferred to the surface of the layer 12 (transfer process), and the resin mold is released from the resin layer 12 to which the fine uneven structure is transferred (release process).

  In the resin layer 12 forming step, the resin layer 12 is formed by applying the above-described photopolymerizable mixture or the like onto the inorganic substrate 11 by spin coating or bar coating. Examples of the method for forming the resin layer 12 include a dipping method, a casting method, a spin coating method, a bar coating method, and a die coating method.

  In the resin layer 12 formation step, the surface of the inorganic base material 11 may be treated with ozone treatment, oxygen ashing treatment, piranha solution, KOH solution, or piranha solution or a combination of KOH solution and ultrasonic treatment as necessary. Processing may be performed. By such surface treatment, the surface of the inorganic base material 11 is activated, and the adhesion between the resin layer 12 and the inorganic base material 11 is improved.

  In the transfer step, the resin mold 21 is bonded to the resin layer 12 in the order of resin mold 21 / resin layer 12 / inorganic substrate 11 so that the surface of the resin layer 12 and the surface of the resin mold 21 facing the fine uneven structure are opposed. Thus, a laminated body 22 is obtained. Then, the resin layer 12 is cured by UV irradiation to transfer the fine uneven structure of the resin mold 21. The resin mold 21 is not particularly limited as long as it is a resin mold composed of a fluorine-containing resin, but it is more preferable that the resin mold 21 contains a photopolymerizable mixture in the same manner as the resin layer 12.

  In the transfer process, UV irradiation is performed in a state where the fine uneven structure forming surface of the resin mold 21 is pressed against the surface of the resin layer 12 or in a state where the pressure is released after pressing, thereby transferring accuracy and the film of the resin layer 12. This is preferable because the thickness accuracy is improved. The pressing pressure when pressing the resin mold 21 against the resin layer 12 is preferably more than 0 MPa to 10 MPa, more preferably 0.01 MPa to 5 MPa, and further preferably 0.01 MPa to 1 MPa.

  In the transfer step, it is preferable to perform heat treatment after UV irradiation. By performing this heat treatment, unreacted groups in the photopolymerizable mixture constituting the resin layer 12 can be reduced, and mold release becomes easy. As temperature of heat processing, 50 to 120 degreeC is preferable, 50 to 105 degreeC is more preferable, and 60 to 105 degreeC is further more preferable. The heating time for the heat treatment is preferably 15 seconds to 10 minutes, more preferably 15 seconds to 5 minutes, and even more preferably 30 seconds to 5 minutes.

  In the mold release process, the resin mold 21 is peeled from the resin layer 12 of the laminate 22 to obtain a resin mold for spin coating. In the peeling step, heat treatment may be performed after the resin mold 21 is peeled off. By this heat treatment, the reaction of unreacted groups in the photopolymerizable mixture constituting the resin layer 12 is promoted, so that the releasability of the resin mold 21 from the resin layer 12 is improved. Further, since the heat treatment can obtain a spin-coat resin mold that is stable at the heating temperature, when transferring from the spin-coat resin mold to the transfer material, the resin material from the spin-coat resin mold to the transfer material Penetration is suppressed and the mold release property of the resin mold for spin coating is improved.

  As temperature of heat processing, 50 to 250 degreeC is preferable and 105 to 200 degreeC is more preferable. The heating time for the heat treatment is preferably 30 seconds to 60 minutes, more preferably 5 minutes to 60 minutes, and even more preferably 10 minutes to 30 minutes.

  In addition, when manufacturing the resin mold for spin coating (refer FIG. 1B) which has the contact bonding layer 13 between the inorganic base material 11 and the resin layer 12, before forming the resin layer 12 in the resin layer 12 formation process. The adhesive layer 13 is formed by coating or the like. For example, when using a silane coupling agent as the adhesive layer 13, the silane coupling agent or a mixture of the silane coupling agent and the photopolymerization initiator is diluted with a solvent, and then the pH of the solution is adjusted as necessary. The hydrolysis reaction is promoted in the lowered state, and a solution is formed on the inorganic substrate 11. Then, the adhesive layer 13 is formed by volatilizing the solvent. Examples of the method for forming the adhesive layer 13 include dipping, casting, spin coating, bar coating, and die coating. As temperature at the time of volatilizing a solvent, 20 to 200 degreeC is preferable and 60 to 180 degreeC is more preferable. Alternatively, the adhesive layer 13 may be formed by exposing the inorganic substrate 11 to vapor of a silane coupling agent to form a monomolecular film.

  Moreover, when manufacturing the laminated body 2 (refer FIG. 2A, FIG. 2B) which has the thin film 14, the thin film 14 is formed on the fine concavo-convex structure of the resin layer 12 after a mold release process. As a method for forming the thin film 14 (pellicle film), a known film forming method can be used. For example, the film can be formed by the following film forming method. Pellicle film raw material, for example, transparent fluororesin Cytop (Asahi Glass Co., Ltd.), cellulose acetate propionate (Eastman Kodak Co., Ltd.), etc. are diluted with a solvent, and the fine concavo-convex structure of the resin layer 12 of the resin mold 1 for spin coating A film is formed on the formation surface by spin coating and then heated. As temperature of a heating process, 60 to 105 degreeC is preferable and 70 to 90 degreeC is more preferable. You may heat-process at another temperature after a heating process. The time for the heating treatment is preferably 1 minute to 10 minutes, more preferably 3 minutes to 7 minutes. As temperature of heat processing, 150 to 200 degreeC is preferable and 170 to 190 degreeC is more preferable. The time for the heat treatment is preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

  In addition, in the manufacturing method of the resin mold 1 for spin coating mentioned above, although the manufacturing method which forms the resin layer 12 on the inorganic base material 11 by application | coating was demonstrated, as a manufacturing method of the resin mold 1 for spin coating, it is a film. A resin mold in which a resin layer 12 is formed on a base material can be bonded to the inorganic base material 11 to manufacture. In this case, the film base of the resin mold may be selected on the basis of the environmental resistance using the spin coat resin mold. For example, in applications that undergo a process of volatilizing a high-boiling solvent, examples of the film substrate include PC (polycarbonate), PES (polyethersulfone), and PEN (polyethylene naphthalate).

  The resin mold 1 for spin coating according to the present invention is variously used in nanoimprint applications. Specifically, it is used in the production of optical devices such as microlens arrays, wire grid type polarized light, moth-eye type non-reflective films, diffraction gratings, and photonic crystal elements, and nanoimprint applications such as patterned media. In addition, it can be used for production of biodevices such as cell culture sheets, fat culture chips, and biosensor electrodes. In addition, it can be applied to the manufacture of various battery and capacitor electrodes, micro / nano channels, heat dissipation surfaces, heat insulation surfaces, and the like.

  As described above, according to the resin mold 1 for spin mold according to the present embodiment, the fluorine element concentration (Es) on the fine uneven structure forming surface side on the inorganic substrate 11 and the average fluorine in the resin layer 12 Since the resin layer 12 having a different element concentration (Eb) is provided, the surface free energy on the surface with the fine concavo-convex structure is relatively lowered with respect to the surface free energy on the inorganic substrate 11 side. Thereby, the release property of the transfer material resin from the resin mold for spin coating is improved, and the adhesion between the inorganic base material 11 and the resin layer 12 is improved. Therefore, the resin mold 1 for spin coating having excellent transferability and releasability can be realized.

  Examples carried out to clarify the effects of the present invention will be described below. In addition, this invention is not limited at all by the following examples.

[Fluorine element concentration measurement]
The surface fluorine element concentration of the resin layer was measured by X-ray photoelectron spectroscopy (hereinafter, XPS). Since the penetration depth of X-rays into the sample surface in XPS is as shallow as several nm, the measured value of XPS was adopted as the fluorine element concentration (Es) on the surface portion of the resin layer in the present invention. The resin mold was cut out as a small piece of about 2 mm square and covered with a 1 mm × 2 mm slot type mask and subjected to XPS measurement under the following conditions.
XPS measurement conditions Equipment used: Thermo Fisher ESCALAB250
Excitation source; mono. AlKα 15kV × 10mA
Analysis size: approx. 1 mm (shape is oval)
Capture area Survey scan; 0 to 1, 100 eV
Narrow scan; F 1s, C 1s, O 1s, N 1s
Pass energy
Survey scan; 100 eV
Narrow scan; 20 eV

  On the other hand, in order to measure the average fluorine element concentration (Eb) in the resin constituting the resin layer, the physically peeled section is decomposed by a flask combustion method and subsequently subjected to ion chromatography analysis. The average fluorine element concentration (Eb) in the resin was measured.

(A) Cylindrical mold production (production of resin mold production mold)
Quartz glass was used for the base material of the cylindrical mold, and a fine concavo-convex structure was formed on the surface of the quartz glass by a direct drawing lithography method using a semiconductor laser. Durasurf HD-1110Z (manufactured by Daikin Chemical Industry Co., Ltd.) was applied to the surface of the quartz glass roll on which fine surface irregularities were formed, heated at 60 ° C. for 1 hour, and then allowed to stand at room temperature for 24 hours to be fixed. Then, it wash | cleaned 3 times by Durasurf HD-ZV (made by Daikin Chemical Industries), and the mold release process was implemented. Three quartz glasses were used (quartz 1 to quartz 3). A fine uneven structure 1 was formed on the quartz 1, a fine uneven structure 2 was formed on the quartz 2, and a fine uneven structure 3 was formed on the quartz 3. Hereinafter, in resin mold production, the same process was obtained for all of quartz 1 to quartz 3 to produce resin molds.

(B) Production of resin mold Raw materials corresponding to the resin numbers shown in Table 1 below were mixed. The following steps were performed on all solutions. In the step of making the resin mold (B) from the resin mold (A) described later, the resin similar to the resin used when the resin mold (A) was produced was used to form the resin mold (B). In Table 1 below, DACHP is OPTOOL DAC HP (manufactured by Daikin Industries), M350 is trimethylolpropane triacrylate (manufactured by Toagosei Co., Ltd.), and l. 184 is IRGACURE 184 (manufactured by Ciba), l. 369 is IRGACURE 369 (manufactured by Ciba).

A PET film: A4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm) was coated on the easy-adhesion surface of the PET film by microgravure coating (manufactured by Yurai Seiki Co., Ltd.) so that the coating film thickness was 6 μm. Next, a PET film coated with a photocurable resin was pressed against the cylindrical mold with a nip roll (0.1 MPa), and the accumulated exposure amount under the center of the lamp at 25 ° C. and 60% humidity in the atmosphere. Ultraviolet rays were irradiated using a UV exposure apparatus (H bulb, manufactured by Fusion UV Systems Japan Co., Ltd.) so as to be 600 mJ / cm ^2, and photocuring was continuously performed. A reel-shaped resin mold (A) (length 200 m, width 300 mm) was obtained. The shape of the surface unevenness of the reel-shaped resin mold (A) was confirmed by observation with a scanning electron microscope. As a result, when using quartz 1, the adjacent distance between the protrusions was 200 nm and the height of the protrusions was 200 nm. It was. In the case of using quartz 2, the adjacent distance between the convex portions was 150 nm, and the convex portion height was 200 nm. In the case of using quartz 3, the adjacent distance between the convex portions was 130 nm, and the convex portion height was 100 nm. Table 1 below shows the ratio of the surface fluorine element concentration (Es) to the average fluorine element concentration (Eb), Es / Eb, of the obtained resin mold (A). In addition, in the following resin mold (B) production, the same operation was performed in all of the resin mold (A) derived from quartz 1 to the resin mold (A) derived from quartz 3.

PET film: A4100 (manufactured by Toyobo Co., Ltd .: width 300 mm, thickness 100 μm), a resin similar to the resin used when the resin mold (A) was produced, and microgravure coating (Yurui) Applied to a coating film thickness of 6 μm. Next, the PET film coated with the photocurable resin was pressed with a nip roll (0.1 MPa) against the surface of the resin mold (A) obtained by transferring directly from the cylindrical mold with a nip roll (0.1 MPa), Irradiate ultraviolet rays using a UV exposure apparatus (H bulb, manufactured by Fusion UV Systems Japan) so that the integrated exposure amount at the temperature of 25 ° C. and humidity of 60% is 600 mJ / cm ² under the center of the lamp. A plurality of reel-shaped resin molds (B) (200 m in length and 300 mm in width) having a fine concavo-convex structure similar to a cylindrical mold, which is continuously photocured and has a fine concavo-convex structure transferred to the surface. Obtained. The shape of the surface unevenness of the reel-shaped resin mold (B) was confirmed by observation with a scanning electron microscope. As a result, when the resin mold (A) derived from quartz 1 was used, the adjacent distance between the recesses was 200 nm, and the recess height was high. The thickness was 200 nm. In the case of using the resin mold (A) derived from quartz 2, the adjacent distance between the recesses was 150 nm, and the recess height was 200 nm. In the case of using the resin mold (A) derived from quartz 3, the adjacent distance between the recesses was 130 nm and the recess height was 100 nm. Moreover, in the test described below, in the test using a resin mold, the same test was performed for all of nine types of resin molds made from resin numbers 1 to 3 and quartz 1 to quartz 3.

(C) Preparation of resin mold for spin coating A 500 mm square glass substrate was used as the inorganic substrate. The glass substrate was subjected to ozone treatment for 15 minutes before use.

<Resin mold 1 for spin coating>
By the bar coating method, the same resin as the resin that produced the resin mold was applied to the inorganic base material, and at the same time, the surface of the resin mold with the fine concavo-convex structure was bonded. Then, after irradiating UV light from the resin mold side, the resin mold was peeled off to obtain a resin mold for spin coating. The resin mold for spin coating was stabilized by heating at 180 ° C. for 30 minutes. As a result of confirming the surface fine unevenness of the resin mold for spin coating obtained by observation with a scanning electron microscope, the one using the resin mold (A) derived from quartz 1 has an adjacent distance between the recesses of 200 nm. The height was 200 nm. In the case of using the resin mold (A) derived from quartz 2, the adjacent distance between the recesses was 150 nm, and the recess height was 200 nm. In the case of using the resin mold (A) derived from quartz 3, the adjacent distance between the recesses was 130 nm and the recess height was 100 nm. In the case of using the resin mold (B) derived from quartz 1, the adjacent distance between the convex portions was 200 nm, and the height of the convex portions was 200 nm. In the case of using the resin mold (B) derived from quartz 2, the adjacent distance between the convex portions was 150 nm, and the convex portion height was 200 nm. In the case of using the resin mold (B) derived from quartz 3, the adjacent distance between the convex portions was 130 nm, and the convex portion height was 100 nm. In the obtained resin mold for spin coating, the resin layer was slightly peeled off at the end of the glass substrate.

<Resin mold 2 for spin coating>
For 100 parts by mass of 3APTMS (3-acryloxypropyltrimethoxysilane, KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by mass of 184 (IRGACURE 184 Ciba) was added and stirred at room temperature for 15 minutes. Subsequently, using an ethanol solution adjusted to pH 3.5 with hydrochloric acid, the solution was diluted to 0.1% and stirred for 15 minutes. After forming into a film by the bar coating method on the glass substrate which performed the ozone treatment, it was made to dry at 60 degreeC for 10 minute (s). (Laminated body (A)). Subsequently, the same resin as the resin from which the resin mold was produced was applied to the laminate (A) by the bar coating method, and at the same time, the fine uneven structure forming surface of the resin mold was bonded.

  After irradiating UV light from the resin mold side, the resin mold was peeled off to obtain a resin mold for spin coating. The resin mold for spin coating was stabilized by heating at 180 ° C. for 30 minutes. As a result of confirming the surface fine unevenness of the resin mold for spin coating obtained by observation with a scanning electron microscope, the one using the resin mold (A) derived from quartz 1 has an adjacent distance between the recesses of 200 nm. The height was 200 nm. In the case of using the resin mold (A) derived from quartz 2, the adjacent distance between the recesses was 150 nm, and the recess height was 200 nm. In the case of using the resin mold (A) derived from quartz 3, the adjacent distance between the recesses was 130 nm and the recess height was 100 nm. In the case of using the resin mold (B) derived from quartz 1, the adjacent distance between the convex portions was 200 nm, and the height of the convex portions was 200 nm. In the case of using the resin mold (B) derived from quartz 2, the adjacent distance between the convex portions was 150 nm, and the convex portion height was 200 nm. In the case of using the resin mold (B) derived from quartz 3, the adjacent distance between the convex portions was 130 nm, and the convex portion height was 100 nm. The obtained resin mold for spin coating was produced neatly over the entire glass substrate.

<Resin mold 3 for spin coating>
The silicon wafer was exposed to the vapor of 3APTMS (3-acryloxypropyltrimethoxysilane, KBM5103 manufactured by Shin-Etsu Chemical Co., Ltd.). The temperature was 60 ° C. for 1 hour. Then, it heated at 105 degreeC for 10 minute (laminate (A)). Subsequently, the same resin as the resin from which the resin mold was produced was applied to the inorganic base material by the bar coating method, and at the same time, the fine uneven structure forming surface of the resin mold was bonded.

  After irradiating UV light from the resin mold side, the resin mold was peeled off to obtain a resin mold for spin coating. The resin mold for spin coating was stabilized by heating at 180 ° C. for 30 minutes. As a result of confirming the surface fine unevenness of the resin mold for spin coating obtained by observation with a scanning electron microscope, the one using the resin mold (A) derived from quartz 1 has an adjacent distance between the recesses of 200 nm. The height was 200 nm. In the case of using the resin mold (A) derived from quartz 2, the adjacent distance between the recesses was 150 nm, and the recess height was 200 nm. In the case of using the resin mold (A) derived from quartz 3, the adjacent distance between the recesses was 130 nm and the recess height was 100 nm. In the case of using the resin mold (B) derived from quartz 1, the adjacent distance between the convex portions was 200 nm, and the height of the convex portions was 200 nm. In the case of using the resin mold (B) derived from quartz 2, the adjacent distance between the convex portions was 150 nm, and the convex portion height was 200 nm. In the case of using the resin mold (B) derived from quartz 3, the adjacent distance between the convex portions was 130 nm, and the convex portion height was 100 nm. The obtained resin mold for spin coating was produced neatly over the entire surface of the glass substrate.

<Resin mold 4 for spin coating>
To 100 parts by mass of G0210 (Glycidyloxypropyl trimethoxysilane, manufactured by Tokyo Chemical Industry Co., Ltd.), 0.09 parts by mass of water and 2.75 parts by mass of ethanol were added and stirred at room temperature for 30 minutes. Subsequently, the resultant was diluted 10 times with a methyl ethyl ketone solvent and formed on a silicon wafer subjected to ozone treatment by spin coating. After film formation, it was allowed to stand at room temperature for 3 minutes, and then heated at 105 ° C. for 10 minutes (laminate (A)). Subsequently, the same resin as the resin from which the resin mold was produced was applied to the inorganic base material by the bar coating method, and at the same time, the fine uneven structure forming surface of the resin mold was bonded.

  UV light was irradiated from the resin mold side, followed by heating at 105 ° C. for 30 seconds. After heating, the resin mold was peeled off to obtain a resin mold for spin coating. The resin mold for spin coating was stabilized by heating at 180 ° C. for 30 minutes. As a result of confirming the surface fine unevenness of the resin mold for spin coating obtained by observation with a scanning electron microscope, the one using the resin mold (A) derived from quartz 1 has an adjacent distance between the recesses of 200 nm, The height of the recess was 200 nm. In the case of using the resin mold (A) derived from quartz 2, the adjacent distance between the recesses was 150 nm, and the recess height was 200 nm. In the case of using the resin mold (A) derived from quartz 3, the adjacent distance between the recesses was 130 nm and the recess height was 100 nm. In the case of using the resin mold (B) derived from quartz 1, the adjacent distance between the convex portions was 200 nm, and the height of the convex portions was 200 nm. In the case of using the resin mold (B) derived from quartz 2, the adjacent distance between the convex portions was 150 nm, and the convex portion height was 200 nm. In the case of using the resin mold (B) derived from quartz 3, the adjacent distance between the convex portions was 130 nm, and the convex portion height was 100 nm. The obtained resin mold for spin coating was produced neatly over the entire glass substrate.

<Resin mold 5 for spin coating>
0.09 parts by mass of water and 2.75 parts by mass of ethanol were added to 100 parts by mass of 3APTMS (KBM5103, 3 acryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.), and the mixture was stirred for 30 minutes. Subsequently, I.I. 5 parts by mass of 184 (IRGACURE 184 Ciba) was added and stirred at room temperature for 15 minutes. Subsequently, it was diluted 100 times with a methyl ethyl ketone solvent, and a film was formed on a glass substrate subjected to ozone treatment by a bar coating method. After film formation, it was allowed to stand at room temperature for 3 minutes, and then heated at 105 ° C. for 10 minutes (laminate (A)).

  Subsequently, the same resin as the resin that produced the resin mold was formed on the film forming surface of the laminate (A) by the bar coating method, and at the same time, the resin mold was bonded. Thereafter, UV light was irradiated from the resin mold side, and subsequently heated at 105 ° C. for 30 seconds. After heating, the resin mold was peeled off to obtain a resin mold for spin coating. The resin mold for spin coating was stabilized by heating at 180 ° C. for 30 minutes. As a result of confirming the surface fine unevenness of the resin mold for spin coating obtained by observation with a scanning electron microscope, the one using the resin mold (A) derived from quartz 1 has an adjacent distance between the recesses of 200 nm. The height was 200 nm. In the case of using the resin mold (A) derived from quartz 2, the adjacent distance between the recesses was 150 nm, and the recess height was 200 nm. In the case of using the resin mold (A) derived from quartz 3, the adjacent distance between the recesses was 130 nm and the recess height was 100 nm. In the case of using the resin mold (B) derived from quartz 1, the adjacent distance between the convex portions was 200 nm, and the height of the convex portions was 200 nm. In the case of using the resin mold (B) derived from quartz 2, the adjacent distance between the convex portions was 150 nm, and the convex portion height was 200 nm. In the case of using the resin mold (B) derived from quartz 3, the adjacent distance between the convex portions was 130 nm, and the convex portion height was 100 nm. The obtained resin mold for spin coating was produced neatly over the entire surface of the glass substrate.

(D) Transfer A transfer test was performed using all the above-described spin coat resin molds 1 to 5. CTX-809SP2 (trade name, manufactured by Asahi Glass Co., Ltd.) is diluted with perfluorotributylamine (trade name, Fluorinert FC-43, manufactured by Sumitomo 3M Co., Ltd.), and dropped on the surface of the spin coat mold on which the fine concavo-convex structure is formed. Above, spin-coated at 310 rpm. Subsequently, the film was dried at 80 degrees for 5 minutes, and then dried at 180 ° C. for 5 minutes. After returning to room temperature, the thin film (pellicle film) was peeled off by pressing and pulling the frame with the adhesive. When the peeled pellicle film surface was observed with an atomic force microscope, the one using the resin mold (A) derived from quartz 1 had an adjacent distance of 200 nm and a protrusion height of 200 nm. In the case of using the resin mold (A) derived from quartz 2, the adjacent distance between the convex portions was 150 nm, and the height of the convex portions was 200 nm. In the case of using the resin mold (A) derived from quartz 3, the adjacent distance between the convex portions was 130 nm and the convex portion height was 100 nm. In the case of using the resin mold (B) derived from quartz 1, the adjacent distance between the recesses was 200 nm, and the recess height was 200 nm. In the case of using the resin mold (B) derived from quartz 2, the adjacent distance between the recesses was 150 nm and the recess height was 200 nm. In the case of using the resin mold (B) derived from quartz 3, the adjacent distance between the recesses was 130 nm, and the recess height was 100 nm.

  As described above, according to the resin molds 1 to 5 for spin coating according to the present embodiment, even when transferring by a spin coater, the resin layer does not peel from the inorganic base material, and the thin film (pelicle) The fine concavo-convex structure could be transferred to the film. Further, the pellicle film itself could be peeled off without being broken, and the spin coating resin molds 1 to 5 before and after transfer and the fine uneven structure of the peeled pellicle film were not broken or deformed. Further, the above results were the same even when a plurality of pellicle films were transferred from the spin coat resin molds 1 to 5 according to this example.

  In addition, this invention is not limited to the said embodiment, It can change and implement variously. In the above-described embodiment, the size, shape, and the like illustrated in the accompanying drawings are not limited to this, and can be appropriately changed within a range in which the effect of the present invention is exhibited. In addition, various modifications can be made without departing from the scope of the object of the present invention.

  The present invention is excellent in releasability with a resin material, has good adhesion to a base material, and has an effect that film formation by a spin coating method is possible, and particularly in film formation by a spin coating method. It can be suitably used as a resin mold for spin coating to be used.

DESCRIPTION OF SYMBOLS 1 Resin mold for spin coating 2, 22 Laminate 11 Inorganic base material 12 Resin layer 13 Adhesive layer 14 Thin film / self-supporting thin film

Claims (6)

  An inorganic base material; and a resin layer provided on a main surface of the inorganic base material and having a fine concavo-convex structure on a surface thereof, wherein the resin layer is formed on a surface portion of the surface on which the fine concavo-convex structure is formed. A resin mold for spin coating, wherein a fluorine element concentration (Es) is higher than an average fluorine element concentration (Eb) in the resin layer.   2. The resin mold for spin coating according to claim 1, further comprising an adhesive layer provided between the inorganic base material and the resin layer. 2. The resin layer according to claim 1, wherein a ratio between a fluorine element concentration (Es) in the surface portion and an average fluorine element concentration (Eb) in the resin layer satisfies the following formula (1): Or the resin mold for spin coats of Claim 2.
20 ≦ Es / Eb ≦ 200 Formula (1)   A laminate comprising: the resin mold for spin coating according to any one of claims 1 to 3; and a thin film provided on a surface of the resin layer on which a fine concavo-convex structure is formed.   A self-supporting thin film manufactured through the step of isolating the thin film from the laminate according to claim 4, wherein the main surface of one of a pair of opposing main surfaces has a fine concavo-convex structure. Thin film.   An application step of applying a resin material on the fine concavo-convex structure of the resin layer of the resin mold for spin coating according to any one of claims 1 to 3, and peeling for peeling the thin film from the resin layer And a process for producing a self-supporting thin film.

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