JP2010074005A - Method of manufacturing surface treatment mask, method for surface treatment, optical device, and method of manufacturing particle-containing film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface treatment mask that is in a single-layer array without causing particles to overlap, is less apt to have variations in quality even if an object to be treated has a large area, can speedily perform uneven processing, and is excellent in mass productivity and cost reduction, to provide a method of manufacturing the surface treatment mask, to provide a method for surface treatment and an optical device having a substrate treated by the method for surface treatment, and also to provide a particle-containing film in a single-layer array without causing particles to overlap and a method of manufacturing the particle-containing film. <P>SOLUTION: A film mask as a surface treatment mask utilized for the surface treatment method for performing etching for forming irregularities on the surface of an object to be treated by performing etching treatment after disposing the film mask on the surface of the object is formed by nearly simultaneously coating and forming a first coating layer containing a binder and a gelling agent and a second coating layer containing particles onto a base material in this order. After gelling of the first coating layer, the first and second coating layers are dried and formed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a surface treatment mask used in a surface treatment method for forming irregularities on the surface of an object to be processed by etching, and a surface treatment method. The present invention also relates to an optical device having a substrate processed by the surface treatment method. The present invention also relates to a method for producing a particle-containing film containing particles arranged in a single layer.

  Conventionally, in the field of optical devices such as solar cells, LEDs, flat panel displays, etc., in order to suppress the reflection phenomenon that occurs when the refractive index difference of the light transmitting interface is large, it is applied to the substrate surface through which light is transmitted by etching treatment. Processing which forms an unevenness is performed.

  On the other hand, in the field of semiconductor devices, for example, in order to suppress peeling of the thin film due to insufficient adhesion between the thin film and the substrate, a process of forming irregularities on the substrate surface with the aim of an anchor effect is performed. It is also done.

Thus, in various fields, processing for forming irregularities on the surface of an object to be processed has been performed, and various proposals relating to irregularities have been made (for example, Patent Documents 1 to 5).
Japanese Patent Laid-Open No. 3-71677 JP 2000-261008 A JP 2005-277295 A JP 2007-27564 A JP-A-2005-279807

  In the surface treatment method for performing the above-described uneven processing, etching is performed after particles having etching resistance are disposed on the surface of the object to be processed by dry or wet, or a film containing the particles is bonded to the surface of the object to be processed. We are processing.

  At this time, in any of the above methods, it is extremely difficult to cause the particles to exist in a single layer on the surface of the object to be processed, and usually the particles are partially overlapped. When an etching process is performed in this state, only the interstices between the particles are etched, so that only scattered irregularities are formed, resulting in variations in quality. Specifically, for example, as shown in FIG. 7, scattered irregularities are easily formed by the overlap of particles. Here, FIGS. 7A and 7B are process diagrams for explaining the etching process in the conventional surface treatment method. FIG. 7A shows the state before the etching process, and FIG. 7B shows the state after the etching process. Moreover, in FIG. 7, 110 shows a to-be-processed object, 111 shows a film mask (particle layer), 112 shows particle | grains.

  Although a method for removing such overlapping particles is also applied, the process becomes complicated, and in particular, an object to be processed having a large area is unsuitable for mass productivity and cost reduction.

  On the other hand, the particle-containing film that suppresses the partial overlap of the particles and exists as a single layer is not limited to the film applied to the surface treatment method, for example, in the field of optical films (for example, antireflection film, luminance Improvement film, diffusion film, retroreflective sheet, etc.), recording media field, semiconductor field and the like.

  Therefore, the problem of the present invention is that the present invention has a single layer with no overlapping of particles, and it is difficult for the quality to vary even if the object to be processed has a large area, and the uneven processing is performed at high speed. It is possible to provide a method for manufacturing a mask for surface treatment that is excellent in mass productivity and cost reduction. Moreover, the subject of this invention is providing the surface treatment method using the mask for surface treatment obtained by the said manufacturing method. Moreover, the subject of this invention is providing the optical device which has the board | substrate processed by the said surface treatment method. Moreover, the subject of this invention is applying the manufacturing method of the particle | grain containing film which existed and contained by the single layer, without particle | grains overlapping.

The above problem is solved by the following means. That is,
The invention according to claim 1
A method for producing a surface treatment mask for forming irregularities on the surface of an object to be treated, comprising a film mask,
A first coating layer containing a binder and a gelling agent and a second coating layer containing particles are applied and formed on the base material substantially simultaneously in this order, and the first coating layer is gelled. The manufacturing method of the surface treatment mask which has the process of drying 1 coating layer and the said 2nd coating layer, and forming the said film mask.

The invention according to claim 2
In the step of forming the film mask, the first coating layer, the second coating layer, and a third coating layer containing a gelling agent are simultaneously coated and formed in this order on the base material, and then the first coating layer is formed. The method for producing a surface-treated mask according to claim 1, which is a step of drying the first coating layer, the second coating layer, and the third coating layer after gelling the layer and the third coating layer.

The invention according to claim 3
The method for manufacturing a surface treatment mask according to claim 1, wherein the gelling agent is water-soluble.

The invention according to claim 4
The method for producing a surface treatment mask according to claim 1, wherein the gelling agent is gelatin.

The invention according to claim 5
The method for producing a surface treatment mask according to claim 1, wherein the layer obtained by drying the third coating layer is an adhesive layer for adhering the film mask to an object to be processed.

The invention according to claim 6
The manufacturing method of the mask for surface treatments of Claim 1 or 2 whose said base material is a support substrate which supports one main surface of the said film mask.

The invention according to claim 7 provides:
The manufacturing method of the mask for surface treatment of any one of Claims 1-3 which has the process of forming a peeling layer between the said base material and the said film mask.

The invention according to claim 8 provides:
The manufacturing method of the mask for surface treatment of any one of Claims 1-4 which has the process of forming a non-adhesion layer in the surface on the opposite side to the film mask formation side in the said base material.

The invention according to claim 9 is:
The manufacturing method of the mask for surface treatment of any one of Claims 1-5 which has the process of forming a protective film on the said film mask.

The invention according to claim 10 is:
The surface treatment mask according to any one of claims 1 to 6, wherein in the step of forming the film mask, a method of applying and forming the respective coating layers substantially simultaneously is selected from a slide coating method and a curtain coating method. Manufacturing method.

The invention according to claim 11 is:
A surface treatment method for forming irregularities on the surface of a workpiece,
In the surface treatment mask obtained by the method for producing a surface treatment mask according to any one of claims 1 to 5, a bonding step of bonding the film mask to a surface of an object to be processed;
Etching process is performed on the surface of the workpiece to which the film mask is bonded, and an unevenness is formed on the surface of the workpiece,
A surface treatment method characterized by comprising:

The invention according to claim 12
One main surface of the film mask is supported by a support substrate,
The surface treatment method according to claim 11, wherein the bonding step is a step of peeling the support substrate from the film mask after bonding the film mask to a surface of an object to be processed.

The invention according to claim 13 is:
The surface treatment method according to claim 12, further comprising a release layer between the support substrate and the film mask.

The invention according to claim 14 is:
The surface treatment method of Claim 12 or 13 which has a non-adhesion layer in the opposite surface to the arrangement | positioning side of the said film mask in the said support substrate.

The invention according to claim 15 is:
The other main surface of the film mask is covered with a protective film,
The surface treatment method of any one of Claims 11-14 which peels the said protective film from the said film mask before the said bonding process.

The invention according to claim 16 provides:
The surface treatment method according to any one of claims 11 to 15, wherein the bonding step is a step of holding the film mask and the object to be processed by a roller.

The invention according to claim 17 provides:
The surface treatment method according to claim 11, wherein the etching process is a dry etching process.

The invention according to claim 18
The surface treatment method according to claim 11, wherein the surface of the object to be processed that forms irregularities is a light incident surface of an optical device.

The invention according to claim 19 is
The optical device which has a board | substrate as a to-be-processed object surface-treated by the surface treatment method of any one of Claims 11-18.

The invention according to claim 20 provides
A first coating layer containing a binder and a gelling agent and a second coating layer containing particles are applied and formed on the base material substantially simultaneously in this order, and the first coating layer is gelled. The manufacturing method of the particle | grain containing film which has the process of drying 1 coating layer and the said 2nd coating layer, and forming a particle | grain containing film.

The invention according to claim 21 is
In the step of forming the particle-containing film, the first coating layer, the second coating layer, and the third coating layer containing a gelling agent are simultaneously formed on the base material in this order, and then the first coating layer is formed. 21. The method for producing a particle-containing film according to claim 20, which is a step of drying the first coating layer, the second coating layer, and the third coating layer after gelling the coating layer and the third coating layer. .

The invention according to claim 22 is
The method for producing a particle-containing film according to claim 20 or 21, wherein the gelling agent is water-soluble.

The invention according to claim 23 is
The method for producing a particle-containing film according to claim 20 or 21, wherein the gelling agent is gelatin.

The invention according to claim 24 provides
The particle-containing film according to any one of claims 20 to 23, wherein in the step of forming the particle-containing film, a method of applying and forming the respective coating layers substantially simultaneously is selected from a slide coating method and a curtain coating method. Manufacturing method.

  According to the present invention, the problem of the present invention is that the overlapping of particles is suppressed and is easily present as a single layer, the quality does not easily vary even when the object to be processed has a large area, and the uneven processing is performed at high speed. Therefore, it is possible to provide a method for manufacturing a mask for surface treatment which is excellent in mass productivity and cost reduction. Moreover, the surface treatment method using the mask for surface treatment obtained by the said manufacturing method can be provided. Moreover, the subject of this invention can provide the optical device which has the board | substrate processed by the said surface treatment method. Moreover, the particle-containing film which existed by arrange | positioning single layer without particle | grains overlapping, and its manufacturing method can be provided.

  Embodiments of the present invention will be described below with reference to the drawings. In addition, the same code | symbol is provided to the member which has the substantially same function and effect | action through all the drawings, and the overlapping description may be abbreviate | omitted.

  FIG. 1 is a process diagram illustrating a surface treatment method according to an embodiment. Drawing 2 is a schematic structure figure showing the film for surface treatment concerning an embodiment, (A) shows a top view and (B) shows a sectional view. Note that FIG. 1B is a cross-sectional view taken along the line AA in FIG.

  In the surface treatment method according to the present embodiment, first, a surface treatment mask 10 is prepared as shown in FIG. Here, as shown in FIG. 2, the surface treatment mask 10 has a film mask 12 laminated on a support substrate 11. The film mask 12 includes particles 13A having etching resistance, a binder and a gelling agent, and a particle layer 13 in which the particles 13A are exposed, and a coating layer 14 that includes the gelling agent and covers the exposed particles 13A. , Including. The details of the surface treatment mask 10 will be described later.

  Next, as shown in FIG. 1B, the surface mask 10 is covered with the film mask 12 (the coating layer 14 of the film mask 12) facing the substrate 20 to be processed (the object to be processed). It is laminated on the processing substrate 20. As a result, the film mask 12 (the coating layer 14 of the film mask 12) in the surface treatment mask 10 is brought into close contact with the surface of the substrate 20 to be processed.

  Here, there is no restriction | limiting in particular as the to-be-processed substrate 20, For example, the board | substrate comprised by a semiconductor (for example, silicon substrate), an electrically conductive material, an insulator, etc., the glass substrate used with a flat panel display, the said A functional layer (for example, a wiring layer, an insulating layer, or the like) may be formed on the substrate.

  Next, as shown in FIG. 1C, the substrate to be processed 20 on which the surface treatment mask 10 is laminated is inserted into the laminating apparatus 30. Then, for example, a cylindrical sandwiching roller 31 disposed in the laminating apparatus 30 (the number of the sandwiching rollers is not particularly limited, and in the present embodiment, the case where there are three pairs of rollers is displayed) The substrate 20 to be processed on which the processing mask 10 is stacked is sandwiched, and pressure is applied between the surface processing mask 10 and the substrate 20 to be processed, that is, between the film mask 12 and the substrate 20 to be processed. Thereby, the mask 10 for surface treatment and the to-be-processed substrate 20 are press-contacted, ie, the film mask 12 and the to-be-processed substrate 20 are press-contacted. Thereby, the film mask 12 is bonded and fixed to the substrate 20 to be processed.

  Here, in the pressure contact with the sandwiching roller 31, when the coating layer 14 of the film mask 12 is a thermal adhesive layer, it is preferable to heat.

  On the other hand, when the coating layer is not an adhesive layer on the film mask 12 (when the particle layer 13 of the film mask 12 is bonded directly to the substrate 20 to be processed), the pressing by the clamping roller 31 is performed under a vacuum pressure reduction condition (for example, 100 hPa or less). And under a condition of a vacuum higher than the glass transition temperature of the binder when the coating layer in the film mask 12 contains a binder. Specifically, for example, from the point of improving the adhesion between the film mask 12 and the substrate to be processed 20 (that is, the point of suppressing the presence of air bubbles), the pressure contact is preferably performed under a vacuum pressure reduction condition. On the other hand, when the coating layer 14 constituting the film mask 12 contains a binder, when the glass transition temperature of the binder is higher than the production environment (room temperature: for example, 25 ° C.), the temperature condition higher than the glass transition temperature. It is better to press down.

  Further, as a suitable pressure contact condition by the sandwiching roller 31, pressure is maintained at 20 psi to 50 psi with respect to the roller at 50 to 150 ° C. and a pressure of 10 hPa, and pressure contact is performed at a speed of 0.1 m / min to 3 m / min. To do. Moreover, it is preferable that this press-contact process is continuously performed from a viewpoint of productivity, In that case, a well-known continuous processing type vacuum laminator can be used.

  In addition, when heating at the time of the above-mentioned press contact, a heating source (not shown) may be provided inside the sandwiching roller, or a heating source may be provided separately.

  Next, as shown in FIG. 1D, the support substrate 11 is peeled from the substrate 20 to which the surface treatment mask 10 (film mask 12) is pressed. Thereby, the film mask 12 is left on the surface of the substrate 20 to be processed (see FIG. 2A).

  In addition, you may peel the support substrate 11 before the press contact by the clamping roller 31 (lamination apparatus 30). In this case, the surface of the clamping roller 31 (the upper roller in FIG. 1C) disposed on the side in contact with the surface treatment mask 10 is made of a material having good releasability (for example, polytetrafluoroethylene). It is preferable to make it.

  Here, the peeling apparatus for peeling off the support substrate is usually a method of sticking and peeling the pressure sensitive adhesive tape on the tip portion of the support substrate, a method in which compressed air is blown to the tip portion of the support substrate, and laser light irradiation. There is a method of peeling.

  Next, as shown in FIG. 1E, the substrate 20 to which the film mask 12 is bonded is etched from the bonding surface side of the film mask 12. As a result, in the region excluding the region covered with the etching resistant particles 13A constituting the film mask 12 (the region in which the particles 13A are projected onto the substrate 20 when viewed from the etching direction), the surface of the substrate 20 to be processed is While the recess is formed by etching, the surface of the substrate to be processed 20 is not etched in the region covered with the particles 13A (see FIG. 2B).

  Specifically, when the etching process is performed, for example, the binder constituting the particle layer 13 and the coating layer 14 excluding the region covered with the particle 13A are etched, and in the etched region, the coating is performed. Etching of the surface of the processing substrate 20 is performed.

  Thus, the etched region becomes a concave portion, and the non-etched region becomes a convex portion, and irregularities are formed on the surface of the substrate 20 to be processed. In the region to be etched (the region excluding the region covered with the particles 13A), the film mask 12 (the particle layer 13 and the coating layer 14) is etched together.

  Here, as the etching process, both a wet etching process and a dry etching process are employed, but a dry etching process is preferably employed. Known dry etching processes include a reactive gas etching process in which etching is performed by exposing the substrate 20 to be processed in a reactive gas, and a reactive ion etching (RIE) in which reactive gas is ionized and radicalized by plasma to perform etching. The dry etching process is employed. A known apparatus is also used as an apparatus for performing the dry etching process.

On the other hand, the conditions for performing the dry etching treatment are appropriately set according to the thickness and type of the film mask 12 (binder type, particle group type, etc.). It is good to be adopted.
1) dry etching, as the reactive _gas, can be performed by using a _{CF 4, C 2 F 6,} Cl 2, ClF 3.
2) As an etching method with strong anisotropy, it is preferable to use RIE or RIBE (reactive ion beam etching) using a gas such as SiCl ₄ + He or CH ₄ + He.
3) Depending on the type of etching gas, it may penetrate into the substrate to be processed and cause chemical and physical changes, so that the time during which the substrate to be processed is exposed to the etching gas can be optimized. .
4) After a desired uneven shape is obtained by etching, if a part of the film mask remains, the residue is removed by introducing a gas such as ozone or oxygen and irradiating light such as ultraviolet rays. It is possible to employ an ashing method or an ashing method in which oxygen gas is turned into plasma by a high frequency and the like, and the residue is removed using the plasma.

  In the etching process, the process of etching the film mask of the surface treatment mask and the etching process of the substrate 20 to be processed may be performed successively by the etching process of the same technique, or by the etching process of different techniques. Each may be given separately.

  Next, as shown in FIG. 1F, the film mask 12 is peeled (removed) from the substrate 20 to be etched.

  Through the above steps, the surface of the substrate to be processed 20 can be subjected to uneven processing.

  In the surface treatment method according to the present embodiment described above, as will be described later, the film mask 12 in which the particles 13A are blended and exist in a single layer arrangement without overlapping particles is used as the surface treatment mask 10 to be processed substrate 20. In this state, the substrate to be processed 20 is etched.

  That is, since the particles 13A are present in a single layer arrangement on the substrate to be processed 20 without overlapping, a sufficient area to be etched of the substrate to be processed 20 is secured, irregularities at irregular pitches, Irregularity processing is performed on the surface of the substrate 20 to be processed while suppressing the formation of scattered irregularities.

  Further, in the surface treatment method according to the present embodiment, the particles 13A for selecting the region to be etched and the region not to be etched are preliminarily blended into the binder, and the film mask 12 is formed in a layer shape to the substrate 20 to be processed. The particles 13A are arranged on the surface of the substrate 20 to be processed by bonding. For this reason, even if the surface of the substrate to be processed 20 has a large area, the particles 13 </ b> A are arranged on the surface of the substrate to be processed 20 by a simple and quick operation of bonding the film mask 12. In addition, since the film mask 12 can be manufactured by the operation of blending the particles 13A into the binder, the film mask 12 can be manufactured to a certain degree of quality (that is, the distance between the particles arranged in a single layer without overlapping particles). Easy to manufacture.

  Therefore, even if the object to be processed has a large area, it is difficult for the quality to vary, and uneven processing can be performed at high speed, which is excellent in mass productivity and cost reduction.

  In addition, by the surface treatment method according to the present embodiment, the equivalent diameter of the uneven shape after the surface treatment of the substrate to be processed 20 (object to be processed) is, for example, at least 60% of the total number in the case of the light incident surface of the solar cell. However, it is more preferable that at least 80% is in the range of 200 nm to 1000 nm. The equivalent diameter is obtained by measuring the surface shape of the concave portion of the surface with a contact type surface shape measuring device such as a surface roughness meter or a non-contact type surface shape measuring device such as AFM, so that a non-processed portion, that is, unevenness is formed. The area of the part surrounded by the part of 10% depth from the reference surface of the distance from the reference surface to the maximum depth of the processed part was obtained using a non-flat part as the reference surface, and the circle was calculated from this area value. The diameter is defined as the equivalent diameter. In this case, when the equivalent diameter is 10 nm or less, the dent is regarded as a flat portion where no irregularities are formed, and is not counted as a dent. At this time, the number of the recessed portions to be measured is suitably at least 10, more preferably 50 or more, still more preferably 100 or more, and most preferably 500 or more. As a specific measuring method, for example, in the contour map of the shape measurement result measured in the non-contact mode by AFM, the depth z0 of the deepest portion is obtained, and the value of 10% of this z0 is 0.1 * z0. Then, the depth zij at each measurement position (i, j) is given by zij = zij−0.1 * z0. Using this zji, the contour map is displayed again and printed out, and the above-mentioned area can be obtained from this output map by a known method. In addition, it is also possible to perform data processing with digital data directly from the AFM measuring machine to obtain the area, and all existing methods can be used.

  Hereinafter, details of the surface treatment mask 10 applied to the surface treatment method according to the present embodiment will be described. In the following description, reference numerals are omitted.

  The surface treatment mask is configured by laminating a film mask on a support substrate. The film mask 12 includes particles having etching resistance, a binder and a gelling agent, and a particle layer in which the particles are exposed, and a coating layer containing the binder and the gelling agent and covering the exposed particles. It is configured to include. The film mask includes a first coating layer containing a binder and a gelling agent on a base material (supporting substrate), a second coating layer containing particles, and a third coating layer containing a gelling agent. After coating and forming simultaneously in this order, the first coating layer and the third coating layer are gelled, and then the first coating layer, the second coating layer, and the third coating layer are dried to form. The layer obtained by drying the first coating layer and the second coating layer corresponds to the particle layer from which the particles are exposed. The layer obtained by drying the third coating layer corresponds to a coating layer that covers the particles.

  In addition, the coating layer which covers particle | grains is not essential, For example, when forming a particle layer directly in a to-be-processed substrate, you may comprise only a particle layer, without providing a coating layer as a film mask. In this case, for example, the film mask is formed by applying a first coating layer containing a binder and a gelling agent and a second coating layer containing particles on the base material (supporting substrate) almost simultaneously in this order, After the one coating layer is gelled, the first coating layer and the second coating layer are formed by drying.

  Here, in order to form a particle layer (film mask), for example, a coating solution containing particles and a binder is used, and this is applied and dried. In the coating film of particles and binder, the concentration of the binder becomes high, the particles are difficult to move, and the particles are difficult to settle, so that the particles are not arranged in a single layer and the particles overlap each other. A layer (film mask) is formed.

  Therefore, first, a first coating liquid layer containing a binder and a gelling agent and a second coating layer (non-binder-containing coating layer) containing particles having etching resistance are applied and formed in this order almost simultaneously. To do. And when the 1st application layer is gelatinized, the 1st application layer will be in the state where mixing of the upper 2nd application layer by gelation was controlled. That is, mixing of the particles of the second coating layer with the lower first coating layer is suppressed. When each layer is dried in this state, in the second coating layer, the state in which the particles easily move is maintained, and a single layer is provided while the particles settle according to the evaporation of the solvent. Further, since the first coating layer is in a gel form, the first coating layer is also dried while a part of the settled particles are embedded in the surface of the first coating layer, and a layer made of a binder is formed. As a result, a particle layer in which the particles are bound by the binder while a single layer is arranged is formed.

  When the third coating layer containing the gelling agent is applied and formed in this order together with the first coating layer and the second coating layer, and the first coating layer and the third coating layer are gelled, the third coating layer is formed. Is in a state where mixing of the lower second coating layer is suppressed by gelation. That is, mixing of the particles of the second coating layer with the upper third coating layer is suppressed. When each layer is dried in this state, since the third coating layer is in the form of a gel, the third coating layer is also dried while covering the particles settled in a single layer arrangement as described above and filling the particle gaps. A particle-coated layer is formed. Thereby, a coating layer is formed covering the exposed particles of the particle layer.

  Accordingly, the surface treatment mask (film mask) is present in a single layer arrangement without overlapping particles, and the particles 13A are blended. As described above, even if the object to be processed has a large area, the quality hardly varies. In addition, it is possible to provide a surface treatment method that can perform uneven processing at high speed and is excellent in mass productivity and cost reduction.

Hereinafter, the surface treatment mask will be described in more detail.
The mask for surface treatment may be provided with the back surface of the support substrate (the surface opposite to the side on which the film mask is provided) and a non-adhesive layer. Further, the surface treatment mask may have a protective film that covers and protects the other surface of the film mask, or a release layer for improving the peelability between the film mask and the support substrate. That is, in the manufacturing method mentioned later, you may have the process of forming a non-adhesion layer, a protective film, and a peeling layer.

  Here, as long as the mask for surface treatment has a film mask, another structure is arbitrary structures. Specifically, for example, if the film mask itself has a self-supporting property, the surface treatment mask may be composed of a film mask. In addition, if the surface treatment masks are not bonded to each other when the surface treatment masks are laminated or rolled, it is not necessary to provide a non-adhesive layer.

Next, the film mask will be described.
The film mask includes a particle layer containing particles having etching resistance, a binder, and a gelling agent and exposing the particles, and a coating layer containing the gelling agent and covering the exposed particles. . In addition, a coating layer is a layer provided arbitrarily.

  The average thickness T1 of the particle layer is preferably, for example, 0 to 1 μm, and more preferably 0 to 0.2 μm. On the other hand, it is preferable that the thickness of a coating layer is 0.3 micrometer-5 micrometers, for example, More preferably, they are 0.5 micrometer-2 micrometers. The thickness of each layer indicates the thickness of the constituent material (for example, binder) excluding the particles (in FIG. 2, T1 indicates the thickness of the particle layer, and T2 indicates the thickness of the coating layer).

  The particle layer includes particles having etching resistance, a binder, and a gelling agent. Although the particles are included in a single layer arrangement as described above, the particles need not be arranged in a close-packed manner, and may be arranged with a gap between the particles. That is, the particle layer is preferably formed by adjusting the amount of particles and the amount of the binder so as to be a single layer arrangement even when randomly arranged on a plane. In addition to the particles having etching resistance, other types of particles may be included.

  The particles are not particularly limited as long as they have etching resistance, and examples thereof include inorganic particles, organic dye / pigment particles containing an inorganic element, latex particles containing an inorganic element, and capsule particles. Among these, inorganic particles are preferable from the viewpoints of etching resistance, availability, and handleability.

Examples of the inorganic particles include non-metallic materials such as titanium oxide, silica, calcium carbonate, and strontium carbonate, metals, and semiconductor materials. For example, the metal includes Cu, Au, Ag, Sn, Pt, Pd, Ni, Co, Rh, Ir, Al, Fe, Ru, Os, Mn, Mo, W, Nb, Ta, Bi, Sb, and Pb. Examples thereof include a single metal selected from the group or an alloy material composed of one or more of the metals selected from the group. Examples of the semiconductor include Si, Ge, AlSb, InP, GaAs, GaP, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, PbTe, SeTe, and CuCl. Moreover, the microcapsule etc. which included these inorganic particles and used silica as the wall membrane material are mentioned.
Examples of organic dye / pigment particles containing an inorganic element include metal element-containing azo dye particles and metal element-containing phthalocyanine dye particles.
Examples of latex particles and capsule particles containing inorganic elements include particles in which acrylic latex is coated with colloidal silica, particles in which acrylic latex is coated in silicate, particles in which polystyrene latex particles are coated with silica, and the like.

  The average particle size of the particles is preferably 0.1 μm to 1 μm, more preferably 0.2 μm to 0.5 μm. The average particle size is preferably in the above range from the viewpoint of thinning the polymer film mask.

  Here, the average particle diameter of a particle means the particle diameter obtained by a dynamic light scattering method, and the measuring method is as follows. In the dynamic light scattering method, it is possible to measure the particle size and particle size distribution in the submicron range or less, and the particles to be measured or dispersions thereof are dispersed by a known method such as ultrasonic irradiation in a medium. Then, after diluting it appropriately, a measurement sample is obtained. In the cumulative frequency curve of the particle size obtained by the dynamic light scattering method, the particle size having a cumulative frequency of 50% is defined as the average particle size, and the ratio of the 10% cumulative particle size to the 90% particle size is similarly determined. An example of a measuring apparatus that employs such a principle that can be used as an index of distribution is LB-500 manufactured by Horiba, Ltd.

  Moreover, it is preferable that the particle size distribution of particle | grains is 2-50, More preferably, it is 2-10. By setting the particle size distribution in the above range, the maximum average particle size does not become too large, a flat polymer film mask layer can be easily obtained, and uniform surface treatment can be easily realized.

  Here, the coverage of the particles functioning as an etching mask is preferably 5% or more and less than 60%, more preferably 10% to 50%, and still more preferably 20% with respect to the surface of the substrate to be processed. ~ 40%. The coverage is selected depending on the extent of the etching area for the uneven processing.

  The coverage is the ratio of the particles covering the substrate to be processed when the film mask is bonded to the substrate to be processed, that is, the ratio of the area where the particles are projected onto the substrate when viewed from the etching direction. . This coverage is measured as follows. After bonding to the substrate to be processed, the surface can be observed using a scanning electron microscope or an optical microscope, and can be calculated from the projected area. In the case of using a scanning electron microscope, it is preferable that the sample can be observed as it is without surface treatment.

  In addition, the specification of the unevenness processing of the surface of the substrate to be processed, that is, the diameter (equivalent diameter), depth, and processing area ratio of the surface unevenness after the etching process can be controlled by the coverage of the particles. It can be arbitrarily designed according to the blending amount of particles in the film mask and the average particle size.

  As the binder constituting the particle layer (film mask), for example, a water-soluble polymer material or an organic solvent-soluble polymer material can be used. Depending on the method of manufacturing the film mask, each polymer The polymerizable monomer forming the material can be mixed with other components constituting the film mask to form a film by polymerization reaction with light or heat. As an example of the polymerizable monomer, (meth) acrylic monomer, (meth) acrylic acid C1-C12 alkyl ester, and these and a known compound as a new acrylic modifier can be used in combination. it can. Examples of the acrylic modifier include carboxy-containing monomers and acid anhydride-containing monomers. These polymerizable monomer monomers can be polymerized by a known polymerization method, and can be appropriately selected from known materials such as an initiator, a chain transfer agent, an oligomer material, and a surfactant necessary for the polymerization. Examples of the polymerizable monomer include known epoxy monomers and isocyanate monomers.

  More specifically, examples of the binder include a glass transition temperature of −100 to 50 ° C., a number average molecular weight of 1,000 to 200,000, preferably 5,000 to 100,000, and a degree of polymerization of about A thing about 50-1000 is mentioned suitably. Examples of such include vinyl chloride, vinyl acetate, vinyl alcohol, maleic acid, acrylic acid, acrylic ester, vinylidene chloride, acrylonitrile, methacrylic acid, methacrylic ester, styrene, butadiene, ethylene, vinyl butyral, vinyl acetal, Examples include polymers or copolymers containing vinyl ether as a structural unit, polyurethane resins, various rubber resins, and modified polyvinyl alcohol having a weight average molecular weight of 100,000 or less.

  Moreover, as a binder, for example, a thermosetting resin or a reactive resin is also preferable. Examples of thermosetting resins or reactive resins include phenol resins, epoxy resins, polyurethane curable resins, urea resins, melamine resins, alkyd resins, acrylic reactive resins, formaldehyde resins, silicone resins, epoxy-polyamide resins, and polyester resins. Examples thereof include a mixture of isocyanate prepolymer, a mixture of polyester polyol and polyisocyanate, and a mixture of polyurethane resin and polyisocyanate. These resins are described in detail in “Plastic Handbook” published by Asakura Shoten. Moreover, it is also possible to use a well-known electron beam curable resin. The above resins can be used alone or in combination.

Here, as the structure of the polyurethane resin, known structures such as polyester polyurethane, polyether polyurethane, polyether polyester polyurethane, polycarbonate polyurethane, polyester polycarbonate polyurethane, and polycaprolactone polyurethane can be used. For all of the polyurethane resin shown here, better dispersibility and necessary in order to obtain a durable _{-COOM, -SO 3 M, -OSO 3} M, -P = O (OM) 2, - O—P═O (OM) ₂ (wherein M represents a hydrogen atom or an alkali metal), —NR ₂ , —N + R ₃ (R is a hydrocarbon group), epoxy group, —SH, —CN, It is preferable to use one in which at least one polar group selected from the above is introduced by copolymerization or addition reaction. The amount of such a polar group is 10 ⁻¹ to 10 ⁻⁸ mol / g, preferably 10 ⁻² to 10 ⁻⁶ mol / g. In addition to these polar groups, it is preferable to have at least one OH group in total at least one at the end of the polyurethane molecule. Since OH groups are cross-linked with polyisocyanate which is a curing agent to form a three-dimensional network structure, it is more preferable that the OH groups are contained in the molecule. In particular, it is preferable that the OH group is at the molecular end because the reactivity with the curing agent is high. The polyurethane preferably has 3 or more OH groups at the molecular terminals, and particularly preferably 4 or more.

  On the other hand, as polyisocyanate, such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, etc. Examples thereof include isocyanates, products of these isocyanates and polyalcohols, and polyisocyanates formed by condensation of isocyanates. Commercially available product names of these isocyanates include Nippon Polyurethane, Coronate L, Coronate HL, Coronate 2030, Coronate 2031, Millionate MR, Millionate MTL, Takeda Pharmaceutical, Takenate D-102, Takenate D- 110N, Takenate D-200, Takenate D-202, manufactured by Sumitomo Bayer, Death Module L, Death Module IL, Death Module N, Death Module HL, etc. Or it can be used in combination more than that.

It is preferable that the glass transition temperature of a binder is 50 degrees C or less, More preferably, it is -60 degreeC-30 degreeC, More preferably, it is -50 degreeC-30 degreeC. The glass transition temperature is preferably in the above range from the viewpoint of improving the storage stability with respect to a film mask (surface treatment mask), the handleability during uneven processing, and the adhesion to the substrate to be processed.
Here, the glass transition temperature can be measured using a film mask material as a sample and using a known thermal analyzer or mechanical property measuring device, but with a dynamic viscoelasticity measuring device, the bending mode and the measurement frequency are 1 Hz. It is preferable to measure at a heating rate of 5 ° C./min.

  As the binder, in addition to the above, polyvinyl alcohol or derivatives thereof, cellulose derivatives (polyvinylpyrrolidone, carboxymethylcellulose, hydroxyethylcellulose, etc.), natural polysaccharides or derivatives thereof (starch, xanthan gum, alginsan, etc.), water dispersible Examples thereof include urethane and acrylic polymer latex.

  The blending amount of the binder resin is appropriately set according to the coverage and the dispersibility of the particles. %.

  Examples of the gelling agent constituting the particle layer (film mask) include substances that cause gelation of the solution (coating layer) when cooled, and substances that cause gelation when used in combination with a gelation promoting substance. In view of gelling the solution (coating layer), the solution (coating layer) is preferably a substance that gels when cooled.

  As the gelling agent, a water-soluble substance is preferable, and specific examples include gelatin, agar, carrageenan, pectin, duran gum, sodium carboxymethylcellulose, xanthan gum, and gelatin is particularly preferable.

  The blending amount of the gelling agent depends on the gelling agent, but is preferably 1% by weight to 20% by weight, more preferably 2% by weight to 10% by weight, and still more preferably 3% by weight with respect to water. % To 6% by weight.

  Moreover, you may mix | blend a thickener with a gelatinizer. Examples of the thickener include water-soluble polymers such as potassium polystyrene sulfonate, styrene-maleic acid copolymer, and dextran sulfate. The blending amount of the thickener is preferably 20% by weight to 100% by weight with respect to the gelling agent, for example.

Other additives that make up the particle layer (film mask) include a dispersant that can stably disperse particles, for example, a release agent that adjusts the adhesive strength with a support substrate and a protective film, And surfactants for adjusting the viscosity and surface tension of the coating solution.
In particular, as a dispersant, phenylphosphonic acid, specifically “PPA” of Nissan Chemical Co., Ltd., α-naphthyl phosphoric acid, phenylphosphoric acid, diphenylphosphoric acid, p-ethylbenzenephosphonic acid, phenylphosphinic acid, aminoquinones, various Silane coupling agents, titanium coupling agents, fluorine-containing alkyl sulfates and alkali metal salts thereof can be used. In addition, nonionic surfactants such as alkylene oxide, glycerin, glycidol, alkylphenol ethylene oxide adducts, cyclic amines, ester amides, quaternary ammonium salts, hydantoin derivatives, heterocycles, phosphonium or sulfoniums, etc. Cationic surfactants, anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfate ester group, phosphate ester group, amino acids, aminosulfonic acids, sulfuric acid or phosphate esters of amino alcohol, alkyl Bedin type amphoteric surfactants and the like can also be used. As the dispersant, polyoxyethylene alkylphenyl ether, polyoxyalkylene block copolymer, polyoxyethylene alkylphenyl ether having a polymerizable unsaturated bond such as an allyl group, or the like may be selected. These dispersants (surfactants) are described in detail in “Surfactant Handbook” (published by Sangyo Tosho Co., Ltd.). These dispersants and the like are not necessarily 100% pure, and may contain impurities such as isomers, unreacted materials, side reaction products, decomposition products, and oxides in addition to the main components. These impurities are preferably 30% or less, more preferably 10% or less. In the present invention, it is also preferable to use a combination of a monoester and a diester as described in the pamphlet of WO 98/35345 as a fatty acid ester.

  Here, the coating liquid for forming the particle layer includes a coating liquid for forming the first coating layer and a coating liquid for forming the second coating layer. The coating liquid for forming the first coating layer is constituted, for example, by dispersing or dissolving at least a binder and a gelling agent in a solvent as necessary, among the above-described components constituting the particle layer. . On the other hand, the coating liquid for forming the second coating layer is constituted, for example, by dispersing at least particles in a solvent among the constituent components constituting the particle layer. Examples of the solvent include an aqueous solvent and an organic solvent, and an aqueous solvent is particularly preferable.

  On the other hand, the coating layer is a particle-free layer formed so as to cover the exposed particles of the particle layer. And a coating layer is comprised including at least a gelatinizer. The coating layer may contain a binder together with the gelling agent, that is, the coating layer may have the same configuration as that of the particle layer except for the particles.

  The covering layer functions as a layer for improving the adhesion between the film mask and the substrate to be processed, and can be used as a layer functioning as an adhesive layer (particularly, a thermal adhesive layer that exhibits adhesiveness by heating). . As the coating layer, for example, it can be made to function as an adhesive layer (thermal adhesive layer) by being composed of the above-described binder.

  Here, the coating liquid (second coating liquid) for forming the coating layer is constituted, for example, by dispersing or dissolving the above-described constituent components in a solvent as necessary. Examples of the solvent include an aqueous solvent and an organic solvent, and an aqueous solvent is particularly preferable.

Next, the support substrate will be described.
For example, a resin film is applied as the support substrate. Examples of the resin film include a resin film formed from polyester (for example, polyethylene terephthalate, polyethylene naphthalate, etc.), polyphenylene sulfide, polyimide, and the like, or a mixture thereof. Further, the surface of the support substrate on the side where the film mask is formed can optimize the peeling force of the film mask by appropriately controlling the interfacial energy. As a specific example, it is preferable to form a silicon-based release agent layer. Examples thereof include a coating of a silicon-based surfactant, a coating-cured layer of an ionizing radiation polymerization type silicon monomer, and a coating layer of an organosiloxane polymer. Similarly, control of the interfacial energy by applying a fluorosurfactant can be exemplified.

  As thickness of a support substrate, 30 micrometers-300 micrometers are preferable, More preferably, they are 50 micrometers-100 micrometers. The thickness is preferably in the above range from the viewpoint of imparting self-supporting property to the mask for surface treatment and improving the handleability during storage and bonding to the substrate to be processed.

The adhesive force between the support substrate and the film mask is preferably lower than the adhesive force between the film mask and the substrate to be processed (adhesive force when peeling the support substrate from the film mask). Thereby, when peeling a support substrate from a film mask, it suppresses that the said film mask peels from a to-be-processed substrate.
Specifically, the adhesive force between the support substrate and the film mask is preferably 5 N / 10 mm or less, more preferably 0.01 N / 10 mm to 1 N / 10 mm, and still more preferably 0.05 N / 10 mm to 1 N / mm. 10 mm.

  Here, the adhesive force can be measured by a method defined by JIS or ASTM, a so-called 180-degree peeling method, and the layer provided on the substrate has an angle of 180 degrees and a speed of 6 in / min (about 152. When it is peeled off at 4 mm / min), it means the average load required for peeling per unit width to which the layer is attached (ASTM D-903).

  In addition, when a support substrate and a film mask cannot acquire the said adhesive force, it is good to arrange | position the peeling layer mentioned later.

Next, the protective film will be described.
The protective film is a layer disposed to cover and protect the other surface of the film mask. As the protective film, a polymer film made of an aliphatic polymer or an aromatic polymer is used, and examples thereof include polyethylene, polypropylene film, and polyethylene terephthalate film. This polymer film can be used alone or can be provided with a layer coated with a polymer material such as an acrylic material called rubber, rubber, or ethylene vinyl copolymer.

  The thickness of the protective film is preferably 30 μm to 100 μm, more preferably 40 μm to 70 μm. The thickness is preferably in the above range from the viewpoint of protecting the bonding surface of the film mask to the substrate to be processed and improving the handleability of the mask for processing.

The adhesive force between the protective film and the film mask is preferably lower than the adhesive force between the film mask and the support substrate (adhesive force when peeling the protective film from the film mask). Thereby, when peeling a protective film from a film mask, it suppresses that the said film mask peels from a to-be-processed substrate.
Specifically, the adhesive force between the protective film and the film mask is preferably 5 N / 10 mm or less, more preferably 0.01 N / 10 mm to 1 N / 10 mm, and still more preferably 0.05 N / 10 mm to 1 N. / 10 mm. If the protective film is not adhered to the film mask and is merely sandwiched as so-called “interleaf”, the adhesive force is substantially zero.

Next, the release layer will be described.
A peeling layer is a layer for improving the peelability of a film mask and a support substrate. As a peeling layer, a thermoplastic resin layer (For example, thickness is less than 15 micrometers (preferably less than 5 micrometers)) is mentioned, for example. As an example of a preferable thermoplastic resin constituting the thermoplastic resin layer, an example of a binder constituting a film mask can be mentioned, but a preferable glass transition temperature is from the glass transition temperature of the binder constituting the film mask. It is preferably 10 ° C to 50 ° C higher. When the glass transition temperature is in the above range, defects such as cracks and cracks are hardly generated in the thermoplastic resin layer as an intermediate layer in the press-contacting process to the substrate to be processed, and the thermoplastic resin layer is supported by the support substrate. It becomes easy to peel from. Moreover, the deterioration of productivity by the increase in the processing time in an etching process is suppressed by making the thickness of a thermoplastic resin layer into the said range.

  For the release layer, for example, a fluorine-based material layer (for example, a thickness of less than 15 μm (preferably less than 5 μm)) may be applied. Examples of the fluorine-based material constituting the fluorine-based material layer include an anionic type (for example, perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate ester) and an amphoteric type (for example, perfluoro). Alkylbetaine, etc.), cation type (perfluoroalkyltrimethylammonium salt, etc.), nonionic type (perfluoroalkylamine oxide; perfluoroalkylethylene oxide adduct; perfluoroalkyl group and hydrophilic group-containing oligomer; perfluoro A fluorine-based material such as an alkyl group, a perfluoroalkyl group and a lipophilic group-containing urethane; Further, these fluorine-based materials may be added to the thermoplastic resin layer as a release layer or a film mask (particle layer) to improve the peelability.

Next, the non-adhesive layer will be described.
The non-adhesion layer is a layer for preventing adhesion between the surface treatment masks when the surface treatment masks are laminated or rolled. As the non-adhesive layer, for example, the above-described fluorine-based material layer (for example, a thickness of less than 15 μm (preferably less than 5 μm)) is preferably exemplified.

  Next, an example of a method for manufacturing a surface treatment mask will be described. FIG. 3 is a process diagram illustrating the method for manufacturing the surface treatment mask according to the embodiment. FIG. 4 is a schematic configuration diagram illustrating a surface treatment mask manufacturing apparatus according to an embodiment.

  In the method for manufacturing a surface treatment mask, as shown in FIG. 4, a support substrate wound in a roll shape is sent out, and each layer is coated, gelled, dried, and conditioned in the transport path, and then wound. This is a method for obtaining a surface treatment mask. In this embodiment, a manufacturing method for forming a film mask on a support substrate will be described. However, when a protective film, a release layer, and a non-adhesive layer are formed, for example, a layer having the above-described structure is formed by coating or lamination. Can be formed.

  Specifically, as shown in FIG. 4, for example, the support substrate 11 (sheet) wound in a roll shape is sent out by a feeding device (not shown) (see FIG. 3A), and curved by the transport roller 40 </ b> A. The first coating layer 15A, the second coating layer 15B, and the third coating layer 15C are applied and formed in this order almost simultaneously on the surface of the support substrate 11 by the slide hopper coating device 50 (FIG. 3B). ).

  Here, as shown in FIGS. 4 and 5, the slide hopper coating apparatus 50 includes, for example, a coating liquid (a binder and a gelling agent) for forming the first coating layer 15 </ b> A on the slide hopper head 51. A storage tank 52A for storing a coating liquid), a storage tank 52B for storing a coating liquid (a coating liquid containing particles) for forming the second coating layer 15B, and a coating liquid for forming the third coating layer 15C. A storage tank 52C for storing (a coating liquid containing a gelling agent) is connected by pipes 54A, 54B, and 54C via pumps 53A, 53B, and 53C, respectively. The pumps 53A, 53B, and 53C supply the coating liquids from the storage tanks 52A, 52B, and 52C to the slide hopper head 51 through the pipes 54A, 54B, and 54C, and the slide surfaces 51A from the slots 55A, 55B, and 55C. The coating liquid for forming the first coating layer 15A, the coating liquid for forming the second coating layer 15B, and the third coating layer 15C are formed while being slid by its own weight on the slide surface 51A. A multilayer film is formed simultaneously with a coating solution for the purpose, and the multilayer film is attached to the surface of the support substrate 11 being conveyed from the slide surface 51A etch (end part). As a result, the respective coating layers are formed by multilayer coating substantially simultaneously. FIG. 5 is a schematic configuration diagram showing the periphery of the slide hopper head of the slide hopper coating apparatus.

  Next, the support substrate 11 on which each coating layer is formed is conveyed into the cooling device 41, and each coating layer is cooled. Thereby, the first coating layer 15A and the third coating layer 15C containing the gelling agent are gelled (see FIG. 3C).

  Next, the support substrate 11 in which the first coating layer 15 </ b> A and the third coating layer 15 </ b> C have been gelled is conveyed into the drying device 42, and each coating layer is dried. As a result, the first coating layer 15A and the second coating layer 15C are dried, thereby forming the particle layer 13 in which the single-layer arranged particles 13A are exposed, and the third coating layer 15C is dried. Thus, the coating layer 14 is formed to cover the exposed particles 13A. (Fig. 3 (D))

  Next, the support substrate 11 on which the particle layer 13 and the coating layer 14 are formed is conveyed into the humidity control device 43. Thereby, generation | occurrence | production of the crack of an application surface, a curl, etc. can be suppressed.

  Thereafter, while being transported by the transport roller 40B, the support substrate 11 (surface treatment mask) formed with each layer is again wound into a roll shape by a winding device (not shown). Thus, the surface treatment mask 10 having the film mask 12 composed of the particle layer 13 and the coating layer 14 is obtained on the support substrate 11.

  In addition, the coating method for forming each coating layer substantially simultaneously is not limited to the slide coating method using the slide hopper coating device, and may be selected from the curtain coating method.

  Here, in the present embodiment, the respective coating layers are formed substantially simultaneously. However, the “substantially simultaneous” means that the simultaneous multi-layer coating method such as the slide coating method or the curtain coating method is used for multi-layer coating. First, it also includes multilayer coating by continuously arranging (or adjacently arranging) a single layer forming type coating apparatus.

  The surface treatment mask described above may be stored, traded and used in the state of being wound in a roll as shown in FIG. 6 (A), or as shown in FIG. 6 (B). It may be stored, traded, and used in a laminated state. Here, FIG. 6 is a perspective view for explaining the storage shape of the surface treatment mask according to the embodiment, in which (A) shows a roll shape, and (B) shows a laminate in a sheet shape.

Note that the surface treatment method (surface treatment mask) according to the present embodiment is suitably applied to, for example, the following uneven processing.
1) In the field of optical devices such as solar cells, LEDs, flat panel displays, etc., in order to suppress the reflection phenomenon that occurs when the refractive index difference of the light transmitting interface is large, it is applied to the substrate surface through which light is transmitted by etching treatment. Concavity and convexity processing for forming concavities and convexities 2) In the field of semiconductor devices, in order to suppress peeling of the thin film due to insufficient adhesion between the thin film and the substrate, the concavity and convexity are formed on the substrate surface with the aim of an anchor effect. Uneven processing to be formed

  In particular, when applied to the field of optical devices, the surface (processing surface) of the workpiece (substrate) on which the irregularities are formed is preferably an optical device light incident surface. Thereby, the reflection phenomenon of the optical device is efficiently suppressed. As described above, a typical example of an optical device including an object processed by the surface treatment method according to the present embodiment is a solar cell having a substrate as the object to be processed. The solar cell has a known configuration, for example, a photovoltaic layer disposed between the substrate, the pair of electrodes, and the pair of electrodes, except that the solar cell includes the substrate treated by the surface treatment method according to the present embodiment. It is set as the structure provided.

  Further, the surface treatment mask (film mask) applied to the surface treatment method according to the present embodiment and the manufacturing method thereof are present in a single-layer arrangement without overlapping particles, and therefore only applied to the surface treatment method. For example, particle-containing films (film masks) used in the fields of optical films (for example, antireflection films, brightness enhancement films, diffusion films, retroreflective sheets, etc.), recording media fields, semiconductor fields, etc. and their production It can be applied as a method.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention.

The coating liquid used is shown below.
-Coating liquid 1
A gelatin (made by Nitta Gelatin) 3% aqueous solution and a PVA (made by Kuraray) 1% aqueous solution were mixed in 50 parts by weight, respectively, and a thickener (manufactured by Sankyo Chemical, polystyrene sulfonate potassium) 5 parts by weight and 0.5 part by weight of a surfactant (2-ethylhexylsulfosuccinate Na) were added to obtain a coating solution 1.

-Coating liquid 2-
10 parts by weight of silica particles (PL-20 manufactured by Fuso Chemical Co., Ltd., average particle size 0.22 μm) and 1 part by weight of surfactant (2-ethylhexylsulfosuccinate Na) per 100 parts by weight of a 1% solution of PVA (made by Kuraray) After mixing and stirring, the mixture was subjected to ultrasonic dispersion to obtain coating solution 2.

-Coating solution 3-
Gelatin (made by Nitta Gelatin) 3% aqueous solution and PVA (made by Kuraray) 3% aqueous solution were mixed in 50 parts by weight, respectively, and thickener (Sankyo Chemical Co., Ltd., polystyrene sulfonate potassium) 1 wt. And 1.0 part by weight of a surfactant (2-ethylhexylsulfosuccinate Na) were added to obtain coating solution 3.

-Coating liquid 4-
A coating solution 4 was obtained by adding 0.5 parts by weight of a surfactant (2-ethylhexylsulfosuccinate Na) to 100 parts by weight of a 2% aqueous solution of PVA (manufactured by Kuraray).

-Coating liquid 5-
A coating solution 5 was obtained by adding 1.0 part by weight of a surfactant (Na-ethyl 2-ethylhexylsulfosuccinate) to 100 parts by weight of a 3% aqueous solution of PVA (manufactured by Kuraray).

Example 1
First, a surface treatment mask was produced as follows (see FIG. 4).
While a roll-shaped polyethylene terephthalate (PET) sheet having a width of 1500 mm and a thickness of 70 μm is run at 50 m / min from the feeding device, the coating liquid 1, the coating liquid 2, and the coating liquid 3 are formed by a slide hopper coating device. Each coating layer was formed by simultaneous multilayer coating in sequence. Each coating layer by coating solution 1, coating solution 2, and coating solution 3 was formed with a wet thickness of 14 μm, 5 μm, and 14 μm, respectively.
Next, the PET sheet on which each coating layer is formed is conveyed into a cooling device, cooled at 15 ° C. for 30 seconds, and coated layer (first coating layer) by coating solution 1 and coating layer (first coating layer by coating solution 3) 3 coating layers) were gelled.
Next, the PET sheet on which each coating layer was formed was conveyed into a drying apparatus and dried at 35 ° C. for 5 minutes to form a particle layer in which the particles were exposed and a coating layer that covered the exposed particles.
Next, the PET sheet on which the particle layer and the coating layer were formed was conveyed into a humidity control device, and the temperature and humidity of each layer were adjusted at 25 ° C. and 35% RH for 30 seconds.
Thereafter, the PET sheet on which each layer was formed was wound up by a winding device to form a roll. In this way, a surface treatment mask was prepared in which a film mask composed of a particle layer and an adhesive layer was disposed on a PET sheet (supporting substrate).

  Then, after cutting the obtained surface treatment mask into a size of 300 × 500 mm, the surface treatment is performed as follows, and a silicon substrate (object to be processed: diameter 100 mm, thickness 0.3 mm) is obtained. The surface of the surface was roughened.

  First, the surface treatment mask is laminated on the surface of the silicon substrate so that the film mask faces the silicon substrate. Next, the silicon substrate on which the surface treatment mask is laminated is inserted into a laminating apparatus, and is sandwiched between sandwiching rolls under conditions of vacuum reduced pressure (50 hPa) and temperature 60 ° C., and the surface treatment mask (film mask) and silicon Press contact with the substrate. Thereafter, the support substrate is peeled off from the film mask, and the film mask is bonded to the silicon substrate surface.

Next, the silicon substrate to which the film mask is bonded is first subjected to reactive ion etching treatment using an oxygen-containing gas, and the region other than the region covered with the silica particles in the particle layer (the acrylic resin particles in the particle layer) And the binder and the thermal adhesive layer) were removed. Thus, dry etching was performed at 150 W for 30 seconds in the presence of SF ₆ gas using silica particles as a mask. Then, after purging with nitrogen gas, oxygen gas was introduced, and surface treatment with oxygen plasma was performed at 300 W for 30 seconds. When the surface of the silicon substrate was observed with a scanning electron microscope and AFM, the diameter of the silicon substrate surface (equivalent diameter of at least 60% based on the total number of irregularities on the surface of the silicon substrate, the same applies hereinafter) of about 0.5 μm An uneven structure having a depth of about 0.2 μm was observed.

A surface treatment mask was produced in the same manner as in Example 1 (see FIG. 4). However, the coating liquid 4, the coating liquid 2, and the coating liquid 5 were simultaneously applied in this order by a slide hopper coating apparatus to form each coating layer. Each coating layer by coating solution 4, coating solution 2, and coating solution 5 was formed with a wet thickness of 14 μm, 5 μm, and 14 μm, respectively.
Similarly, after the obtained surface treatment mask is cut into a size of 300 × 500 mm, surface treatment is performed using this, and the surface treatment is performed on the surface of the silicon substrate (object to be processed: diameter 100 mm, thickness 0.3 mm). Although unevenness processing was performed on the surface, the particles were frequently overlapped and dropped out, and the desired unevenness was not obtained.

It is process drawing which shows the surface treatment method which concerns on embodiment. It is a schematic block diagram which shows the mask for surface treatment which concerns on embodiment, (A) shows a top view, (B) shows sectional drawing. It is process drawing which shows the manufacturing method of the mask for surface treatment which concerns on embodiment. It is a schematic block diagram which shows the manufacturing apparatus of the mask for surface treatment which concerns on embodiment. It is a schematic block diagram which shows the slide hopper head periphery of a slide hopper coating device. It is a schematic sectional drawing which shows the mask for surface treatment which concerns on embodiment. It is process drawing for demonstrating the etching process in the conventional surface treatment method, (A) shows before an etching process, (B) shows after an etching process.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Surface treatment mask 11 Support substrate 12 Film mask 13 Particle layer 13A Particle 14 Coating layer 15A First coating layer 15B Second coating layer 15C Third coating layer 20 Substrate 30 Laminating apparatus 31 Nipping rollers 40A and 40B Conveying roller 41 Cooling device 42 Drying device 43 Humidity adjustment device 50 Slide hopper coating device 51 Slide hopper head 51A Slide surface 52A, 52B, 52C Storage tank 53A, 53B, 53C Pump 54A, 54B, 54C Piping 55A, 55B, 55C Slot

Claims (24)

A method for producing a surface treatment mask for forming irregularities on the surface of an object to be treated, comprising a film mask,
A first coating layer containing a binder and a gelling agent and a second coating layer containing particles are applied and formed on the base material substantially simultaneously in this order, and the first coating layer is gelled. The manufacturing method of the surface treatment mask which has the process of drying 1 coating layer and the said 2nd coating layer, and forming the said film mask.   In the step of forming the film mask, the first coating layer, the second coating layer, and a third coating layer containing a gelling agent are simultaneously coated and formed in this order on the base material, and then the first coating layer is formed. The method for producing a surface-treated mask according to claim 1, which is a step of drying the first coating layer, the second coating layer, and the third coating layer after gelling the layer and the third coating layer.   The method for manufacturing a surface treatment mask according to claim 1, wherein the gelling agent is water-soluble.   The method for producing a surface treatment mask according to claim 1, wherein the gelling agent is gelatin.   The method for producing a surface treatment mask according to claim 1, wherein the layer obtained by drying the third coating layer is an adhesive layer for adhering the film mask to an object to be processed.   The manufacturing method of the mask for surface treatments of Claim 1 or 2 whose said base material is a support substrate which supports one main surface of the said film mask.   The manufacturing method of the mask for surface treatment of any one of Claims 1-3 which has the process of forming a peeling layer between the said base material and the said film mask.   The manufacturing method of the mask for surface treatment of any one of Claims 1-4 which has the process of forming a non-adhesion layer in the surface on the opposite side to the film mask formation side in the said base material.   The manufacturing method of the mask for surface treatment of any one of Claims 1-5 which has the process of forming a protective film on the said film mask.   The surface treatment mask according to any one of claims 1 to 6, wherein in the step of forming the film mask, a method of applying and forming the respective coating layers substantially simultaneously is selected from a slide coating method and a curtain coating method. Manufacturing method. A surface treatment method for forming irregularities on the surface of a workpiece,
In the surface treatment mask obtained by the method for producing a surface treatment mask according to any one of claims 1 to 5, a bonding step of bonding the film mask to a surface of an object to be processed;
Etching process is performed on the surface of the workpiece to which the film mask is bonded, and an unevenness is formed on the surface of the workpiece,
A surface treatment method characterized by comprising: One main surface of the film mask is supported by a support substrate,
The surface treatment method according to claim 11, wherein the bonding step is a step of peeling the support substrate from the film mask after bonding the film mask to a surface of an object to be processed.   The surface treatment method according to claim 12, further comprising a release layer between the support substrate and the film mask.   The surface treatment method of Claim 12 or 13 which has a non-adhesion layer in the opposite surface to the arrangement | positioning side of the said film mask in the said support substrate. The other main surface of the film mask is covered with a protective film,
The surface treatment method of any one of Claims 11-14 which peels the said protective film from the said film mask before the said bonding process.   The surface treatment method according to any one of claims 11 to 15, wherein the bonding step is a step of holding the film mask and the object to be processed by a roller.   The surface treatment method according to claim 11, wherein the etching process is a dry etching process.   The surface treatment method according to claim 11, wherein the surface of the object to be processed that forms irregularities is a light incident surface of an optical device.   The optical device which has a board | substrate as a to-be-processed object surface-treated by the surface treatment method of any one of Claims 11-18.   A first coating layer containing a binder and a gelling agent and a second coating layer containing particles are applied and formed on the base material substantially simultaneously in this order, and the first coating layer is gelled. The manufacturing method of the particle | grain containing film which has the process of drying 1 coating layer and the said 2nd coating layer, and forming a particle | grain containing film.   In the step of forming the particle-containing film, the first coating layer, the second coating layer, and the third coating layer containing a gelling agent are simultaneously formed on the base material in this order, and then the first coating layer is formed. 21. The method for producing a particle-containing film according to claim 20, which is a step of drying the first coating layer, the second coating layer, and the third coating layer after gelling the coating layer and the third coating layer. .   The method for producing a particle-containing film according to claim 20 or 21, wherein the gelling agent is water-soluble.   The method for producing a particle-containing film according to claim 20 or 21, wherein the gelling agent is gelatin.   The particle-containing film according to any one of claims 20 to 23, wherein in the step of forming the particle-containing film, a method of applying and forming the respective coating layers substantially simultaneously is selected from a slide coating method and a curtain coating method. Manufacturing method.

Images