JP2015111639A - Optical substrate, light-emitting element, and method of manufacturing optical substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical substrate or the like, equipped with a flat electrode formation part together with a fine structure layer.SOLUTION: Disclosed is an optical substrate (1) formed by having a substrate (2); and a fine structure layer (3) formed on the main surface (2a) of the substrate. On the surface of the fine structure layer (3), a plurality of dots (6) are formed constituted of a plurality of protrusions or recesses. On the main surface side of the substrate (2), the fine structure layer (3) and a flat surface capable of being used as an electrode formation part of a light-emitting element are provided.

Description

  The present invention relates to an optical substrate having a microstructure layer including dots composed of a plurality of convex portions or concave portions on the main surface of the substrate, a light emitting element, and a method for manufacturing the optical substrate.

  Patent Document 1 discloses an invention relating to a light-emitting element in which the surface of a base material is an uneven surface. And as shown in patent document 1, the semiconductor layer is laminated | stacked on the whole surface of the base material.

  In Non-Patent Document 1, a fine dot pattern is formed in a device structure using a nanoimprint method.

  By providing such a fine dot pattern, it is possible to change the traveling direction of light. Therefore, a fine dot pattern has been introduced into a light emitting element. In particular, in the LED, studies are being actively made to improve the light extraction efficiency by forming a dot pattern.

JP 2003-318441 A

IEEE TRANSACTIONS ON NANOTECHNOLOGY VOL. 10 NO. 3 MAY 2011 P587-593

  For example, by using the nanoimprint method described above, it is possible to form a fine dot pattern on the entire surface of the substrate.

  A semiconductor layer can be grown on the surface of the dot pattern to manufacture a light emitting device as shown in Patent Document 1. In the conventional methods and substrates as described above, a dot pattern is formed on the entire surface.

  However, in the process of forming the light emitting element, for example, a flat electrode forming part is preferable, but since the dot pattern is formed on the entire surface of the base material, it cannot be an electrode forming part, and a new electrode forming part is formed. The process to do was needed. For this reason, conventionally, there has been a problem that the manufacturing process of the light emitting element becomes complicated.

  The present invention has been made in view of the above points, and includes an optical substrate having a partially flat principal surface that can be used as an electrode portion together with a fine structure layer, a light emitting element, and an optical substrate. An object is to provide a manufacturing method.

  The inventors left the main surface of the substrate as a flat surface and provided a fine structure layer separately from the substrate. At this time, in the present invention, since a flat surface is formed in a region other than the fine structure layer, it can be used as an electrode formation portion, and thus it is not necessary to form an electrode formation portion in the manufacturing process of the light emitting element, and light emission The device manufacturing process can be made easier than before. The configuration of the present invention will be described below.

  The present invention is an optical substrate for forming a light-emitting element comprising a substrate and a microstructure layer formed on the main surface of the substrate, and a plurality of layers are formed on the surface of the microstructure layer. A plurality of dots composed of convex portions or concave portions are formed, and on the main surface side of the base material, the fine structure layer and a flat surface that can be used as an electrode forming portion of a light emitting element are provided. It is characterized by being.

  Moreover, in this invention, it is preferable that the said flat surface is a surface where the main surface of the said base material was exposed.

  In the present invention, the main surface is preferably on the p-plane electrode side. In the present invention, the flat surface is preferably a surface produced by photolithography, and more preferably a development surface. The optical base material provided with the flat electrode forming part together with the created fine structure layer may be further processed by ashing, etching or the like. Examples of the p-plane electrode include an LED electrode.

  Moreover, in this invention, the said base material is comprised including a base-material main body and the conductive layer formed in the surface of the said base-material main body, and the surface of the said conductive layer may make the main surface of the said base material. preferable.

  In the present invention, the microstructure layer contains a compound containing at least one of an aromatic group, a polycyclic group, or a heterocyclic group, or Al, Si, P, Ti, Ga, Ge, Zr, Nb. It is preferable to contain at least one element selected from Ta, In and Sn.

  In the present invention, the photosensitive resin material for forming the microstructure layer includes at least one of an antioxidant, a polymerization inhibitor, an ultraviolet absorber, a radical scavenger, a sensitizer, and an adhesion aid. It is preferable.

  In the present invention, the photosensitive resin material for forming the fine structure layer is preferably a negative resist.

  Moreover, in this invention, it is preferable that the photosensitive resin material for forming the said microstructure layer is resin which can be alkali developed.

  Moreover, in this invention, it is preferable that the sensitive resin material for forming the said microstructure layer contains the compound which has a carboxylic acid group.

  Further, the present invention is a light emitting element formed using the optical substrate described above, wherein a laminated semiconductor layer having a semiconductor layer and a light emitting layer is formed on the surface of the microstructure layer, An electrode layer is formed on the flat surface.

  Moreover, the manufacturing method of the optical base material in the present invention includes a mold having a plurality of dots formed from a plurality of convex portions or concave portions on the surface, a base material, the surface of the mold, and a main surface of the base material. A step of forming an optical base material precursor formed by laminating a photosensitive resin material interposed between the optical base material precursor, exposing the optical base material precursor through a mask, A step of making the area smaller than the formation area of the dots formed on the mold, peeling the mold and exposing the exposed photosensitive resin material as the microstructure layer having the dots formed on the surface And removing the unexposed portion of the photosensitive resin material by development to form the fine structure layer and the flat surface on the main surface.

  Moreover, in this invention, it is preferable to include the process of heating the said optical base material precursor after the said image development.

  Moreover, in this invention, it is preferable to expose a part of said main surface by the removal of the unexposed part of the said photosensitive resin material.

  Moreover, in this invention, it is preferable to remove the unexposed part of the said photosensitive resin material with a solvent.

  Moreover, in this invention, after removing the unexposed part of the said photosensitive resin material with a solvent, it is preferable to rinse using water.

  Moreover, in this invention, it is preferable to rinse using water, after removing the unexposed part of the said photosensitive resin material with aqueous alkali solution.

  Moreover, in this invention, when removing the unexposed part of the said photosensitive resin material, it is preferable to use an ultrasonic wave.

  In the present invention, the optical substrate precursor is formed by bonding the substrate to the photosensitive resin material side of the sheet filled with the photosensitive resin material on the surface of the mold, or the substrate It is preferable that the optical base material precursor is formed by applying the photosensitive resin material to the main surface and pressing and bonding the surface of the mold on which the dots are formed to the photosensitive resin material.

  Moreover, in this invention, it is preferable to include the process of heating the said optical base material precursor after the said exposure.

  Moreover, in this invention, it is preferable to pressurize between the said base material and the said molds at the time of bonding in the formation process of the said optical base material precursor.

  Moreover, in this invention, it is preferable to add a heat | fever at the time of the bonding in the formation process of the said optical base material precursor.

  According to the optical substrate of the present invention, a fine structure layer and a flat surface are provided on the main surface side of the substrate, and this flat surface can be used as at least an electrode forming portion of the light emitting device. At the time of manufacturing, it is not necessary to form a flat electrode forming portion, and the manufacturing process of the light emitting element can be facilitated as compared with the conventional case.

  Further, according to the method for producing an optical substrate of the present invention, a fine structure layer having a plurality of dots formed on the surface can be formed with high precision, and a flat surface as an electrode forming portion can be formed on the substrate by a simple process. It can be formed on the main surface side.

  Furthermore, by processing a base material having a fine structure layer in a part of the above, it is easy to produce a base material in which a flat surface and a fine structure portion are formed only from the material constituting the main surface.

1A and 1B are schematic cross-sectional views of the optical base material according to the present embodiment. FIGS. 1C and 1D are schematic partial plan views of the optical base material. FIGS. 1E and 1F are microstructures. It is the partial plane schematic diagram which expanded and showed the dot formed in the surface of the layer. It is a cross-sectional schematic diagram which shows the light emitting element which concerns on this Embodiment. It is a perspective schematic diagram which shows an example of the fine structure layer which concerns on this Embodiment. It is a perspective schematic diagram for demonstrating the other example of the fine structure layer which concerns on this Embodiment. It is a cross-sectional schematic diagram for demonstrating the manufacturing process of the light emitting element which concerns on this Embodiment. It is a cross-sectional schematic diagram for demonstrating the manufacturing process of the light emitting element which replaces with FIG. 5A and shows another example.

  1A and 1B are schematic cross-sectional views of the optical base material according to the present embodiment. FIGS. 1C and 1D are schematic partial plan views of the optical base material. FIGS. 1E and 1F are microstructures. It is the partial plane schematic diagram which expanded and showed the dot formed in the surface of the layer.

  As shown in FIG. 1A, the optical substrate 1 according to the present embodiment is configured to include a substrate 2 and a microstructure layer 3 formed on the main surface 2 a of the substrate 2.

  The substrate 2 includes a substrate body 4 and a conductive layer 5 formed on the surface of the substrate body 4.

  The material of the substrate body 4 is not particularly limited as long as it can be used as a substrate for a semiconductor light emitting element or a semiconductor light emitting element laminate, and a semiconductor layer, a conductor layer, a light emitting layer, a buffer layer, etc. are formed on the substrate. May be present. For example, the material of the base material is quartz glass, sapphire, SiC, SiN, GaN, silicon, zinc oxide, magnesium oxide, manganese oxide, zirconium oxide, manganese zinc iron oxide, magnesium aluminum oxide, zirconium boride, gallium oxide, oxidation Indium, lithium gallium oxide, lithium aluminum oxide, neodymium gallium oxide, lanthanum strontium aluminum tantalum oxide, strontium titanium oxide, titanium oxide, hafnium, tungsten, molybdenum, Ga-based semiconductors such as GaN, GaP, GaAs, InGaN, AlGaN, etc. A substrate for a semiconductor light emitting element and a laminated material can be used. Examples of stacking include (1) AlGaN low temperature buffer layer, (2) n-type GaN layer, (3) n-type AlGaN cladding layer, (4) InGaN light emitting layer (MQW), (5) p-type AlGaN cladding layer, (6) p-type GaN layer and the like.

A conductive layer 5 such as ITO is formed on the surface of the base body 4. The conductive layer 5 may be omitted, but by providing the conductive layer 5 on the surface of the insulating base body 4, the exposed main surface 2 a of the base 2 can be appropriately used as an electrode forming portion. As the material of the conductive layer 5, metals such as Al, Mo, Au, Ag, Cu, Cr and Ti, ZnO, SnO, TiO ₂ , ITO (tin-doped indium tin oxide), IZO (zinc-doped indium oxide), ATO ( Examples include metal oxides such as antimony-doped tin oxide, TTO (tantalum-doped tin oxide), AZO (aluminum-doped zinc oxide), NTO (niobium-doped titanium oxide), and GZO (gallium-doped tin oxide), and composite metal oxides. .

  In FIG. 1A, the conductive layer 5 is provided on the surface of the substrate body 4, and the surface of the conductive layer 5 is the main surface 2 a of the substrate 2. In the form in which the conductive layer 5 is not formed, the surface of the base body 4 is the main surface 2 a of the base 2.

  The main surface 2a of the base material 2 refers to a wide surface for transmitting light generated in or under the base material 2 in manufacturing a light emitting element such as an LED. The main surface 2a refers to the p-plane electrode side.

  As shown in FIG. 1A, the fine structure layer 3 is formed on the main surface 2 a of the substrate 2. The fine structure layer 3 is not formed on the entire main surface 2a, but is formed on a part of the main surface 2a. In this embodiment, the amount of reflected light (light confined in the device) can be reduced by diffracting the emitted light, and as a result, a light-emitting element such as an LED having high luminous efficiency is manufactured. It is possible.

As shown in FIG. 1C, a plurality of fine structure layers 3 may be formed independently. Alternatively, as shown in FIG. 1D, the fine structure layer 3 may be formed with a part lacking. The size of each independent area is 25μm ² ~1000000μm ² about.

  In the region where the fine structure layer 3 is not formed, the main surface 2a (conductive layer 5) of the substrate 2 is exposed. The exposed main surface 2a is a flat surface. At this time, the flat surface is preferably present at a position lower than the fine structure layer 3 (position on the main surface 2a or near the main surface 2a) as shown in FIG. 1A.

  As shown in FIG. 1A, a plurality of dots 6 composed of a plurality of convex portions or a plurality of concave portions are formed on the surface of the fine structure layer 3. The surface of the fine structure layer 3 is a growth formation surface of a semiconductor layer constituting the light emitting element. Hereinafter, the plurality of dots 6 may be referred to as a dot pattern, or the surface on which the plurality of dots 6 are formed may be referred to as a dot pattern surface.

  In the present embodiment, the dots 6 can be finely formed on the surface of the fine structure layer 3 by, for example, a nanoimprint method.

  The microstructure layer 3 is made of a material different from that of the substrate 2. The material constituting the microstructure layer 3 may be an inorganic material or an organic material. Inorganic materials are preferable from the viewpoints of durability such as heat resistance and light resistance, etching resistance, and transparency. Organic materials and organic-inorganic hybrid materials can be selected from various materials and solvents for forming the microstructure layer 3. It is preferable because it is possible. Furthermore, by using an organic material, it is easy to process the conductive layer 5 and / or the base body 4 while leaving a flat surface by ashing or etching. The microstructure layer 3 may be composed of a plurality of materials or a plurality of layers.

  The dot pattern may or may not have periodicity, but it is more preferable that it has periodicity.

  For example, as shown in FIG. 1E, each dot 6 may be formed at a constant pitch P, and as shown in FIG. 1F, a dot group 7 in which a plurality of dots 6 are combined has a constant periodicity. In addition, each dot 6 may be arranged. For example, the dots 6 may be arranged in a regular hexagonal arrangement, a hexagonal arrangement, a quasi-hexagonal arrangement, a quasi-tetragonal arrangement, a tetragonal arrangement, and a regular tetragonal arrangement. Further, all the dots 6 may not have periodicity, some of the dots 6 may be arranged to have periodicity, and the remaining dots 6 may be arranged at random.

  When the dot pattern has periodicity, it is preferable in terms of improving the light extraction efficiency when used in a light emitting element such as an LED. Moreover, the lower limit of the distance (pitch) between the dots 6 (between the nearest dots 6) is 50 nm from the viewpoint of light extraction efficiency and from the viewpoint of adhesion to the mold and releasability in the light emitting element manufacturing process. Preferably, it is 100 nm or more, more preferably 150 nm or more. The upper limit value of the pitch is preferably 3000 nm or less, more preferably 2000 nm or less, and even more preferably 1000 nm or less. As shown in FIG. 1E, the pitch P indicates the distance between the vertices or centers of the closest dots.

  As shown in FIG. 1A, the height (thickness) H of the microstructure layer 3 or the lower limit of the height of each dot 6 or the depth of each dot 6 is a viewpoint for improving the light extraction efficiency of a light emitting element such as an LED. In addition, from the viewpoint of adhesion to the resin mold and the peelability in the light emitting element manufacturing process, 50 nm or more is preferable, 100 nm or more is more preferable, 200 nm or more is more preferable, and 300 nm or more is most preferable. The upper limit of the height (thickness) H of the fine structure layer 3 or the height of each dot 6 or the depth of each dot 6 is preferably 1000 nm or less, more preferably 800 nm or less, further preferably 700 nm or less, and 500 nm. The following are most preferred. The height (thickness) H of the fine structure layer 3 or the height of each dot 6 or the depth of each dot 6 is determined when a residual film such as a photosensitive resin material in the manufacturing process remains on the main surface 2a. Is evaluated only by the fine structure layer 3 and the dots 6 not including the remaining film.

  The lower limit of the width of each dot 6 is preferably 50 nm or more, from the viewpoint of improving the light extraction efficiency of the pitch P and the light emitting element, and from the viewpoint of adhesion to the resin mold and the releasability in the manufacturing process of the light emitting element. The above is more preferable, 200 nm or more is further preferable, and 300 nm or more is most preferable. The upper limit of the width is preferably 1000 nm or less, more preferably 800 nm or less, still more preferably 700 nm or less, and most preferably 500 nm or less. The width of the dot 6 indicates the width of the bottom of the dot 6 when the dot 6 is a convex portion, and indicates the opening width when the dot 6 is a concave portion.

  The dots 6 constituting the microstructure layer 3 may be convex portions or concave portions, and the shape of the dots 6 depends on the design of the resin mold used.

  The optimum shape and size of the fine structure layer 3 and the dots 6 can be variously selected depending on the refractive index of the material used, ashing resistance, etching resistance, optical characteristics such as light extraction improvement, physical characteristics, and the like.

  In the optical base material 1 shown in FIG. 1B, for example, the dots 6 are formed as convex portions, and the main surface 2 a of the base material 2 is exposed from between the dots 6. Or when the dot 6 is formed in the recessed part, it will be in the state which the main surface 2a of the base material 2 was exposed from the bottom face of the recessed part.

  In the configuration shown in FIG. 1B, there may be a photosensitive resin material or a residual film of a cured product of the photosensitive resin material between the dots 6 or on the bottom surface of the dots 6. The thickness of the remaining film is preferably 3000 nm or less, more preferably 1000 nm or less, further preferably 700 nm or less, further preferably 500 nm or less, and most preferably 300 nm or less from the viewpoint of the process time when it is later removed by ashing or the like. ing.

  In the optical base material 1 of the present embodiment, the main surface 2a of the base material 2 is not processed into a dot pattern, the main surface 2a of the base material 2 is left as it is as a flat surface, and is fine separately from the base material 2. A structural layer 3 is provided. In the present embodiment, a flat surface is formed in a region other than the fine structure layer 3. As shown in FIGS. 1A and 1B, this flat surface is a surface where the main surface 2a of the substrate 2 is exposed.

  The flat surface is a development surface by photolithography. That is, the flat surface is not a surface that has been scraped off by etching or the like, or a surface on which nothing has been formed on the main surface 2a of the substrate 2 in the manufacturing process. As will be described later in the manufacturing process, the fine structure layer 3 is once formed on the entire main surface 2a of the substrate 2 by the nanoimprint method or the like, but the unnecessary fine structure layer 3 is formed by exposure and development by photolithography. It is possible to appropriately form a flat surface by removing.

  In the present embodiment, the fine structure layer 3 and a flat surface are formed on the main surface 2a of the substrate 2 of the optical substrate 1, and this flat surface can be used as an electrode forming portion of a light emitting element. . Therefore, the manufacturing process of the flat electrode forming part is not necessary in the manufacturing process of the light emitting element as in the prior art.

In the embodiment of the present invention, as the electrode, for example, metal such as Au, Ag, Cu, Ni, Pd, Al, Ti, Cr, Mn, Mo, Ru, Rh, Pt, ZnO, SnO, TiO ₂ , ITO ( Tin-doped indium tin oxide, IZO (zinc-doped indium oxide), ATO (antimony-doped tin oxide), TTO (tantalum-doped tin oxide), AZO (aluminum-doped zinc oxide), NTO (niobium-doped titanium oxide), GZO (gallium-doped oxide) And metal oxides such as tin) and composite metal oxides.

The area of the electrode portion, so long as it can be used as an electrode, preferably 10 [mu] m ² or more, more preferably 25 [mu] m ² or more, more preferably 100 [mu] m ² or more, more preferably 400 [mu] m ² or more. Moreover, an electrode should just be smaller than the magnitude | size of a base material, For example, when providing an electrode part in the p surface side which is the light emission surface of LED, it is preferable to make it the magnitude | size which does not become the hindrance of light emission.

  In the present embodiment, an electrode part may be formed on the flattened main surface 2a, and another process for forming a flat surface is not required. As described above, by using the optical substrate 1 of the present embodiment, it is possible to facilitate the manufacture of the light emitting element as compared with the conventional case.

  FIG. 2 is a schematic cross-sectional view showing the light-emitting element according to this embodiment. FIG. 3 is a schematic perspective view showing an example of the microstructure layer according to the present embodiment. FIG. 4 is a schematic perspective view for explaining another example of the microstructure layer according to the present embodiment.

  As shown in FIG. 2, in the light emitting element 200, a fine structure layer 113 is provided on a part of the main surface 101 a of the substrate 101. In the region where the fine structure layer 113 is not provided, the surface of the transparent conductive layer 106 formed on the surface of the base body 101 is exposed.

  As shown in FIG. 2, the buffer layer 114, the n-type semiconductor layer 103, the light emitting layer 104, and the p-type semiconductor layer 105 are sequentially stacked on the base body 111. Note that the n-type semiconductor layer 103, the light-emitting layer 104, and the p-type semiconductor layer 105 that are sequentially stacked are referred to as a stacked semiconductor layer 110.

  As shown in FIG. 2, a transparent conductive layer 106 is formed on the p-type semiconductor layer 105. An anode electrode 108 is formed on the surface of the transparent conductive layer 106. A fine structure layer 113 is provided on a part of the surface of the transparent conductive layer 106. As shown in FIG. 2, a part of the main surface of the substrate main body 111 exists on the side of the fine structure layer 113, and the cathode electrode 102 is provided above the main surface.

  As shown in FIG. 3, a fine structure layer 113 having dots 15 composed of a plurality of convex portions 13 on the surface is formed on a part of the main surface 101 a of the base material 101 constituting the light emitting element 200. Alternatively, as shown in FIG. 4, a fine structure layer 113 having dots 16 composed of a plurality of recesses 14 is formed on a part of the main surface 101 a of the base material 101 constituting the light emitting element 200. Also good. The dots 15 and 16 are arranged at a predetermined pitch.

  According to the light emitting element 200 of the present embodiment, an electrode (anode electrode 108) can be formed using a flat electrode forming portion provided on a part of the main surface 101a of the substrate 101. Compared to the conventional method, the manufacturing process of the electrode forming part is not required during the manufacturing process of the light emitting device, and the manufacturing of the light emitting device can be facilitated compared to the conventional method.

  Then, the manufacturing method of the optical base material of this Embodiment is demonstrated. FIG. 5 is a schematic cross-sectional view for explaining a manufacturing process of the light-emitting element according to this embodiment.

  As a method of forming a fine structure layer on the surface of which dots composed of a plurality of convex portions or concave portions are formed, there is a method using a nanoimprint method.

  In the step shown in FIG. 5A, a resin mold 51 having a surface on which dots 50 composed of a plurality of convex portions or concave portions are prepared. And the photosensitive resin material 52 is filled in the surface side in which the dot 50 of the resin mold 51 was formed. Here, the laminate in which the resin mold 51 is filled with the photosensitive resin material 52 is referred to as a sheet 54.

  Moreover, the base material 2 is prepared as shown to FIG. 5A. For example, the substrate 2 includes a substrate body 4 and a conductive layer 5 made of ITO or the like formed on the surface of the substrate body 4.

  As shown in FIG. 5A, the base material 2 is bonded to the sheet 54 with the conductive layer 5 side of the base material 2 facing the photosensitive resin material 52. A laminate in which the photosensitive resin material 52 is interposed between the resin mold 51 and the substrate 2 is referred to as an optical substrate precursor 55.

  Alternatively, as shown in FIG. 6, the photosensitive resin material 52 is applied to the main surface of the substrate 2, and the photosensitive resin material 52 is opposed to the surface side where the dots 50 of the resin mold 51 are formed. The optical base material precursor 55 may be formed by being bonded to the resin mold 51 while being pressed.

  As shown in FIG. 6, when the photosensitive resin material 52 is applied to the substrate 2, spin coating, bar coating, dip, spray coating, or the like can be used as a coating method. From the viewpoint of in-plane uniformity and large area coating, it is preferable to use spin coating or bar coating.

  In the case of spin coating, although depending on the solid content or viscosity of the photosensitive resin material 52, from the viewpoint of film thickness uniformity, the main rotational speed is preferably 300 rpm or more, more preferably 500 rpm or more, and even more preferably 1000 rpm or more. 1500 rpm or more is most preferable. In addition, 5000 rpm or less is preferable from the viewpoint of safety during application. The main rotation time is preferably 3 seconds or more, more preferably 5 seconds or more, and even more preferably 10 seconds or more.

  In the case of bar coating, from the viewpoint of film thickness uniformity, the coating wet film thickness is preferably 1 μm or more, more preferably 2 μm or more, further preferably 3 μm or more, and preferably 100 μm or less, more preferably 50 μm or less.

  As shown in FIG. 5A, methods for applying the photosensitive resin material 52 to the resin mold 51 include spin coating, bar coating, dip, spray coating, and the like. From the viewpoint of in-plane uniformity and filling the unevenness of the resin mold, it is preferable to use a bar coat.

  In the case of bar coating, from the viewpoint of film thickness uniformity, the coating wet film thickness is preferably 1 μm or more, more preferably 2 μm or more, further preferably 3 μm or more, and preferably 100 μm or less, more preferably 50 μm or less.

  After the photosensitive resin material 52 is applied to the substrate 2 or the resin mold 51, it may be dried by heating in order to remove the solvent or to improve the adhesion to the substrate 2.

  When applied by spin coating, although depending on the number of rotations and time, the solvent may have already been removed to some extent, so the solvent may be removed by allowing it to stand at room temperature for several tens of seconds to several hours. .

  When drying by heating, although depending on the type of solvent used and the amount of residual solvent, it is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 80 ° C. or higher. In particular, in the case of application to the resin mold 51, in order to apply the photosensitive resin material 52 with a uniform film thickness and stably hold the photosensitive resin material 52 to the resin mold 51, the temperature is preferably 200 ° C. or lower, 150 C. or lower is preferable. Although it depends on the drying temperature, the drying time is preferably 1 minute or more, more preferably 3 minutes or more, and further preferably 5 minutes or more.

  In the case of application to the resin mold 51, in order to apply the photosensitive resin material 52 with a uniform film thickness and stably hold the photosensitive resin material 52 to the resin mold 51, 10 hours or less is preferable, and 5 hours. The following is more preferable, and 2 hours or less is further preferable.

  The base body 4 can be formed of quartz glass, alkali-free glass, soda glass, sapphire, silicon, or the like. Further, a metal such as Al, Mo, Au, Ag, Cu, Cr and Ti or a metal oxide layer thereof, a semiconductor layer such as ITO and GaN, etc. are formed on the surface (main surface side) of the base body 4. May be. For example, a conductive layer 5 made of ITO is preferably provided.

  The photosensitive resin material 52 will be described. As the photosensitive resin material 52, a compound that generates an active substance in response to light, such as a photopolymerization initiator, a photoacid generator, or a photobase generator, can be used. Preferably, a photopolymerization initiator is preferable from the viewpoint of the reactivity of the photosensitive compound to light and the reactivity of the active substance generated from the photosensitive compound.

<Resin material using photopolymerization initiator>
Examples of the resin material using a photopolymerization initiator include an ethylenically unsaturated addition polymerizable monomer-containing composition. Preferable photopolymerization initiators are compounds that generate radicals by light, and include the following compounds.

  (1) Benzophenone derivatives: for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone

  (2) Acetophenone derivatives: for example, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (Ciba Specialty Chemicals) IRGACURE (registered trademark) 651), 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals, IRGACURE (registered trademark) 184), 2-methyl-1- [4- (methylthio) phenyl] -2 Morpholinopropan-1-one (Ciba Specialty Chemicals, IRGACURE (registered trademark) 907), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -Phenyl} -2-methylpropan-1-one (Ciba-su Sharuti Chemicals Inc., IRGACURE (TM) 127), phenyl glyoxylic acid methyl

  (3) Thioxanthone derivatives: for example, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone

  (4) Benzyl derivatives: for example, benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal

  (5) Benzoin derivatives: for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by Ciba Specialty Chemicals, DAROCURE 1173)

  (6) Oxime compounds: for example, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl) Oxime)] (Ciba Specialty Chemicals, IRGACURE (registered trademark) OXE01), Ethanon, 1 [9-ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl] -, 1- (O- acetyloxime) (manufactured by Ciba Specialty Chemicals, IRGACURE (TM) OXE02)

  (7) α-hydroxy ketone compounds: for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl} -2-methylpropane

  (8) α-aminoalkylphenone compounds: for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by Ciba Specialty Chemicals, IRGACURE (registered trademark) 369) ), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, IRGACURE (registered trademark) 379) )

  (9) Phosphine oxide compound: For example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Specialty Chemicals, IRGACURE (registered trademark) 819), bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (manufactured by Ciba Specialty Chemicals, DAROCUR TPO (registered trademark))

  (10) Titanocene compound: for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (Ciba Specialty) -Chemicals, IRGACURE (registered trademark) 784)

  Moreover, when using these photoinitiators, it may be individual or a mixture of 2 or more types.

  Among the photopolymerization initiators described above, the benzoin derivative (5) or the phosphine oxide compound (9) is more preferable particularly from the viewpoint of photosensitivity. From the viewpoint of stability to light, (1 ) Benzophenone derivatives, (2) acetophenone derivatives, or (7) α-hydroxy ketone compounds. The addition amount is 0.01 to 30 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 2 parts by mass with respect to the acrylic / methacrylic compound (100 parts by mass). And more preferably 0.3 to 1.5 parts by mass. From the viewpoint of obtaining a fine concavo-convex structure with practical hardness, the addition amount of the photopolymerization initiator is 0.01 parts by mass or more, and from the viewpoint of stability of the composition, it is preferably 30 parts by mass or less. .

  The photosensitive resin material 52 preferably contains an ethylenically unsaturated addition polymerizable monomer (hereinafter also referred to as “acrylic monomer”). As the acrylic monomer added to the photosensitive resin material 52, it is preferable to use a compound containing an acryloyl group or a methacryloyl group from the viewpoint of improving etching resistance, hardness, and heat resistance.

  From the viewpoint of ashing resistance, etching resistance, film strength, hardness, and heat resistance, the photosensitive resin material 52 preferably contains a monomer containing an aromatic group, a polycyclic group, or a heterocyclic group (one compound) Are compounds classified into two or more types among aromatic groups, polycyclic groups, and heterocyclic groups). Examples of the aromatic group include a compound having a phenyl, naphthalene, or anthracene skeleton. In addition, as the skeleton containing a phenyl group, a compound in which a plurality of aromatic groups such as biphenyl are directly bonded to each other, and a plurality of aromatic groups such as a bisphenol A skeleton are carbon, oxygen, nitrogen, silicon, It includes a compound bonded with a crosslinking group containing at least one kind of sulfur.

Examples of compounds to which an aromatic group is added include phenyl, naphthalene, and anthracene as substituents: —R ¹ —O (C═O) —CR ² ═CH ₂ group (R ¹ is carbon, oxygen, nitrogen, A substituent containing at least one element of silicon and sulfur, preferably a substituent composed of carbon and / or oxygen, and R ² is hydrogen or a methyl group). What you are doing. Specific examples thereof include phenyl acrylate, phenyl methacrylate, 1-naphthalene acrylate, 1-naphthalene methacrylate, 2-naphthalene acrylate, 2-naphthalene methacrylate, 1-anthracene acrylate, 1-anthracene methacrylate, 2-anthracene acrylate, 2- Anthracene methacrylate, 9-anthracene acrylate, 9-anthracene methacrylate and the like can be mentioned. As a substituent for phenyl, naphthalene and anthracene, a plurality of acryloyl groups or methacryloyl groups may be bonded to these compounds. Further, a structure in which another hydrogen atom is substituted with a functional group containing carbon, oxygen, nitrogen, silicon, sulfur, fluorine, chlorine, bromine, or iodine may be used. Development with an aqueous alkali solution is possible when such a compound has a substituent such as a carboxylic acid group, a carboxylic acid anhydride group, or a hydroxy group that improves the solubility in an aqueous alkali solution. Therefore, it is preferable.

  Examples of the compound in which a plurality of aromatic groups are directly bonded include at least one of compounds including the structure of the following chemical formula group A.

Chemical formula group A

  Examples of the compound in which a plurality of aromatic groups are bonded with a bridging group containing at least one of carbon, oxygen, nitrogen, silicon, and sulfur include at least one of compounds having the structure of the following chemical formula group B: It is done.

Chemical formula group B

  Examples of the polycyclic compound include at least one of compounds including the structure of the following chemical formula group C.

Chemical formula group C

  Examples of the heterocyclic compound include at least one of compounds including the structure of the following chemical formula group D.

Chemical formula group D

The substitution position of the aromatic group, polycyclic group, or heterocyclic group described above may be substituted anywhere as long as it can be bonded, may be substituted, and the substituent may be- ^{R 1 -O (C = O)} -CR 2 = CH 2 and the like ^{(R 1} is a substituent containing carbon, oxygen, nitrogen, silicon, at least one kind of element of sulfur, preferably, A substituent composed of carbon and / or oxygen, and R ² is hydrogen or a methyl group). Further, a structure in which another hydrogen atom is substituted with a functional group containing carbon, oxygen, nitrogen, silicon, sulfur, fluorine, chlorine, bromine, or iodine may be used. Further, as the substituents replacing a hydrogen bonded to the nitrogen ^{- (C = O) -CR 2} = CH 2 or -CH = CH ₂ even better ^{(R 2} is hydrogen or a methyl group). In addition, development with an alkaline aqueous solution is possible if such a compound has a substituent such as a carboxylic acid group, a carboxylic anhydride group, or a hydroxy group that improves the solubility in an alkaline aqueous solution. Therefore, it is preferable.

  In the above, good acrylic monomers such as ashing resistance, etching resistance, heat resistance, etc. were mentioned, but it is sufficient that the entire composition contains an aromatic group, a polycyclic group, or a heterocyclic group. An acrylate monomer or an acrylic monomer having an ethylene oxide chain may be added.

  Addition amount includes the aromatic group, polycyclic group, or heterocyclic group with respect to the acrylic monomer compound (100 parts by mass) from the viewpoints of ashing resistance, etching resistance, film strength, hardness, and heat resistance. The monomer is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and most preferably 70 parts by mass or more.

  An oligomer or a polymer may be added to the resin material for viscosity adjustment, ashing resistance, and etching resistance. As the oligomer or polymer to be added, it is more preferable to use an oligomer or polymer having an acryloyl group or a methacryloyl group.

  Preferred structures include the above-described phenol novolac oligomer / polymer, cresol novolac oligomer / polymer, styrene oligomer / polymer, norbornene ring-opening polymer oligomer / polymer, norbornene addition polymer oligomer / polymer, norbornadiene system Examples thereof include ring-opening polymerized oligomers / polymers, norbornadiene-based addition polymerized oligomers / polymers, and oligomers / polymers of acrylic monomers described above. Furthermore, it is preferable that an acryloyl group or a methacryloyl group is bonded to the side chain of the oligomer / polymer because physical properties such as ashing resistance, etching resistance and hardness are further improved. In addition, if the oligomer / polymer has side groups such as a carboxylic acid group, a carboxylic anhydride group, or a hydroxy group that improve the solubility in an alkaline aqueous solution, development with an alkaline aqueous solution is possible. It is preferable to make it possible.

  The addition amount is preferably 10 parts by mass or more and 20 parts by mass or more with respect to the acrylic monomer compound (100 parts by mass) from the viewpoints of ashing resistance, etching resistance, film strength, hardness, and heat resistance. More preferably, it is more preferably 30 parts by mass or more, from the viewpoint of curability of the composition, it is preferably 1000 parts by mass or less, and more preferably 500 parts by mass or less.

  Moreover, an inorganic material and an organic-inorganic hybrid material can be used from a viewpoint of ashing resistance, etching resistance, heat resistance, and transparency. Alternatively, an inorganic material or an organic-inorganic hybrid material can be added to the organic material.

  As an inorganic material, sol-gel material and an inorganic filler (inorganic fine particle) can be included, for example. Moreover, as an inorganic material, you may be comprised only with sol-gel material. Examples of inorganic materials include inorganic oxides such as silica, titania, zirconia, and zinc oxide, metal composite oxides such as barium titanate, strontium titanate, and ITO, and metals such as gold, silver, copper, aluminum, and chromium. It is done.

  Moreover, it is preferable to contain at least one element selected from Al, Si, P, Ti, Ga, Ge, Zr, Nb, Ta, In, and Sn. In particular, Ti, Zr, and Si are preferable.

  As the organic-inorganic hybrid material, metal alkoxides, metal chlorides, and their hydrolysates and hydrolysis condensates may be used. From the viewpoint of crack resistance and stability, it is preferable to use a condensate.

  Examples of the metal alkoxide include silane alkoxide, titanium alkoxide, zirconium alkoxide, and tantalum alkoxide. From the viewpoint of stability, silane alkoxide, titanium alkoxide, or zirconium alkoxide is preferable, and silane alkoxide is more preferable. Examples of the metal chloride include tetrachlorosilane, titanium chloride, zirconium chloride, and tantalum chloride.

  Examples of the silane alkoxide or chlorosilane include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and vinyltrimethoxy. Silane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, di Cyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, diphenyldimethoxysila , Diphenyldiethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxy Silane, 3-acryloxypropyltriethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethylmethyldimethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acrylic Roxyethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysila , Acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3 4-epoxycyclohexyl) ethyldimethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethylmethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ) Ethylethoxydimethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropylmethoxydimethylsilane, 3-glycidoxypropylethoxydimethylsilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Triethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) ) -2-Aminoethyl-3-a Nopropyltrimethoxysilane hydrochloride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, methyltrichlorosilane, phenyltrichlorosilane, Examples thereof include dimethyldichlorosilane, trimethylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, and tri-i-propylchlorosilane.

  From the viewpoint of the stability, hardness, ashing resistance, and etching resistance of the cured product, it preferably has a functional group capable of reacting with a photopolymerization initiator, such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl. Triethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2 -Methacryloxyethylmethyldimethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacrylo Shi methyl dimethoxy silane, acryloxymethyl trimethoxy silane, and the like acryloxymethyl triethoxysilane.

  Other metal alkoxides or metal chlorides include titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, zirconium tetramethoxide, zirconium tetraethoxide, Zirconium tetra n-propoxide, zirconium tetraisopropoxide, zirconium tetra n-butoxide, tantalum pentamethoxide, tantalum pentaethoxide, tantalum penta n-propoxide, tantalum pentaisopropoxide, tantalum penta n-butoxide, etc. It is done.

  Fine particles such as titanium oxide, zirconium oxide, silica, ITO, ZnO, SnO, IZO, ATO, and AZO may be contained. In that case, from the viewpoint of film physical properties and transparency, the particle size is preferably 1000 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. These may be used alone or in combination of two or more.

  When a metal oxide, a metal composite oxide, a metal, or an organic-inorganic hybrid material is added for the purpose of improving or controlling the etching resistance and ashing resistance of the composition, the dot is composed of a plurality of convex portions or concave portions. It is necessary to blend in a well-balanced manner in the entire composition in the microstructure layer containing. On the other hand, in order to improve physical properties such as heat resistance and transparency, the addition amount is preferably 10 parts by mass or more, and 20 parts by mass or more with respect to the composition (100 parts by mass) of the microstructure layer. More preferably, it is more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, further preferably 70 parts by mass or more, and most preferably 90 parts by mass or more.

<Photoacid generator composition>
The photoacid generator is not particularly limited as long as it generates a photoacid by light irradiation. Examples thereof include aromatic onium salts such as sulfonium salts and iodonium salts. Examples of the photoacid generator include sulfonium hexafluoroantimonate, benzyltriphenylphosphonium hexafluorophosphate, benzylpyridinium hexafluorophosphate, diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, benzoin tosylate, adekatopomer ( (Registered trademark) sp-170 (manufactured by ADEKA), ADEKA OPTMER (registered trademark) sp-172 (manufactured by ADEKA), WPAG-145 (manufactured by Wako Pure Chemical Industries), WPAG-170 (manufactured by Wako Pure Chemical Industries, Ltd.) ), WPAG-199 (made by Wako Pure Chemical Industries), WPAG-281 (made by Wako Pure Chemical Industries), WPAG-336 (made by Wako Pure Chemical Industries), WPAG-367 (made by Wako Pure Chemical Industries), CPI-100P San Apro), CPI-101A (San Apro), CPI-200K (San Apro), CPI-210S (San Apro), DTS-102 (Midori Kagaku), TPS-TF (Toyo Gosei Co., Ltd.) And DTBPI-PFBS (manufactured by Toyo Gosei Co., Ltd.).

  The addition amount of a photo-acid generator is 0.01-30 mass parts with respect to a cationic curable monomer compound (100 mass parts), Preferably it is 0.1-20 mass parts, More preferably, it is 0.00. It is 2-10 mass parts, More preferably, it is 0.3-5 mass parts. From the viewpoint of obtaining a dot pattern having a practical hardness, the addition amount of the photoacid generator is 0.01 parts by mass or more, and from the viewpoint of the stability of the composition, it is 30 parts by mass or less.

  It is preferable to add a cationic curable monomer and / or polymer to the photoacid generator composition.

From the viewpoint of ashing resistance, etching resistance, film strength, hardness, and heat resistance, the photosensitive resin material 52 preferably contains a monomer containing an aromatic group, a polycyclic group, or a heterocyclic group (one compound) Are compounds classified into two or more types among aromatic groups, polycyclic groups, and heterocyclic groups). Examples of the aromatic group include a compound having a phenyl, naphthalene, or anthracene skeleton. As the skeleton containing a phenyl group, a compound in which a plurality of aromatic groups such as biphenyl are directly bonded to each other, and a plurality of aromatic groups such as a bisphenol A skeleton are carbon, oxygen, nitrogen, silicon, sulfur. The compound couple | bonded by the crosslinking group containing at least 1 type is included. Examples of aromatic groups include phenyl, naphthalene, and anthracene as substituents —R ¹ —R ⁴ (R ¹ is at least one element of carbon, oxygen, nitrogen, silicon, and sulfur) Which is preferably a substituent composed of carbon and / or oxygen, and R ⁴ is an epoxycyclohexyl group, a glycidyl group, or a vinyl ether group). Another hydrogen atom may be substituted with a functional group containing carbon, oxygen, nitrogen, silicon, sulfur, fluorine, chlorine, bromine, or iodine. In addition, development with an alkaline aqueous solution is possible if such a compound has a substituent such as a carboxylic acid group, a carboxylic anhydride group, or a hydroxy group that improves the solubility in an alkaline aqueous solution. Therefore, it is preferable.

  Examples of the compound in which a plurality of aromatic groups are directly bonded include at least one of compounds including the structure of the following chemical formula group E.

Chemical formula group E

  Examples of the compound in which a plurality of aromatic groups are bonded with a bridging group containing at least one of carbon, oxygen, nitrogen, silicon, and sulfur include at least one of compounds having the structure of the following chemical formula group F: It is done.

Chemical formula group F

  Examples of the polycyclic compound include at least one of compounds including the structure of the following chemical formula group G.

Chemical formula group G

  Examples of the heterocyclic compound include at least one of compounds including the structure of the following chemical formula group H.

Chemical formula group H

The substitution position of the aromatic group, polycyclic group, or heterocyclic group described above may be substituted anywhere as long as it can be bonded, may be substituted, and the substituent may be- R ¹ -R ⁴ may be mentioned (R ¹ is a substituent containing at least one element selected from the group consisting of carbon, oxygen, nitrogen, silicon and sulfur, and preferably composed of carbon and / or oxygen. A substituent, and R ⁴ is an epoxycyclohexyl group, a glycidyl group, or a vinyl ether group). Further, a structure in which another hydrogen atom is substituted with a functional group containing carbon, oxygen, nitrogen, silicon, sulfur, fluorine, chlorine, bromine, or iodine may be used. In addition, development with an alkaline aqueous solution is possible if such a compound has a substituent such as a carboxylic acid group, a carboxylic anhydride group, or a hydroxy group that improves the solubility in an alkaline aqueous solution. Therefore, it is preferable.

  In the above, good acrylic monomers such as ashing resistance, etching resistance, heat resistance, etc. were mentioned, but it is sufficient that the entire composition contains an aromatic group, a polycyclic group, or a heterocyclic group. Or a cationic curable monomer having an ethylene oxide chain may be added.

  Specific examples of the cationic curable monomer include the following. Examples of the alicyclic epoxy compound include 3 ′, 4′-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl, 3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylic acid-3,4-epoxy. Examples include -6′-cyclohexylmethyl, vinylcyclohexylene monooxide 1,2-epoxy-4-vinylcyclohexane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  Examples of the glycidyl ether include bisphenol A glycidyl ether, bisphenol F glycidyl ether, hydrogenated bisphenol A glycidyl ether, hydrogenated bisphenol F glycidyl ether, 1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether, Examples include methylolpropane triglycidyl ether, glycidyl methacrylate, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylethyldiethoxysilane, and 3-glycidyloxypropyltriethoxysilane.

  Examples of the oxetane compound include 3-ethyl-3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3allyloxymethyloxetane, 3-ethyl-3- ( 2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane.

  Examples of the vinyl ether include 2-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, and 1,4-butanediol divinyl ether. It is done.

  Among these, an alicyclic epoxy compound improves polymerization initiation rate, and an oxetane compound has an effect of improving the polymerization rate. Therefore, it is preferable to use alicyclic epoxy compound, and glycidyl ether reduces the viscosity of a cation-curable resin material. Since it is effective in workability, it is preferable to use it. More preferably, from the viewpoint of increasing the reaction rate of the initial reaction and the initial stage of the reaction, the alicyclic epoxy compound and the oxetane compound are used in combination, and more preferably the weight ratio of the alicyclic epoxy compound and the oxetane compound is It is to use together in the range of 99: 1 to 51:49. From the viewpoint of increasing the heat resistance of the cured product, an inorganic compound such as Si or Ti atom is preferably included.

  The addition amount is the above-mentioned aromatic group, polycyclic group, or heterocyclic group with respect to the cationic curable monomer compound (100 parts by mass) from the viewpoint of ashing resistance, etching resistance, film strength, hardness, and heat resistance. The content monomer is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and most preferably 70 parts by mass or more.

  An oligomer or a polymer may be added to the resin material for viscosity adjustment, ashing resistance, and etching resistance.

  Preferred structures include phenol novolac oligomer / polymer, cresol novolac oligomer / polymer, styrene oligomer / polymer, norbornene ring-opening polymer oligomer / polymer, norbornene addition polymer oligomer / polymer, norbornadiene ring-opening polymer. Examples thereof include oligomers / polymers, norbornadiene addition polymer oligomers / polymers, and oligomers / polymers of acrylic monomers described above. Furthermore, it is preferable that an epoxycyclohexyl group, a glycidyl group, or a vinyl ether group is bonded to the side chain of the oligomer / polymer because physical properties such as ashing resistance, etching resistance, and hardness are further improved. In addition, if the oligomer / polymer has side groups such as a carboxylic acid group, a carboxylic anhydride group, or a hydroxy group that improve the solubility in an alkaline aqueous solution, development with an alkaline aqueous solution is possible. It is preferable to make it possible.

  The addition amount is preferably 10 parts by mass or more with respect to the cationic curable monomer compound (100 parts by mass) from the viewpoint of ashing resistance, etching resistance, film strength, hardness, and heat resistance, and 20 parts by mass. More preferably, it is more preferably 30 parts by mass or more, from the viewpoint of curability of the composition, it is preferably 1000 parts by mass or less, and more preferably 500 parts by mass or less.

  Metal alkoxides, metal chlorides, and their hydrolysates and hydrolysis condensates may be used. From the viewpoint of crack resistance and stability, it is preferable to use a condensate.

  Examples of the metal alkoxide include silane alkoxide, titanium alkoxide, zirconium alkoxide, and tantalum alkoxide. From the viewpoint of stability, silane alkoxide, titanium alkoxide, or zirconium alkoxide is preferable, and silane alkoxide is more preferable. Examples of the metal chloride include tetrachlorosilane, titanium chloride, zirconium chloride, and tantalum chloride.

  Examples of the silane alkoxide or chlorosilane include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and vinyltrimethoxy. Silane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, di Cyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, diphenyldimethoxysila , Diphenyldiethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxy Silane, 3-acryloxypropyltriethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethylmethyldimethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acrylic Roxyethyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysila , Acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3 4-epoxycyclohexyl) ethyldimethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethylmethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ) Ethylethoxydimethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropylmethoxydimethylsilane, 3-glycidoxypropylethoxydimethylsilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltri Ethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) 2-aminoethyl-3-amino Propyltrimethoxysilane hydrochloride, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, methyltrichlorosilane, phenyltrichlorosilane, dimethyl Examples include dichlorosilane, trimethylchlorosilane, triethylchlorosilane, t-butyldimethylchlorosilane, and tri-i-propylchlorosilane. From the viewpoint of the stability, hardness, ashing resistance, and etching resistance of the cured product, it is more preferable to have a functional group capable of reacting with a photoacid generator. 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethylmethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethylethoxydimethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 3 Glycidoxypropyl methyl diethoxy silane, 3-glycidoxypropyl methoxydimethyl silane, such as 3-glycidoxypropyl ethoxydimethylsilyl silane and the like.

  Other metal alkoxides or metal chlorides include titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide, zirconium tetramethoxide, zirconium tetraethoxide, Zirconium tetra n-propoxide, zirconium tetraisopropoxide, zirconium tetra n-butoxide, tantalum pentamethoxide, tantalum pentaethoxide, tantalum penta n-propoxide, tantalum pentaisopropoxide, tantalum penta n-butoxide, etc. It is done.

  Fine particles such as titanium oxide, zirconium oxide, silica, ITO, ZnO, SnO, IZO, ATO, and AZO may be contained. In that case, from the viewpoint of film physical properties and transparency, the particle size is preferably 1000 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. These may be used alone or in combination of two or more.

  When a metal oxide, a metal composite oxide, a metal, or an organic-inorganic hybrid material is added for the purpose of improving or controlling the etching resistance and ashing resistance of the composition, the dot is composed of a plurality of convex portions or concave portions. It is necessary to blend in a well-balanced manner in the entire composition in the microstructure layer containing. On the other hand, in order to improve physical properties such as heat resistance and transparency, the addition amount is preferably 10 parts by mass or more, and 20 parts by mass or more with respect to the composition (100 parts by mass) of the microstructure layer. More preferably, it is more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, further preferably 70 parts by mass or more, and most preferably 90 parts by mass or more.

<Photobase generator>
The photobase generator is not particularly limited as long as it generates a base by light irradiation. For example, WPBG-018 (manufactured by Wako Pure Chemical Industries), WPBG-027 (manufactured by Wako Pure Chemical Industries), WPBG-082 (manufactured by Wako Pure Chemical Industries), WPBG-140 (manufactured by Wako Pure Chemical Industries), etc. Is mentioned.

  As the reactive monomer used in the photobase generator composition, an epoxy group, an oxetane group, a metal alkoxide, a hydrolyzate thereof, a hydrolysis condensate, and the like can be used.

  The addition amount of a photobase generator is 0.01-30 mass parts with respect to a reactive monomer compound (100 mass parts), Preferably it is 0.1-20 mass parts, More preferably, it is 0.2. -10 parts by mass, more preferably 0.3-5 parts by mass. From the viewpoint of obtaining a dot pattern having a practical hardness, the addition amount of the photoacid generator is 0.01 parts by mass or more, and from the viewpoint of the stability of the composition, it is 30 parts by mass or less.

  About the photosensitive resin material 52, the structure which laminated | stacked the some photosensitive resin material in order may be sufficient. When the ashing and etching steps are performed, it is preferable to use a material having excellent ashing resistance on the surface (dot pattern surface) of the photosensitive resin material 52 and a material having excellent etching resistance on the lower side opposite to the surface. For example, a photosensitive resin material containing a titanium compound is used on the surface side of the photosensitive resin material 52, and a photosensitive resin material having a high carbon ratio is used on the back surface side of the photosensitive resin material 52. The photosensitive composition may contain an organic solvent.

  (1) Aliphatic alcohol: methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, 1-pentanol, isoamyl alcohol, s-amyl alcohol, t- Amyl alcohol, 2-methyl-1-butanol, 1-hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, isohexyl alcohol, methyl-1-pentanol, s-hexanol, 1-heptanol , Isoheptyl alcohol, 2,3-dimethyl-1-pentanol, 1-octanol, 2-ethylhexanol, isooctyl alcohol, 2-octanol, 3-octanol, 1-nonanol, isononyl alcohol, 3, 5, 5 -Trimethyl hex Nord, 1-decanol, isodecyl alcohol, 3,7-dimethyl-1-octanol, 1-Hendekanoru, 1-dodecanol, isododecyl alcohol, allyl alcohol, propargyl alcohol, Hekishinoru

  (2) Aromatic alcohol: benzyl alcohol, (2-hydroxyphenyl) methanol, (methoxyphenyl) methanol, (3,4-dihydroxyphenyl) methanol, 4- (hydroxymethyl) benzene-1,2-diol, (4 -Hydroxy-3-methoxyphenyl) methanol, (3,4-dimethoxyphenyl) methanol, (4-isopropylphenyl) methanol, 2-phenylethanol, 1-phenylethanol, 2-phenyl-1-propanol, p-tolyl alcohol 2- (4-hydroxy-3-methoxyphenyl) ethane-1-ol, 2- (3,4-dimethoxyphenyl) ethane-1-ol, 3-phenylpropan-1-ol, 2-phenylpropane-2 -Ol, cinnamyl alcohol, 3- (4- Loxy-3-methoxyphenyl) prop-2-en-1-ol, 3- (4-hydroxy-3,5-methoxyphenyl) prop-2-en-1-ol, diphenylmethanol, trityl alcohol, 1,2 -Diphenylethane-1,2-diol, 1,1,2,2, -tetraphenylethane-1,2-diol, benzene-1,2-dimethanol, benzene-1,3-dimethanol, benzene-1 4-dimethanol

  (3) Alicyclic alcohol: cyclohexanol, methylcyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, tetrahydro-2-furanmethanol

  (4) Glycol and derivatives thereof: for example, ethylene glycol, ethylene glycol monoalkyl (1 to 8 carbon atoms) ether, ethylene glycol monovinyl ether, ethylene glycol monophenyl ether, dioxane, diethylene glycol monoalkyl (1 to 6 carbon atoms) ) Ether, diethylene glycol monovinyl ether, diethylene glycol monophenyl ether, triethylene glycol monoalkyl (1 to 3 carbon atoms) ether, triethylene glycol monovinyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, propylene glycol, Propylene glycol monoalkyl (1 to 4 carbon atoms) ether, propylene glycol monophenyl Ether, dipropylene glycol monoalkyl (1-3 carbon atoms) ether, ethylene glycol monoacetate, propylene glycol monoacrylate, propylene glycol monoacetate

  (5) Ketone compounds: acetone, methyl ethyl ketone, 3-butyn-2-one, methyl-n-propyl ketone, methyl isopropyl ketone, 3-pentyn-2-one, methyl isopropenyl ketone, methyl n-butyl ketone, methyl isobutyl Ketone, mesityl oxide, 4-hydroxy-4-methyl-2-pentanone, methyl-n-amyl ketone, methyl isoamyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisopropyl ketone, 2-octanone, 3- Octanone, 5-methyl-3-heptanone, 5-nonanone, diisobutylketone, trimethylnonanone, 2,4-pentanedione, 2,5-hexanedione, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, propiophenone Isophorone

  (6) Others: N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, pyridine, γ-butyrolactone, α-acetyl-γ- Butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone

  These can be used alone or in combination of two or more. Among these, acetone, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, gamma butyrolactone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether and the like are preferable.

  These solvents can be appropriately added to the photosensitive resin material 52 depending on the coating film thickness and viscosity, but are 50 to 10,000 masses based on the mass of all components other than the solvent in the photosensitive resin material 52. % Is preferably used.

  The photosensitive resin material 52 includes an antioxidant, a polymerization inhibitor, an ultraviolet absorber, a radical scavenger, a sensitizer, and an adhesion assistant for the storage stability of the photosensitive resin material and the high definition of photolithography. It is preferable to include at least one kind of agent. A plurality of these additives may be added. Multiple types may be added for the same purpose.

  An antioxidant can be added for the purpose of improving stability during storage in the presence of oxygen, heat resistance of the resin, and light resistance. Examples of such antioxidants include hindered phenols, phosphoruss, lactones, vitamin Es, and sulfurs. Specifically, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX (registered trademark) 245 manufactured by BASF), 1,6-hexanediol- Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) (IRGANOX (registered trademark) 259 manufactured by BASF), 2,4-bis- (n-octylthio) -6- (4 -Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (IRGANOX (registered trademark) 565 manufactured by BASF), pentaerythrityl tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate) (IRGANOX (registered trademark) 1010 manufactured by BASF), 2,2-thio-diethylenebis [ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (IRGANOX (registered trademark) 1035 manufactured by BASF), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate (IRGANOX (registered trademark) 1076 manufactured by BASF), N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) (IRGANOX (registered trademark) manufactured by BASF) 1098), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester (IRGAMOD (registered trademark) 295, manufactured by BASF), 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (IRGANOX (registered trademark) manufactured by BASF) 330), tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate (IRGANOX (registered trademark) 3114 manufactured by BASF), octylated diphenylamine (IRGANOX (registered trademark) 5057 manufactured by BASF) ), 2,4-bis [(octylthio) methyl) -o-cresol (IRGANOX (registered trademark) 1520L manufactured by BASF), isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX (registered trademark) 1135 manufactured by BASF), 2,4-bis (dodecylthiomethyl) -6-methylphenol (IRGANOX (registered trademark) 1726 manufactured by BASF), 2,5,7,8-tetramethyl- 2- (4,8,12-trimethyltridecyl) chroman-6-ol (BA SFGA IRGANOX (registered trademark) E201), 5,7-di-t-butyl-3- (3,4-dimethylphenyl) benzofuran-2 (3H) -one (IRGANOX (registered trademark) HP-136), Tris (2,4-di-t-butylphenyl) phosphite (IRGAFOS (registered trademark) 168 manufactured by BASF), Tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl)] Dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine (manufactured by BASF, IRGAFOS® 12), bis (2,4-di-t -Butyl-6-methylphenyl) ethyl phosphite (IRGAFOS (registered trademark) 38, manufactured by BASF), 3,3-thiobispropionic acid didodecyl ester (IR, manufactured by BASF) ANOX (registered trademark) PS800), 3,3-thiobispropionic acid dioctadecyl ester (IRGANOX (registered trademark) PS802 manufactured by BASF), 3,9-bis [2- [3- (3-t-butyl-4 -Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (SUMIZER® GA-80 manufactured by Sumitomo Chemical Co., Ltd.) ), 2,2′-methylenebis (6-t-butyl-4-methylphenol) (SUMILIZER® MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 4,4′-butylidenebis (6-t-butyl-3-) Methylphenol) (SUMILIZER (registered trademark) BBM-S, manufactured by Sumitomo Chemical Co., Ltd.), 4,4′-thiobis (6-tert-butyl-3-methyl) Ruphenol) (SUMILIZER (registered trademark) WX-R manufactured by Sumitomo Chemical Co., Ltd.), pentaerythrityl tetrakis (3-laurylthiopropionate) (SUMILIZER (registered trademark) TP-D manufactured by Sumitomo Chemical), 2-mercaptobenz Imidazole (SUMILIZER (registered trademark) MB manufactured by Sumitomo Chemical Co., Ltd.), biphenyl-4,4′-diylbis [bis (2,4-di-t-butyl-5-methylphenoxy) phosphine] (GSY-P101 manufactured by Osaki Kogyo Co., Ltd.) ) And the like are exemplified, but not limited thereto. These antioxidants can be used alone or as a mixture of two or more. When the antioxidant is added, the addition amount is preferably 0.001 to 30 parts by mass and more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound.

  A polymerization inhibitor can be added to the photosensitive resin material of the present invention for the purpose of improving the viscosity during storage or the stability of photosensitivity and the accuracy of photolithography. Examples of such polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid. 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N- Ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt ,Screw 4-hydroxy-3,5-di-tert- butyl) phenyl methane, or the like can be used. When the polymerization inhibitor is added, the addition amount is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound.

  An ultraviolet absorber can be added to the photosensitive resin material of the present invention in order to reduce stability during storage, light resistance of the resin, and residues during photolithography development. Examples of such ultraviolet absorbers include benzotriazole compounds and benzophenone compounds. Specifically, the reaction product of 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester Product (TINUVIN (registered trademark) 405 manufactured by BASF), 2- (2Hbenzotriazol-2-yl) phenol, 2- (2Hbenzotriazol-2-yl) -4,6-t-pentylphenol, 2- ( 2H benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- ( 2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2-hydroxy-4-methoxybenzophenone, etc. . The addition amount in the case of adding the ultraviolet absorber is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound. More preferably, it is 2 to 5 parts by mass.

  A radical scavenger can be added to the photosensitive resin material of the present invention in order to reduce stability during storage and residues during photolithography development. Examples of such radical scavengers include nitroxy radical compounds. For example, di-tert-butyl nitroxide, di-1,1-dimethylpropyl nitroxide, di-1,2-dimethylpropyl nitroxide, di-2,2-dimethylpropyl nitroxide, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4- Carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-cyano-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-methacrylic acid-2,2,6 , 6-Tetramethylpiperidine 1-oxyl free radical, 4-acrylic acid-2, , 6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4- (2-chloroacetamido) -2,2,6,6-tetramethylpiperidine 1-oxyl Free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxylbenzoate free radical, 4-isothiocyanato-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4- ( 2-Iodoacetamide) -2,2,6,6-tetramethylpiperidine 1 -Oxyl free radical, 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical. The addition amount in the case of adding the radical scavenger produces an effect even in a small amount, but is preferably 0.00001 to 10 parts by mass, and 0.001 to 5 parts by mass with respect to 100 parts by mass of the polymerizable compound. More preferably, it is more preferably 0.01 to 2 parts by mass. Further, it is preferable to use an ultraviolet absorber in combination with a radical scavenger because the resolution of photolithography can be greatly improved.

  A sensitizer for improving photosensitivity can be added to the photosensitive resin material of the present invention. Examples of such a sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6-bis (4′-diethylamino). Benzylidene) cyclohexanone, 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) ) Chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylamino) Biphenyl) benzothiazole, 1,3-bis (4-dimethyla) Nobenzylidene) acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7- Dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine , Np-tolyldiethanolamine, N-phenylethanolamine, N, N-bis (2-hydroxyethyl) aniline, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, 4-diethylamino Isoamyl benzoate, benztriazole, 2-mercaptobenzimidazole, 1-phenyl-5-mercapto-1,2,3,4-tetrazole, 1-cyclohexyl-5-mercapto-1,2,3,4-tetrazole, 1- (tert-butyl) -5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benz Examples include thiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-p) thiazole, 2- (p-dimethylaminobenzoyl) styrene, and the like. Moreover, these compounds can be used alone or as a mixture of two or more. Although the addition amount in the case of adding a sensitizer is dependent on the amount of another additive component, it is preferable that it is 0.01-10 mass parts with respect to 100 mass parts of polymeric compounds, and 0.1-5 More preferably, it is part by mass.

  To the photosensitive resin material of the present invention, an adhesion assistant for improving the adhesion to the substrate during photolithography development or baking can be added. Examples of such adhesion assistants include silane coupling agents, thiol compounds, and phosphate acrylates. Examples of silane coupling agents include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Triethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethylmethyldimethoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysilane, methacryl Roxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethylmethyldimethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethylto Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane, 2- (3,4-epoxycyclohexyl) ethylmethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethylethoxydimethylsilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethoxydimethylsilane, 3-glycidoxy Propylethoxydimethylsisilane N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3- Aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3- Aminopropyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane Hydrochloride, 3-mercaptopropylto Examples include limethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. In particular, 3-glycidoxypropyltrimethoxysilane (KBE-403 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-aminopropyltriethoxysilane (Shin-Etsu) Chemical industry KBE-903) is preferred. Examples of thiol compounds include pentaerythritol tetrakis (3-mercaptobutyrate) (Karenz (registered trademark) MT-PE1 manufactured by Showa Denko KK), 1,4-bis (3-mercaptobutyryloxy) butane (Showa Denko KK). Karenz (registered trademark) MT-BD1), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione ( Karenz (registered trademark) MT-NR1 manufactured by Showa Denko KK, trimethylolpropane tris (3-mercaptobutyrate) (TPMB manufactured by Showa Denko KK), trimethylol ethane tris (3-mercaptobutyrate) (TEMB manufactured by Showa Denko KK) ), Etc. The addition amount of the adhesion assistant is preferably 1 to 100 parts by mass and more preferably 2 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound. If the addition amount is 1 part by mass or more, a cured molded article having excellent adhesion to an inorganic material substrate such as glass or metal can be obtained. When the addition amount is 250 parts by mass or less, a practical cured molded product can be obtained while maintaining other characteristics.

  A light stabilizer can be added to the photosensitive resin material of the present invention for stability during storage. Examples of such light stabilizers include hindered amine compounds. Specifically, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate (manufactured by ADEKA, ADK STAB (registered trademark) LA-52), Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate (manufactured by ADEKA, ADK STAB (registered trademark) LA-57), bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate (manufactured by ADEKA, Adekastab (registered trademark) LA-72), bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (Adeka, ADK STAB (registered trademark) LA-81), 1,2,6,6-pentamethyl-4-piperidyl methacrylate (Adeka) ADK STAB (R) LA-82), 2,6,6- tetramethyl-4-piperidyl methacrylate (ADEKA Co., Ltd., ADK STAB (R) LA-87), and the like. The addition amount in the case of adding the light stabilizer is preferably 0.001 to 30 parts by mass, and more preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound.

  If necessary, the photosensitive resin material of the present invention may contain other additives such as a coating film smoothness-imparting agent, as long as the properties required for the photosensitive resin composition according to the present invention are not impaired. It can mix | blend suitably.

  Photolithography is a method of patterning based on the difference in solubility of the resist in the developer due to exposure. The negative resist is insoluble in the developer or the solubility is lowered in the exposed portion, and the unexposed portion is in the developer. It is possible to leave the exposed portion as a pattern. A negative resist can be used for the photosensitive resin material 52.

  When the photosensitive resin material 52 is alkali-soluble, it can be developed with an aqueous alkali solution, which is preferable from the viewpoint of environmental considerations.

  In order to give the photosensitive resin 52 alkali solubility, a polymer or monomer having an alkali-soluble group can be added.

Examples of the alkali-soluble polymer include polymers having an alkali-soluble group such as a carboxylic acid group, a phenol group, a phosphoric acid group, a sulfonic acid group, and a silanol group. Specific examples include the following (1) to (5).
(1) Vinyl polymer composed mainly of a reaction product obtained by reaction of a compound having a polymerizable unsaturated double bond (2) Epoxy polymer composed mainly of an addition reaction product of an epoxy group and a hydroxyl group (3) Aromatic methylene polymer composed mainly of reaction product of phenol and formaldehyde (4) Urethane polymer composed mainly of reaction product of dialcohol and diisocyanate (5) Reaction of dicarboxylic acid and diepoxide Ester polymer composed mainly of products

  It is preferably at least one polymer selected from the group consisting of the polymers (1) to (5). In addition, in said polymer (1)-(5), a main body means containing 70 mol% or more of the component in a molecule | numerator.

  The alkali-soluble polymer has a polymerizable group such as an acryloxy group, a methacryloxy group, a glycidyl group, a 1,2-epoxycyclohexyl group, a vinyl group, or an allyl group in the side chain. More preferable in terms of elastic modulus and the like.

The polymers (1) to (5) will be described in detail below.
(About polymer (1))
A vinyl polymer mainly composed of a reactant of a polymerizable unsaturated double bond is obtained by polymerizing a compound having an acryloyl group, a methacryloyl group, a vinyl group, an allyl group or the like (hereinafter referred to as a monomer). Can be mentioned.

Examples of the method for obtaining the alkali-soluble group-containing vinyl polymer include the following two methods.
(I) A method of polymerizing one or more monomers including an alkali-soluble group-containing monomer. It may be a copolymer with a monomer that does not contain an alkali-soluble group.
(Ii) a vinyl polymer obtained by polymerizing one or more monomers including a monomer containing a reactive group such as a hydroxy group, an amino group, a glycidyl group, or a 1,2-epoxycyclohexyl group; By reacting at least one functional group capable of reacting with the reactive group with at least one compound having an alkali-soluble group, or a carboxylic acid anhydride, an alkali-soluble group is added to the side chain of the vinyl polymer. How to introduce.

  When a carboxylic acid group is selected as the alkali-soluble group, examples of the monomer used for the preparation of the carboxylic acid group-containing vinyl polymer include (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, and And maleic acid half ester. These may be used alone or in combination of two or more.

  Examples of the monomer having no alkali-soluble group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, and n-butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone (meth) acrylate, nonylphenoxy polypropylene glycol (meta ) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylamide, N-methylolacrylamide, N-but Cymethylacrylamide, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, benzyl (meth) acrylate, 4-hydroxybenzyl (meth) acrylate, 4-methoxybenzyl (meth) acrylate, 4-methylbenzyl ( (Meth) acrylate, 4-chlorobenzyl (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, 3-methyl-3- (meth) acrylate, 3-ethyl-3- (meth) acryloxymethyloxetane, Examples include hexafluoropropyl (meth) acrylate, 3- (meth) acryloylpropyltrimethoxysilane, and 3- (meth) acryloylpropyltriethoxysilane. Other examples include the acrylic monomers from the viewpoint of ashing resistance and etching resistance. These may be used alone or in combination of two or more.

  As a monomer used to give a reactive group to the side chain, an epoxy (meth) acrylate obtained by reacting an epoxy resin having two epoxy groups and (meth) acrylic acid in a conventional manner. A half ester is mentioned. For example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, vinylcyclohexene monooxide, hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol di Phenyl diglycidyl ether such as glycidyl ether and (meth) acrylic acid half ester, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound and the like bisphenol type epoxy compound and (meth) acrylic acid half ester, hydrogenated bisphenol-A type Xy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Hydrogenated bisphenol type epoxy compound such as epoxy compound and half ester of (meth) acrylic acid, cycloaliphatic diglycidyl ether compound such as cyclohexanedimethanol diglycidyl ether compound and half ester of (meth) acrylic acid, 1,6 -Aliphatic diglycidyl ether compounds such as hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether, and (meth) acrylic acid half esters. These may be used alone or in combination of two or more. Other examples include monomers having a hydroxyl group and monomers having an amino group. Specific examples include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, 2-hydroxy methacrylate. Examples include propyl, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, and the like.

  Examples of the acid anhydride for introducing a carboxylic acid into the side chain of the vinyl polymer include succinic anhydride, cyclohexanedicarboxylic anhydride, 4-methyl-cyclohexanedicarboxylic anhydride, and 5-methyl-cyclohexanedicarboxylic anhydride. , Bicycloheptanedicarboxylic anhydride, 7-oxabicycloheptanedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3-tri And polybasic acid anhydrides such as (methoxysilylpropyl) succinic anhydride and (3-triethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more. Other examples include ring-opened products (dicarboxylic acid compounds) of these anhydrides.

  It is preferable to introduce a polymerizable group into the side chain of the vinyl polymer, but in this case, by reaction of a vinyl polymer having a carboxylic acid in the side chain with a monomer having a glycidyl group or a 1,2-epoxycyclohexyl group. It is possible to easily introduce a polymerizable group into the side chain.

  The vinyl copolymerization in the preparation of the carboxyl group-containing vinyl polymer can be carried out by a conventional method, and known methods such as solution polymerization, suspension polymerization method and emulsion polymerization method are possible. Polymerization is preferred. As the polymerization initiator that can be used in this case, those having a 10-hour half-life temperature in the range of 60 ° C to 120 ° C are preferable. Such polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutylnitrile). 2,2′-azobis (2-methylpropionate), 2,2′-azobis (N-cyanohexyl-2-methylpropionamide), 2,2′-azobis (N- (2-propenyl)- Azos such as 2-methylpropionamide), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-amylperoxy-2- Ethyl hexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-amino Peroxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-hexylperoxybenzoate, t-butylperoxyacetate, t-butylperoxy-m-tolylbenzoate, peroxy such as t-butylperoxybenzoate Esters, peroxymonocarbonates such as t-hexylperoxyisopropylmonocarbonate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, bis-3,5,5-trimethylhexanoyl peroxide, octa Diacyl peroxides such as noyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, dicumyl peroxide, t- Dialkyl peroxides such as chill cumyl peroxide, and the like. These may be used alone or in combination of two or more.

  In the preparation of a carboxyl group-containing vinyl polymer, the addition reaction between a carboxyl group and a compound having an epoxy group and a (meth) acryl group is preferably performed in a solvent using a polymerization inhibitor and a catalyst. The temperature is preferably 50 ° C to 120 ° C.

  Examples of the reaction solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl Teracetate, ethylene glycol monobutyl ether Acetates such as cetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; octane, decane, etc. Aliphatic hydrocarbons; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more.

  Examples of the reaction catalyst in the preparation of the carboxyl group-containing vinyl polymer include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, Examples thereof include phosphorus compounds such as triphenylphosphine, metal salts of organic acids such as lithium, chromium, zirconium, potassium and sodium of naphthenic acid, lauric acid, stearic acid, oleic acid or octoenoic acid. These may be used alone or in combination of two or more.

  Examples of the polymerization inhibitor in the preparation of the carboxyl group-containing vinyl polymer include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and phenothiazine. These may be used alone or in combination of two or more.

  Furthermore, although a dicarboxylic acid anhydride can be partially added to the hydroxyl group of the reaction product, the reaction temperature is preferably 50 ° C to 120 ° C.

  Examples of the structure of the carboxyl group-containing vinyl polymer include a carboxyl group-containing vinyl polymer represented by the following general formula (1) or the following general formula (4).

｛式中、Ｒｄは、炭素原子数が０〜５０、好ましくは０〜２０の直鎖状、分岐鎖状又は環状の２価の有機基であり、Ｒｅは、下記一般式（２）で表される１価の有機基、又は水素であり、Ｒｆは、炭素原子数１〜５０、好ましくは１〜２０の直鎖状、分岐鎖状又は環状の１価の有機基であり、Ｒｈは、メチル基又は水素であり、ｍは、０〜５，０００、好ましくは０〜５００から選ばれる整数であり、そしてｎは、１０〜１０，０００、好ましくは１０〜１，０００から選ばれる整数である。ｍ＝０の場合は、複数のＲｆのうち、少なくとも一つのＲｆがアルカリ可溶性基を有している。｝

{In the formula, Rd is a linear, branched or cyclic divalent organic group having 0 to 50 carbon atoms, preferably 0 to 20 carbon atoms, and Re is represented by the following general formula (2). Rf is a linear, branched or cyclic monovalent organic group having 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, and Rh is A methyl group or hydrogen, m is an integer selected from 0 to 5,000, preferably 0 to 500, and n is an integer selected from 10 to 10,000, preferably 10 to 1,000. is there. When m = 0, at least one Rf among the plurality of Rf has an alkali-soluble group. }

｛式中、Ｒｂは、炭素原子数が１〜２０の直鎖状、分岐鎖状若しくは環状の１価の有機基、又は光重合性不飽和二重結合基を有する１価の有機基であり、そしてＲｃは、下記一般式（３）で表される基、又は水素である。｝

{Wherein, Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or a monovalent organic group having a photopolymerizable unsaturated double bond group. , And Rc is a group represented by the following general formula (3) or hydrogen. }

｛式中、Ｒａは、炭素原子数が２〜１６の直鎖状、分岐鎖状又は環状の２価の有機基である。｝

{In the formula, Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms. }

｛式中、Ｒｂは、炭素原子数が１〜２０の直鎖状、分岐鎖状若しくは環状の１価の有機基、又は光重合性不飽和二重結合基を有する１価の有機基であり、Ｒｃは、上記一般式（３）で表される基又は水素であり、Ｒｄは、炭素原子数が０〜５０、好ましくは０〜２０の直鎖状、分岐鎖状若しくは環状の２価の有機基、又は光重合性不飽和二重結合を有してもよい２価の有機基であり、Ｒｆは、炭素原子数１〜５０、好ましくは１〜２０の直鎖状、分岐鎖状又は環状の１価の有機基であり、Ｒｈはメチル基又は水素であり、ｍは、０〜５，０００、好ましくは０〜５００から選ばれる整数であり、そしてｎは、１０〜１０，０００、好ましくは１０〜１，０００から選ばれる整数である。ｍ＝０の場合は、複数のＲｆのうち、少なくとも一つのＲｆがアルカリ可溶性基を有している。｝

{Wherein, Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or a monovalent organic group having a photopolymerizable unsaturated double bond group. , Rc is a group represented by the above general formula (3) or hydrogen, and Rd is a linear, branched or cyclic divalent group having 0 to 50 carbon atoms, preferably 0 to 20 carbon atoms. It is an organic group or a divalent organic group that may have a photopolymerizable unsaturated double bond, and Rf is a straight chain, branched chain or 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms. A cyclic monovalent organic group, Rh is a methyl group or hydrogen, m is an integer selected from 0 to 5,000, preferably 0 to 500, and n is 10 to 10,000, Preferably, it is an integer selected from 10 to 1,000. When m = 0, at least one Rf among the plurality of Rf has an alkali-soluble group. }

(Polymer (2) (Epoxy polymer mainly composed of addition reaction product of epoxy group and hydroxyl group))
Examples of the polymer include a carboxyl group-containing epoxy polymer represented by the following general formula (5).

｛式中、Ｒｃは、上記一般式（３）で表される基又は水素であり、Ｒｇは、炭素原子数が２〜２０の直鎖状、分岐鎖状又は環状の２価の有機基であり、Ｒｉは、上記一般式（２）又は下記一般式（６）で表される１価の有機基であり、そしてｍは０〜１，０００から選ばれる整数である。｝

{In the formula, Rc is a group represented by the general formula (3) or hydrogen, and Rg is a linear, branched or cyclic divalent organic group having 2 to 20 carbon atoms. Yes, Ri is a monovalent organic group represented by the general formula (2) or the following general formula (6), and m is an integer selected from 0 to 1,000. }

  The carboxyl group-containing epoxy polymer used in the present invention is obtained by reacting a dialcohol compound with epihalohydrin to form a double-ended epoxy compound having an ether bond by reaction of an epoxy group and an alcohol group in the skeleton. It is obtained by reacting the hydroxyl group of the product with dicarboxylic anhydride. Furthermore, the both end epoxy groups of the reaction product may be subjected to an addition reaction with a carboxyl group or a (meth) acrylate compound having a hydroxyl group, or the hydroxyl group of the reaction product may be reacted with a dicarboxylic acid anhydride.

Examples of dialcohol compounds used in the preparation of carboxyl group-containing epoxy polymers include bisphenols such as bisphenol A, bisphenol F, and bisphenol S, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, and the like. Bisphenol end products, such as bisphenols, bisphenol A, bisphenol F, bisphenol S, and the like, adducts of both ends ethylene oxide (ethylene oxide moles 1 to 10), bisphenol A, bisphenol, both ends propylene oxide (propylene oxide, etc.) Mole number 1-10) Addition, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, etc. 10) adduct, hydrogenated bisphenol A, hydrogenated bisphenol F, both ends of propylene oxide of bisphenol, such as hydrogenated bisphenol S (propylene oxide mole number of 1 to 10) adducts, alkyl _(C 2 _{-C 10)} dialcohol, Examples include polyethylene glycol (ethylene oxide moles 1 to 10), polypropylene glycol (propylene oxide moles 1 to 10), and the like. These may be used alone or in combination of two or more.

  Examples of the epihalohydrin used for the preparation of the carboxyl group-containing epoxy polymer include epichlorohydrin and epibromohydrin. These may be used alone or in combination of two or more.

  Examples of compounds having a carboxyl group and a (meth) acrylate group in one molecule used for the preparation of a carboxyl group-containing epoxy polymer include (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth). Acrylate, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, And maleic acid half ester. These may be used alone or in combination of two or more.

  Examples of compounds having a hydroxyl group and a (meth) acrylate group in one molecule used for the preparation of a carboxyl group-containing epoxy polymer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, Examples thereof include glycerol methacrylate acrylate, pentaerythritol tri (meth) acrylate, and caprolactone adducts of these monomers.

  Examples of epoxy (meth) acrylate compounds in which an epoxy group is (meth) acrylate-modified include epoxy (meth) acrylates of phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, and bisphenol. -A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Epoxy (meth) acrylates of bisphenol type epoxy compounds, such as hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bi Fatty compounds such as epoxy (meth) acrylates of hydrogenated bisphenol type epoxy compounds such as epoxy compounds of (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, cyclohexanedimethanol diglycidyl ether compounds Epoxy (meth) of aliphatic diglycidyl ether compound such as epoxy (meth) acrylate of cyclic diglycidyl ether compound, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether An acrylate etc. are mentioned.

  Examples of the dicarboxylic acid anhydride used for the preparation of the carboxyl group-containing epoxy polymer include succinic anhydride, cyclohexanedicarboxylic acid anhydride, 4-methyl-cyclohexanedicarboxylic acid anhydride, 5-methyl-cyclohexanedicarboxylic acid anhydride, bicycloheptane. Dicarboxylic anhydride, 7-oxabicycloheptanedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) And polybasic acid anhydrides such as succinic anhydride and (3-triethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more.

  The reaction of epihalohydrin in the preparation of the carboxyl group-containing epoxy polymer can be performed by a conventional method. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to or dissolved in a dissolved mixture of a dialcohol compound and an epihalohydrin such as epichlorohydrin or epibromohydrin for 1 hour to 10 hours at 20 ° C to 120 ° C. An epoxy resin can be obtained by reacting for a period of time. After the reaction product of these epoxidation reactions is washed with water or without washing, epihalohydrin or other added solvent is removed under reduced pressure by heating at 110 ° C. to 250 ° C. and a pressure of 10 mmHg or less. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Can be further reacted to ensure ring closure. The reaction temperature is usually 50 ° C. to 120 ° C., and the reaction time is usually 0.5 hours to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent of toluene, methyl isobutyl ketone, etc. is distilled off under heating and reduced pressure to obtain the epoxy compound of the present invention.

  The addition reaction between the epoxy group and the compound having a carboxyl group or a hydroxyl group and a (meth) acryl group in the preparation of the carboxyl group-containing epoxy polymer is preferably performed in a solvent using a polymerization inhibitor and a catalyst. The reaction temperature is preferably 50 ° C to 120 ° C.

  In the preparation of the carboxyl group-containing epoxy polymer, the reaction solvent, the reaction catalyst, and the polymerization inhibitor are each composed of a vinyl polymer (polymer (1 The same reaction solvent, reaction catalyst and polymerization inhibitor as described in the preparation of)) can be used.

  Furthermore, although a dicarboxylic acid anhydride can be partially added to the hydroxyl group of the reaction product, the reaction temperature is preferably 50 ° C to 120 ° C.

(Polymer (3) (aromatic methylene polymer composed mainly of a reaction product of phenol and formaldehyde))
Examples of the polymer (3) include novolak type phenol polymers represented by the following general formula (7).

｛式中、Ｒｂは、炭素原子数が１〜２０の直鎖状、分岐鎖状若しくは環状の１価の有機基、又は光重合性不飽和二重結合基を有する１価の有機基であり、Ｒｃは、上記一般式（３）で表される基又は水素であり、Ｒｊは、メチル基、水酸基又は水素であり、Ｒｋは、上記一般式（２）若しくは上記一般式（６）で表される１価の有機基、又は水素であり、ｍは、１〜１，０００、好ましくは１〜１００から選ばれる整数であり、そしてｎは、０〜１，０００、好ましくは０〜１００から選ばれる整数であり、ｍ＋ｎが２より大きい整数である。ｎ＝０の場合は、複数のＲｋのうち少なくとも一つのＲｋは水素である。｝

{Wherein, Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or a monovalent organic group having a photopolymerizable unsaturated double bond group. , Rc is a group represented by the above general formula (3) or hydrogen, Rj is a methyl group, a hydroxyl group or hydrogen, and Rk is represented by the above general formula (2) or the above general formula (6). A hydrogen atom, m is an integer selected from 1 to 1,000, preferably 1 to 100, and n is 0 to 1,000, preferably 0 to 100. It is an integer selected, and m + n is an integer greater than 2. When n = 0, at least one Rk of the plurality of Rk is hydrogen. }

  The novolak type phenol polymer used in the present invention can be obtained by reacting an epihalohydrin with a condensation reaction product of phenol and formaldehyde. Furthermore, an epoxy group of the reaction product may be subjected to an addition reaction between a carboxyl group or a (meth) acrylate compound having a hydroxyl group, and the hydroxyl group of the reaction product may be reacted with a dicarboxylic acid anhydride.

  Examples of the phenol used for the preparation of the novolak type phenol polymer include phenol, cresol, xylenol, trimethylphenol and the like. These may be used alone or in combination of two or more.

  Examples of the epihalohydrin used in the novolac type phenol polymer include epichlorohydrin and epibromohydrin. These may be used alone or in combination of two or more.

  Examples of compounds having a carboxyl group and a (meth) acrylate group in one molecule used for the preparation of a novolak type phenol polymer include (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth) acrylate. 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, and And maleic acid half ester. These may be used alone or in combination of two or more.

  Examples of the hydroxyl group and (meth) acrylate compound used in the preparation of the novolak type phenol polymer in one molecule include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerol methacrylate acrylate, Examples thereof include pentaerythritol tri (meth) acrylate or caprolactone adducts of these monomers.

  Examples of epoxy (meth) acrylate compounds in which an epoxy group is (meth) acrylate-modified include epoxy (meth) acrylates of phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, and bisphenol. -A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Epoxy (meth) acrylates of bisphenol type epoxy compounds, such as hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bi Fatty compounds such as epoxy (meth) acrylates of hydrogenated bisphenol type epoxy compounds such as epoxy compounds of (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, cyclohexanedimethanol diglycidyl ether compounds Epoxy (meth) of aliphatic diglycidyl ether compound such as epoxy (meth) acrylate of cyclic diglycidyl ether compound, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether An acrylate etc. are mentioned.

  Dicarboxylic acid anhydrides used for the preparation of novolak type phenol polymers include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, 5-methyl-cyclohexane dicarboxylic acid anhydride, bicycloheptane dicarboxylic acid. Acid anhydride, 7-oxabicycloheptanedicarboxylic acid anhydride, tetrahydrophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, adipic acid anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) succinate And polybasic acid anhydrides such as acid anhydride and (3-triethoxysilylpropyl) succinic acid anhydride. These may be used alone or in combination of two or more.

  When the condensation reaction of phenol and formaldehyde in the preparation of the novolak type phenol polymer is carried out, it is preferable to use an acid catalyst. Various acid catalysts can be used, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, Acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride and the like are preferable, and p-toluenesulfonic acid, sulfuric acid and hydrochloric acid are particularly preferable.

  The condensation reaction of phenol and formaldehyde can be performed in the absence of a solvent or in the presence of an organic solvent. Specific examples in the case of using an organic solvent include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone and the like. The amount of the organic solvent used is usually 50% by mass to 300% by mass, preferably 100% by mass to 250% by mass, based on the total mass of the raw materials charged. The reaction temperature is usually 40 to 180 ° C., and the reaction time is usually 1 hour to 10 hours. These solvents may be used alone or in combination of two or more.

  After completion of the reaction, the water washing treatment is performed until the pH value of the water washing liquid of the reaction mixture becomes 3 to 7, preferably 5 to 7. When washing with water, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate, diethylenetriamine, You may process using various basic substances, such as organic amines, such as ethylenetetramine, aniline, and phenylenediamine, as a neutralizing agent. Moreover, what is necessary is just to perform according to a conventional method in the case of a water-washing process. For example, water in which the neutralizing agent is dissolved is added to the reaction mixture, and the liquid separation extraction operation is repeated.

  An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide was added to the dissolved mixture of the phenol / formaldehyde condensate obtained in the above reaction and epihalohydrin such as epichlorohydrin or epibromohydrin, or 20 ° C. with addition. An epoxy resin can be obtained by reacting at ˜120 ° C. for 1 hour to 10 hours. After the reaction product of these epoxidation reactions is washed with water or without washing, epihalohydrin or other added solvent is removed under reduced pressure by heating at 110 ° C. to 250 ° C. and a pressure of 10 mmHg or less. In addition, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. Further reaction can be performed by adding an aqueous solution to ensure ring closure. The reaction temperature is usually 50 ° C. to 120 ° C., and the reaction time is usually 0.5 hours to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent of toluene, methyl isobutyl ketone, etc. is distilled off under heating and reduced pressure to obtain the epoxy compound of the present invention.

  The addition reaction between the epoxy group and the compound having a carboxyl group or a hydroxyl group and a (meth) acryl group in the preparation of the novolak-type phenol polymer is preferably performed in a solvent using a polymerization inhibitor and a catalyst, The reaction temperature is preferably 50 ° C to 120 ° C.

  In the preparation of the novolak-type phenol polymer, the reaction solvent, the reaction catalyst, and the polymerization inhibitor are each a vinyl polymer (polymer (1)) mainly composed of the above-described reactant of the polymerizable unsaturated double bond. The same reaction solvent, reaction catalyst, and polymerization inhibitor as described in the preparation of) can be used.

  Furthermore, although a dicarboxylic acid anhydride can be partially added to the hydroxyl group of the reaction product, the reaction temperature is preferably 50 ° C to 120 ° C.

(About polymer (4) (urethane polymer composed mainly of a reaction product of dialcohol and diisocyanate))
Examples of the polymer (4) include a carboxyl group-containing urethane polymer represented by the following general formula (8).

｛式中、Ｒｂは、炭素原子数が１〜２０の直鎖状、分岐鎖状若しくは環状の１価の有機基、又は光重合性不飽和二重結合基を有する１価の有機基であり、Ｒｃは、上記一般式（３）で表される基又は水素であり、Ｒｇは、炭素原子数が２〜２０の直鎖状、分岐鎖状又は環状の２価の有機基であり、Ｒｌは、炭素原子数が４〜２０の直鎖状、分岐鎖状又は環状の２価の有機基であり、そしてｍは、１〜６００から選ばれる整数である。｝

{Wherein, Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or a monovalent organic group having a photopolymerizable unsaturated double bond group. , Rc is a group represented by the above general formula (3) or hydrogen, Rg is a linear, branched or cyclic divalent organic group having 2 to 20 carbon atoms, Rl Is a linear, branched or cyclic divalent organic group having 4 to 20 carbon atoms, and m is an integer selected from 1 to 600. }

  The carboxyl group-containing urethane polymer used in the present invention is obtained by subjecting a compound having two hydroxyl groups in one molecule and a compound having two isocyanate groups in one molecule to addition polymerization, and both terminal hydroxyl groups of the polymer. And addition reaction of a compound having an epoxy group and a (meth) acryl group in one molecule, and addition reaction of a dicarboxylic anhydride to the generated hydroxyl group.

  Examples of the compound having two hydroxyl groups in one molecule used for the preparation of the carboxyl group-containing urethane polymer include the following compounds (a) to (c).

(A) Dialcohol compounds: bisphenols such as bisphenol A, bisphenol F and bisphenol S, hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S, bisphenol A, bisphenol F and bisphenol S Bisphenol end-to-end ethylene oxide (ethylene oxide mole number 1 to 10) adduct, bisphenol A end-to-end propylene oxide (propylene oxide mole number 1 to 10) adduct, bisphenol A, bisphenol F, bisphenol S, etc., hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S and other bisphenol end-to-end ethylene oxide (ethylene oxide moles 1 to 10) adducts, hydrogenated bisphenol A, hydrogenated bisphenol , Both ends of propylene oxide (propylene oxide mole number of 1 to 10) adduct of bisphenol such as hydrogenated bisphenol S, alkyl _(C 2 _{-C 10)} di-alcohol, polyethylene glycol (ethylene oxide mole number of 1 to 10), polypropylene glycol (Propylene oxide mole number 1 to 10), hydroxyl-terminated liquid polybutadiene (Poly bd, manufactured by Idemitsu Kosan Co., Ltd.), hydroxyl-terminated polyolefin polyol (Epol, manufactured by Idemitsu Kosan), hydroxyl-terminated liquid polybutadiene hydrogenated product (Polytail H, Mitsubishi Chemical), polycarbonate diol (Duranol (registered trademark) T-5651, manufactured by Asahi Kasei Chemicals), and the like.

  (B) Epoxy (meth) acrylate compound in which both end epoxy groups are (meth) acrylate-modified: epoxy (meth) acrylate of phenyl diglycidyl ether such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, bisphenol- A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Epoxy (meth) acrylate of bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4 Hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound and other hydrogenated bisphenol type epoxy compounds such as epoxy (meth) acrylate and cyclohexanedimethanol diglycidyl ether compound Epoxy (meth) acrylates of glycidyl ether compounds, epoxy (meth) acrylates of aliphatic diglycidyl ether compounds such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether, and the like.

  (C) A dialcohol compound having a carboxyl group: dimethylolpropionic acid, dimethylolbutanoic acid, and the like.

  The compounds (a) to (c) may be used alone or in combination of two or more.

  Examples of the both-end diisocyanate used for the preparation of the carboxyl group-containing urethane polymer include aromatic, aliphatic, cycloaliphatic or alicyclic polyisocyanates. For example, tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, α, α′-dimethyl-o-xylylene Diisocyanate, α, α′-dimethyl-m-xylylene diisocyanate, α, α′-dimethyl-p-xylylene diisocyanate, α, α, α′-trimethyl-o-xylylene diisocyanate, α, α, α ′ -Trimethyl-m-xylylene diisocyanate, α, α, α'-trimethyl-p-xylylene diisocyanate, α, α, α ', α'-tetramethyl-o-xylylene diisocyanate, α, α, α', α'-tetramethyl-m-xylylene Examples include isocyanate, α, α, α ′, α′-tetramethyl-p-xylylene diisocyanate, and cyclohexane diisocyanate. A compound obtained by hydrogenating an aromatic ring of a diisocyanate compound, for example, a hydrogenated product of m-xylylene diisocyanate (Takenate (registered trademark) 600 manufactured by Mitsui Takeda Chemical Co., Ltd.), hydrogenated diphenylmethane diisocyanate and the like can also be mentioned. These may be used alone or in combination of two or more.

  A compound having an epoxy group and a (meth) acryl group in one molecule used for the preparation of a carboxyl group-containing urethane polymer is obtained by reacting an epoxy resin having an epoxy group with (meth) acrylic acid in a conventional manner. If it is a (meth) acrylate, it will not specifically limit. For example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, vinylcyclohexene monooxide, hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol di Phenyl diglycidyl ether such as glycidyl ether and (meth) acrylic acid half ester, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound and the like bisphenol type epoxy compound and (meth) acrylic acid half ester, hydrogenated bisphenol-A type Xy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Hydrogenated bisphenol type epoxy compound such as epoxy compound and half ester of (meth) acrylic acid, cycloaliphatic diglycidyl ether compound such as cyclohexanedimethanol diglycidyl ether compound and half ester of (meth) acrylic acid, 1,6 -Aliphatic diglycidyl ether compounds such as hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether, and (meth) acrylic acid half esters. These may be used alone or in combination of two or more.

  Examples of the dicarboxylic acid anhydride used for the preparation of the carboxyl group-containing urethane polymer include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, 5-methyl-cyclohexane dicarboxylic acid anhydride, bicycloheptane. Dicarboxylic anhydride, 7-oxabicycloheptanedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) And polybasic acid anhydrides such as succinic anhydride and (3-triethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more.

  A carboxyl group-containing urethane polymer can be performed by a conventional method. The dialcohol and diisocyanate are reacted under a nitrogen atmosphere. The reaction temperature is usually 30 ° C. to 140 ° C., preferably 50 ° C. to 120 ° C. from the viewpoint of improving reactivity and preventing side reactions. This reaction is usually carried out in the absence of a solvent, but if necessary, an inert solvent having no reactivity with an isocyanate group [for example, aromatic hydrocarbons (toluene, xylene, etc.), ketones (methyl ethyl ketone and methyl isobutyl). Ketone, etc.) and a mixture of two or more of these], and these solvents may later be removed by distillation.

  The addition reaction of both terminal hydroxyl groups obtained by the above reaction in the preparation of the carboxyl group-containing urethane polymer and the compound having an epoxy group and a (meth) acryl group in one molecule is carried out using a polymerization inhibitor and a catalyst. It is preferable to carry out the reaction in the medium. The reaction is preferably performed at a reaction temperature of 50 ° C to 120 ° C.

  In the preparation of the carboxyl group-containing urethane polymer, the reaction solvent, the reaction catalyst, and the polymerization inhibitor are each composed of a vinyl polymer (polymer (1 The same reaction solvent, reaction catalyst and polymerization inhibitor as described in the preparation of)) can be used.

  Furthermore, although a dicarboxylic acid anhydride can be partially added to the hydroxyl group of the reaction product, the reaction temperature is preferably 50 ° C to 120 ° C.

(About polymer (5) (ester polymer composed mainly of a reaction product of dicarboxylic acid and diepoxide))
Examples of the polymer (5) include a carboxyl group-containing ester polymer represented by the following general formula (9).

｛式中、Ｒａは、炭素原子数が２〜１６の直鎖状、分岐鎖状又は環状の２価の有機基であり、Ｒｃは、上記一般式（３）で表される基又は水素であり、Ｒｇは、炭素原子数が２〜２０の直鎖状、分岐鎖状又は環状の２価の有機基であり、Ｒｉは、上記一般式（２）又は上記一般式（６）で表される１価の有機基であり、そしてｍは、１〜６００から選ばれる整数である。｝

{In the formula, Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms, and Rc is a group represented by the general formula (3) or hydrogen. Rg is a linear, branched or cyclic divalent organic group having 2 to 20 carbon atoms, and Ri is represented by the general formula (2) or the general formula (6). And m is an integer selected from 1 to 600. }

  The carboxyl group-containing ester polymer used in the present invention is obtained by addition polymerization of a compound having two carboxyl groups in one molecule and a compound having two epoxy groups in one molecule. Further, a compound having a carboxyl group or a hydroxyl group and a (meth) acrylate group in one molecule may be added to the terminal epoxy group of the reaction product, and the hydroxyl group of the reaction product may be reacted with a dicarboxylic acid anhydride. .

  The compounds having two carboxyl groups in one molecule used for the preparation of the carboxyl group-containing ester polymer include succinic acid, cyclohexanedicarboxylic acid, 4-methyl-cyclohexanedicarboxylic acid, 5-methyl-cyclohexanedicarboxylic acid, and bicycloheptane. Dicarboxylic acid, 7-oxabicycloheptanedicarboxylic acid, tetrahydrophthalic acid, trimellitic acid, pyromellitic acid, adipic acid, phthalic acid, (3-trimethoxysilylpropyl) succinic acid, (3-triethoxysilylpropyl) succinic acid Etc. These may be used alone or in combination of two or more.

  Examples of compounds having two epoxy groups in one molecule used for the preparation of a carboxyl group-containing ester polymer include phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, bisphenol -A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Bisphenol type epoxy compound, hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bis (4-hydroxyphenyl) -1, 1,1,3,3 -Hydrogenated bisphenol type epoxy compound such as hexafluoropropane epoxy compound, cycloaliphatic diglycidyl ether compound such as cyclohexanedimethanol diglycidyl ether compound, 1,6-hexanediol diglycidyl ether, 1,4-butanediol di Examples thereof include aliphatic diglycidyl ether compounds such as glycidyl ether, diethylene glycol diglycidyl ether, and polyethylene glycol diglycidyl ether. These may be used alone or in combination of two or more.

  Examples of compounds having a carboxyl group and a (meth) acrylate group in one molecule used for the preparation of a carboxyl group-containing ester polymer include (meth) acrylic acid, carboxyethyl (meth) acrylate, and carboxypentyl (meth). Acrylate, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, And maleic acid half ester. These may be used alone or in combination of two or more.

  Examples of compounds having a hydroxyl group and a (meth) acrylate group in one molecule used for a carboxyl group-containing ester polymer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerol methacrylate Examples thereof include acrylate, pentaerythritol tri (meth) acrylate, and caprolactone adducts of these monomers.

  Examples of epoxy (meth) acrylate compounds in which an epoxy group is (meth) acrylate-modified include epoxy (meth) acrylates of phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, and bisphenol. -A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, epoxy compound of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Epoxy (meth) acrylates of bisphenol type epoxy compounds, such as hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2-bi Fatty compounds such as epoxy (meth) acrylates of hydrogenated bisphenol type epoxy compounds such as epoxy compounds of (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, cyclohexanedimethanol diglycidyl ether compounds Epoxy (meth) of aliphatic diglycidyl ether compound such as epoxy (meth) acrylate of cyclic diglycidyl ether compound, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether An acrylate etc. are mentioned.

  Examples of the dicarboxylic acid anhydride used for the preparation of the carboxyl group-containing ester polymer include succinic anhydride, cyclohexanedicarboxylic acid anhydride, 4-methyl-cyclohexanedicarboxylic acid anhydride, 5-methyl-cyclohexanedicarboxylic acid anhydride, bicycloheptane. Dicarboxylic anhydride, 7-oxabicycloheptanedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) And polybasic acid anhydrides such as succinic anhydride and (3-triethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more.

  The carboxyl group-containing ester polymer used in the present invention can be performed by a conventional method. In the carboxyl group-containing ester polymer, an addition reaction between a compound having two carboxyl groups in one molecule and a compound having two epoxy groups in one molecule is carried out in a solvent using a polymerization inhibitor and a catalyst. It is preferable to carry out the reaction. The reaction is preferably performed at a reaction temperature of 50 ° C to 120 ° C.

  In the preparation of the carboxyl group-containing ester polymer, the reaction solvent, the reaction catalyst, and the polymerization inhibitor are each a vinyl polymer (polymer (1)) composed mainly of the above-mentioned reactant of the polymerizable unsaturated double bond. The same reaction solvent, reaction catalyst and polymerization inhibitor as described in the preparation of)) can be used.

  Furthermore, although a dicarboxylic acid anhydride can be partially added to the hydroxyl group of the reaction product, the reaction temperature is preferably 50 ° C to 120 ° C.

  The alkali-soluble photosensitive resin material 52 used in the present invention is a vinyl polymer composed mainly of a reactant of a polymerizable unsaturated double bond from the viewpoint of heat resistance of the reactant mainly of the polymer, Epoxy polymer composed mainly of addition reaction product of epoxy group and hydroxyl group, aromatic methylene polymer composed mainly of reaction product of phenol and formaldehyde, ester composed mainly of reaction product of dicarboxylic acid and diepoxide It is preferably at least one polymer selected from the group consisting of polymers.

  Examples of the alkali-soluble monomer include compounds having a functional group such as a carboxylic acid group, a poly or oligoalkyleneoxy group, a phenol group, a phosphoric acid group, and a sulfonic acid group.

  Specific examples of the carboxylic acid group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acrylic acid. Roxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, 2,2,2-triacryloyloxymethyl ethyl succinic acid and the like can be mentioned.

  Specific examples of the monomer having a poly or oligoalkyleneoxy group include polyethylene glycol diacrylate [number of ethylene glycol units 2 to 20], polyethylene glycol dimethacrylate [number of ethylene glycol units 2 to 20], poly (1 , 2-propylene glycol) diacrylate [1,2-propylene glycol unit number 2-20] and poly (1,2-propylene glycol) dimethacrylate [1,2-propylene glycol unit number 2-20], ethoxylation Bisphenol A diacrylate [number of ethylene glycol units 2 to 30], ethoxylated bisphenol A dimethacrylate [number of ethylene glycol units 2 to 30], ethoxylated (hydrogenated bisphenol A) diacrylate [ethylene Number 2-30] recall units, ethoxylated (hydrogenated bisphenol A) dimethacrylate [2-30 ethylene glycol units], and the like.

  The acid value of the photosensitive resin material 52 used in the present invention is not particularly specified as long as the unexposed portion is removed by dissolution or dispersion in the developer during the development process. It also depends on the type of alkali solution to be developed and the amount of alkali-soluble monomer that does not exhibit an acid value.

  As a composition which comprises the photosensitive resin material 52, it is preferable that the ratio of the number of carbon atoms in the total number of atoms in a composition is large from a viewpoint of ashing tolerance and etching tolerance. In particular, it is preferable that the ratio of (number of carbon atoms−number of oxygen atoms) in all atoms is large.

  In terms of solid content of the photosensitive resin material 52 (part excluding the organic solvent in the photosensitive resin material 52), the molar concentration of the photopolymerizable functional group is determined by the adhesion of the pattern, the hardness of the film, and the crack resistance. From a viewpoint, 0.01 mmol / g or more is preferable, More preferably, it is 0.1 mmol / g or more, More preferably, it is 0.5 mmol / g or more. From the viewpoint of reducing residues during development and reducing shrinkage, the molar concentration is preferably 10.0 mmol / g or less, more preferably 7.5 mmol / g or less, and even more preferably 5.0 mmol / g or less.

  The molar concentration of the alkali-soluble functional group when using the alkali-soluble resin is preferably 0.05 mmol / g or more from the viewpoint of solubility in an alkaline developer during development, in terms of solid content of the photosensitive resin material 52, 0.1 mmol / g or more is more preferable, 0.2 mmol / g or more is more preferable, and 0.5 mmol / g or more is most preferable. On the other hand, from the viewpoint of peeling or cracking during development, it is preferably 10 mmol / g or less, more preferably 5 mmol or less, further preferably 3 mmol / g or less, and most preferably 2 mmol / g or less.

  It is preferable that the photosensitive resin material 52 has light absorption at the exposure wavelength, and it is more preferable that the absorption is due to a compound other than the photoinitiator. By having absorption at the exposure wavelength, it is possible to change the light intensity or exposure amount between the surface and the bottom or inside, and to bring the surface curability close to the degree of cure or reaction rate at the bottom or inside. I can do it. Furthermore, the bottom part is hardened | cured by the penetration | invasion of the light to the unexposed part of a photolitho pattern, and the footing which becomes a residue can be suppressed.

  Although it depends on the film thickness to be used, the optical substrate precursor has a transmittance of preferably 1 to 99.9%, more preferably 20 to 99%, more preferably 30 to 95% when a PET film is used as a reference. More preferably, 40 to 90% is more preferable. The transmittance wavelength is the exposure wavelength, which is 365 nm for i-line and 405 nm for g-line, and the transmittance at 365 nm when ultraviolet rays are broadband.

The absorption coefficient per weight, when defined by the following formula (I), the is preferably 10~10000cm ² / g, more preferably 20~1000cm ² / g, is 100~500cm ² / g More preferably.
A = αLC (I)
A represents the absorbance, α represents the extinction coefficient per weight (cm ² / g), L represents the path length (cm), and C represents the concentration per weight (g / cm ³ ).

  The concentration per weight is a concentration calculated by using only the solid content of the photosensitive resin material 52 as the weight. From the optical substrate precursor 55, the optical substrate precursor 55 weighed in advance is immersed in a solvent, and the photosensitivity is obtained. After the resin material 52 is dissolved, the weight of the photosensitive resin material 52 can be calculated by measuring the optical substrate precursor 55 without the dried photosensitive resin material 52 taken out.

  When the transmittance is low or the extinction coefficient per weight is large, the exposure light does not reach the bottom, resulting in insufficient curing of the bottom or peeling during development. On the other hand, when the transmittance is high or the extinction coefficient per weight is small, the above effect is reduced.

  It is preferable to use the photosensitive resin material 52 that absorbs light at the exposure wavelength as described above. From the ease of the bonding process, the optical base precursor 55 is in the form of a sheet. It is more preferable.

  You may pressurize at the time of the bonding in the formation process of the optical base material precursor 55 by the process of FIG. 5A or FIG. The pressure at the time of pressurization depends on the physical properties and state (for example, dry state) of the photosensitive resin material 52. However, the pressurization is more effective between the dots 50 of the resin mold 51 (when the dots 50 are formed of convex portions). ) Or from the viewpoint of filling the photosensitive resin material 52 into the dots 50 (when the dots 50 are formed of recesses).

  Moreover, you may heat at the time of the bonding in the formation process of the optical base material precursor 55 by the process of FIG. 5A or FIG. The object to be heated may be a bonding atmosphere or a substrate, but it is preferable to heat the substrate from the viewpoint of simplicity in the process. By heating, adhesion with the photosensitive resin material 52 can be improved.

  Next, in the step shown in FIG. 5B, the optical base material precursor 55 is irradiated with ultraviolet rays through the patterning mask 60.

  As shown in FIG. 5B, a patterning mask 60 is disposed on the optical base precursor 55 on the resin mold 51 side. The patterning mask 60 may be brought into contact with the resin mold 51, or the patterning mask 60 may be arranged in a state slightly separated from the resin mold 51.

  As shown in FIG. 5B, the patterning mask 60 is provided with an exposure region 60a and a non-exposure region 60b. As shown in FIG. 5B, the exposure region 60 a is formed only on a part of the patterning mask 60, and the exposure region 60 a is a region narrower than the formation region of the dots 50 formed on the resin mold 51. .

As the shape of the exposure region 60a or the non-exposure region 60b of the patterning mask 60, any shape such as a circle, a square, a rectangle, a trapezoid, and a line and space can be used. The shape may be a blank pattern (the photosensitive resin material inside the shape dissolves) or a remaining pattern (the photosensitive resin material outside the shape dissolves). The area of their shape, in terms of patterning accuracy, preferably 2 [mu] m ² or more, more preferably 25 [mu] m ² or more, more preferably 100 [mu] m ² or more, 400 [mu] m ² or more is most preferred.

  The exposure may be any of a reduction projection method, contact exposure, and proximity exposure. The reduction projection method is preferable from the viewpoint of patterning accuracy, and contact exposure or proximity exposure is preferable from the viewpoint of throughput.

  Since a fine dot pattern exists in the optical base material precursor 55, light may be scattered due to a difference in refractive index between the resin mold 51 and the photosensitive resin material 52. In such a case, a reduction projection method or contact exposure is preferable from the viewpoint of patterning accuracy.

As the exposure amount, the optimum value can be changed depending on the addition amount of the photoactive substance added to the photosensitive resin material 52, but is preferably 3000 mJ / cm ² or less from the viewpoint of process throughput, and 2000 mJ / cm ² or less is more preferable, and 1000 mJ / cm ² or less is more preferable. Further, from the viewpoint of process reproducibility, 10 mJ / cm ² or more is preferable, 20 mJ / cm ² or more is more preferable, and 50 mJ / cm ² or more is more preferable.

  It is preferable to heat the optical base material precursor 55 after the exposure. By heating, the active substance generated by the exposure is further activated, and the contrast between the exposed portion and the unexposed portion can be increased. The heating temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 80 ° C. or higher from the viewpoint of activation of the active substance. On the other hand, from the stability of the resin mold 51 and the stability of the dot pattern, 200 ° C. or lower is preferable, and 150 ° C. or lower is more preferable.

  The heating time depends on the heating temperature, but is preferably 5 seconds or more from the viewpoint of process stability, more preferably 10 seconds or more, and preferably 10 minutes or less from the viewpoint of throughput.

  Subsequently, the resin mold 51 is peeled from the optical substrate precursor 55. In the peeling step, the peeling direction may be the same as or different from the direction at the time of attachment. From the viewpoint of throughput, the peeling speed is preferably 0.1 cm or more, more preferably 0.5 cm or more, and further preferably 2.0 cm or more. A state where the resin mold 51 is peeled from the optical base material precursor 55 is shown in FIG. 5C.

  As shown in FIG. 5C, a photosensitive resin material 52 is formed on the entire main surface 2a of the substrate 2, and the entire surface of the photosensitive resin material 52 has a fine dot pattern. The photosensitive resin material 52 shown in FIG. 5C is divided into an exposed portion 52a and an unexposed portion 52b. A region surrounded by a dotted line between the exposed portions 52a is an unexposed portion 52b.

  Subsequently, in the step of FIG. 5D, the unexposed portion 52b of the photosensitive resin material 52 is removed by development. As a result, the fine structure layer 3 is left on a part of the main surface 2a of the substrate 2, and the main surface 2a is exposed at other portions. The exposed surface of the main surface 2a is a flat surface and is configured as at least an electrode forming portion of the light emitting element.

  Examples of the developing method include dip, dispense spin, spray, shower, ultrasonic, and the like, and dip, dispense spin, spray, and ultrasonic are preferred. In particular, the insoluble component in the developer is included in the photosensitive resin material 52. In some cases, ultrasound is more preferred. Examples of the developer include organic solvents, alkaline aqueous solutions, and acidic aqueous solutions. From the viewpoint of influence on the substrate 2, an organic solvent or an alkaline aqueous solution is preferable. Further, an alkaline aqueous solution is more preferable from the viewpoint of environmental harmony and safety.

  The organic solvent used as the developer may be any organic solvent that can be added to the photosensitive resin material 52. From the viewpoints of boiling point and flash point, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, gamma butyrolactone. Etc.

  After washing the unexposed portion 52b with a developer, it may be rinsed with a low-boiling organic solvent. For example, acetone, ethanol, methanol, isopropanol, etc. are mentioned.

  After developing with a solvent, it may be rinsed with water. By rinsing with water, it is possible to prevent elution of the finely dissolved component in the developer in the exposed area.

  Examples of suitable alkaline aqueous solutions include, for example, ammonium hydroxides such as alkali metal or alkaline earth metal carbonate aqueous solutions, alkali metal hydroxide aqueous solutions, tetraethylammonium hydroxide, tetrapropylammonium hydroxide aqueous solutions, and the like. And amines such as diethylamine, triethylamine, diethanolamine, and triethanolamine. In particular, weak carbonate containing 0.05 to 10% by mass of carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and amines such as diethylamine and diethanolamine. Development is preferably performed using an alkaline aqueous solution.

  When developing with an alkaline aqueous solution, it is preferable to use pure water as the rinsing liquid. Development and rinsing are preferably performed at a temperature of 20 ° C. or higher and 35 ° C. or lower.

  You may heat after image development and / or rinse. By heating, the developing solution and the rinsing solution that have penetrated into the pattern can be removed. In addition, the microstructure layer 3 can be further cured.

  The main surface 2a is exposed in the unexposed portion after development, but even if a part or all of the components of the fine structure layer 3 remain due to residues or the like, they can be removed by ashing or the like.

  Hereinafter, the method of the present invention will be described in detail according to examples. However, the present invention is not limited to the following examples.

  As the resin mold used, a mold having a dot pattern consisting of the following concave portions on its surface was used.

Concave diameter: 650 nm
Concave depth: 800 nm
Pitch Px in the X axis direction: 700 nm
Y-axis direction pitch Py: 700 nm

  The resin mold is formed through a transfer process from a mold for producing a resin mold having a fine dot pattern by a direct writing lithography method using a semiconductor pulse laser.

  Each optical base material precursor of the following Production Examples 1 to 8 was produced using the above resin mold.

[Production Example 1]
The photosensitive resin material (A) adjusted as shown in Table 1 below was used. The photosensitive resin material (A) was applied onto a resin mold using a bar coater (No. 4) to obtain a sheet. The sheet was then dried in an oven at 105 ° C. for 15 minutes. Then, the quartz base material with which ITO was formed into a film heated beforehand at 85 degreeC was bonded to the sheet | seat, and optical base material precursor A-1 was obtained.

[Production Example 2]
Although the optical base material precursor was produced by the method similar to the manufacture example 1, it bonded, applying 0.01 MPa in the case of bonding, and obtained optical base material precursor A-2.

[Production Example 3]
The photosensitive resin material (B) was adjusted as shown in Table 1 below. The photosensitive resin material (B) was applied onto a resin mold using a bar coater (No. 4) to obtain a sheet. The sheet was then dried in an oven at 105 ° C. for 10 minutes. A photosensitive resin material (A) was further applied to the obtained sheet using a bar coater (No. 4) to obtain a sheet. The sheet was then dried in an oven at 105 ° C. for 15 minutes. Using the obtained sheet, an optical substrate precursor was produced in the same manner as in Production Example 2 to obtain an optical substrate precursor A-3.

[Production Example 4]
The photosensitive resin material (C) was adjusted as shown in Table 1 below. The photosensitive resin material (C) was formed on a quartz base material on which ITO was formed by spin coating, and was allowed to stand at room temperature for 3 minutes. Then, it bonded together in the state with which the fine uneven surface of the resin mold and the photosensitive resin material were made to oppose. Thereafter, pressing was performed at 0.05 MPa for 5 minutes to obtain an optical substrate precursor B-1.

[Production Example 5]
The photosensitive resin material (B) was applied onto a resin mold using a bar coater (No. 4) to obtain a sheet. The sheet was then dried in an oven at 105 ° C. for 15 minutes. Then, the photosensitive resin material (C) was formed into a film by the spin coat method on the quartz base material by the method similar to the manufacture example 4. And using the sheet | seat obtained instead of the resin mold, the optical base material precursor was produced by the method similar to the manufacture example 4, and optical base material precursor B-2 was obtained.

[Production Example 6]
The photosensitive resin material (D) was adjusted as shown in Table 1 below. An optical substrate precursor was prepared in the same manner as in Preparation Example 3, but using the photosensitive resin material (D) instead of the photosensitive resin material (A) in Preparation Example 3, an optical substrate precursor C- 1 was obtained.

[Production Example 7]
The photosensitive resin material (E) was adjusted as shown in Table 1 below. An optical substrate precursor was prepared in the same manner as in Preparation Example 3, but using the photosensitive resin material (E) instead of the photosensitive resin material (A) in Preparation Example 3, an optical substrate precursor C- 2 was obtained.

[Production Example 8]
The photosensitive resin material (F) was adjusted as shown in Table 1 below. An optical substrate precursor was prepared in the same manner as in Preparation Example 3, but using the photosensitive resin material (F) instead of the photosensitive resin material (A) in Preparation Example 3, an optical substrate precursor D- 1 was obtained.

  EA-HG001 described in Table 1 is 9,9′-bis (4- (acryloxyethoxy) phenyl) fluorene (manufactured by Osaka Gas Chemical Company).

  ACMO is 3-acryloxypropyltrimethoxysilane. CNEA-100 is novolak acrylate (manufactured by KSM, solid content 50%). TTB is tetra n-butoxy titanium (manufactured by Tokyo Chemical Industry Co., Ltd.). SH710 is trimethyl-terminated phenylmethylsiloxane (manufactured by Toray Dow Corning). EA-6340 is acid-modified epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). EA-1020 is bisphenol A type epoxy acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.). Cyclomer P-ACA200M is a vinyl polymer acrylate adduct (manufactured by Daicel Ornex). M-510 is a polybasic acid-modified acrylic oligomer (manufactured by Toagosei Co., Ltd.). Irg184 is 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE (registered trademark) 184, manufactured by BASF). Irg369 is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (IRGACURE (registered trademark) 369, manufactured by BASF). Irg819 is bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (IRGACURE (registered trademark) 819, manufactured by BASF). Tin 405 is a reaction of 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester. Product (TINUVIN® 405, manufactured by BASF). PGME is propylene glycol monomethyl ether.

  Table 2 below summarizes the optical base material precursors obtained from Production Examples 1 to 8 described above.

  Then, the following Example 1-Example 12 and Comparative Example 1-Comparative Example 2 were produced using the optical base material precursor shown in Table 2.

[Example 1]
A patterning mask was placed on the optical base precursor A-1 on the resin mold side, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 100 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 30 seconds. Subsequently, after the resin mold was peeled off, dip development was performed with PGME for 30 seconds, followed by rinsing with ethanol for 10 seconds, followed by drying under pressure to produce optical substrate A-I.

[Example 2]
Optical substrate A-II was produced in the same manner as in Example 1 except that optical substrate precursor A-2 was used.

[Example 3]
Optical substrate A-III was produced in the same manner as in Example 1 except that optical substrate precursor A-3 was used.

[Example 4]
A patterning mask was placed above the resin mold side of the optical substrate precursor A-3, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 30 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 30 seconds. Subsequently, after the resin mold is peeled off, dip development is performed with PGME for 30 seconds, followed by rinsing with ethanol for 10 seconds, drying under pressure, and then baking in an oven at 100 ° C. for 5 minutes to form the optical substrate A-IV. Produced.

[Example 5]
A patterning mask was placed above the resin mold side of the optical substrate precursor B-1, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 25 mJ / cm ² . After the exposure, the resin mold was peeled off, followed by dip development with PGME for 30 seconds, followed by rinsing with ethanol for 10 seconds and drying under pressure to produce optical substrate BI.

[Example 6]
A patterning mask was placed above the resin mold side of the optical substrate precursor B-2, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 25 mJ / cm ² . After the exposure, the resin mold was peeled off, followed by dip development with PGME for 30 seconds, followed by rinsing with ethanol for 10 seconds and drying under pressure to produce an optical substrate B-IV.

[Example 7]
A patterning mask was placed above the resin mold side of the optical substrate precursor B-2, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 25 mJ / cm ² . After the exposure, the resin mold was peeled off, followed by dip development with PGME for 30 seconds, followed by rinsing with ethanol for 10 seconds and drying under pressure. Furthermore, optical base material B-V was produced by baking for 5 minutes in 100 degreeC oven.

[Comparative Example 1]
A patterning mask was placed above the resin mold side of the optical substrate precursor A-3, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 100 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 30 seconds. Subsequently, the resin mold was peeled off to produce an optical substrate AV.

Note that EXF-2828 (manufactured by Oak Manufacturing Co., Ltd.) was used as the exposure machine. The illuminance was 12 mW / cm ² .

[Evaluation method]
Each of the obtained optical substrates was observed with an optical microscope, and it was confirmed whether or not 50 μm square patterning was formed. The evaluation results are shown in Table 3 below.
○: It is formed into a beautiful square, and there is no or very little residue inside the square.
Δ: A part of the square is jagged and / or a residue remains inside the square.
X: It is not formed squarely.

  In Example 1-7, the area | region where the dot pattern was not formed in the area | region larger than 50 micrometers square was observed, and it turned out that the area | region is a flat surface. In contrast, in Comparative Example 1, it was found that the dot pattern was formed on the entire surface of the substrate, and there was no flat surface. Therefore, when the optical base material of Comparative Example 1 is used, for example, when attaching an electrode to the p-plane electrode side of the LED, a part of the fine structure layer including the dot pattern must be deleted by ashing or etching. I understood.

  The post-exposure baking shown in Table 3 was performed at 120 ° C. for 30 seconds, and the development was performed by setting the PGME dip for 30 seconds and EtOH rinse for 10 seconds. The post-development baking was performed at 100 ° C. for 5 minutes.

[Example 8]
A patterning mask was placed above the resin substrate side of the optical substrate precursor C-1, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 200 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 240 seconds. Subsequently, after the resin mold is peeled off, ultrasonic development is performed with PGME for 30 seconds, followed by rinsing with ethanol for 10 seconds, drying under pressure, and then baking in an oven at 100 ° C. for 5 minutes to form an optical substrate CI Was made.

[Example 9]
A patterning mask was placed above the resin mold side of the optical substrate precursor C-2, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 200 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 240 seconds. Subsequently, after the resin mold is peeled off, ultrasonic development is performed with PGME for 30 seconds, followed by rinsing with ethanol for 10 seconds, drying under pressure, and then baking in an oven at 100 ° C. for 5 minutes to form the optical substrate C-II. Was made.

[Example 10]
A patterning mask was placed above the resin mold side of the optical substrate precursor C-2, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 200 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 240 seconds. Subsequently, after the resin mold is peeled off, ultrasonic development is performed with PGME for 30 seconds, followed by rinsing with ethanol for 10 seconds, further rinsing with ion-exchanged water for 10 seconds, drying with pressurized air, and further at 100 ° C. An optical substrate C-III was produced by baking in an oven for 5 minutes.

[Example 11]
A patterning mask was placed above the resin mold side of the optical substrate precursor D-1, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 200 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 240 seconds. Next, after the resin mold is peeled off, dip development is performed with 2.38% TMAH aqueous solution for 30 seconds, followed by rinsing with ion exchange water for 30 seconds, drying under pressure, and baking in a 100 ° C. oven for 5 minutes. An optical substrate DI was prepared.

[Example 12]
A patterning mask was placed above the resin mold side of the optical substrate precursor D-1, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 200 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 240 seconds. Next, after the resin mold is peeled off, dip development is performed with 2.38% TMAH aqueous solution for 30 seconds, then rinsed with ion-exchanged water for 30 seconds, dried under pressure, and further baked in an oven at 220 ° C. for 30 minutes. Optical base material D-II was produced.

[Comparative Example 2]
A patterning mask was placed above the resin mold side of the optical substrate precursor A-3, and contact exposure was performed using a parallel light exposure machine. The exposure amount was 200 mJ / cm ² . After the exposure, post-exposure baking was performed at 120 ° C. for 240 seconds. Subsequently, after the resin mold is peeled off, ultrasonic development is performed with PGME for 30 seconds, followed by rinsing with ethanol for 10 seconds, drying under pressure, and then baking in an oven at 100 ° C. for 5 minutes to form the optical base material A-VI. Was made.

[Evaluation method]
Each of the obtained optical substrates was observed with an optical microscope, and it was confirmed whether or not a predetermined pattern without squares was formed in a square. The evaluation results are shown in Table 4 below.
OO: A 20 μm square pattern is formed in a square shape.
◯: A 30 μm square pattern is formed in a square shape.
A: A 50 μm square pattern is formed in a square shape.
X: It is not formed squarely.

  The post-exposure baking shown in Table 4 is performed at 120 ° C. for 240 seconds, and described in the development method. Solvent development 1 is performed by ultrasonic cleaning in PGME for 30 seconds and then rinsing with EtOH for 10 seconds. Then, ultrasonic cleaning is performed in PGME for 30 seconds, followed by rinsing with EtOH for 10 seconds and further rinsing with ion-exchanged water for 10 seconds. Alkaline development is performed in 2.38% TMAH (tetramethylammonium hydroxide) for 30 seconds. After dipping for 2 seconds, rinsing with ion exchange water for 30 seconds was performed. Further, the post-development baking was performed at 100 ° C. for 5 minutes or at 220 ° C. for 30 minutes.

DESCRIPTION OF SYMBOLS 1 Optical base material 2, 101 Base material 2a, 101a Main surface 3, 113 Fine structure layer 4, 111 Base body 5 Conductive layer 6, 15, 16, 50 Dot 13 Convex part 14 Concave part 51 Resin mold 52 Photosensitive resin material 52a Exposed portion 52b Unexposed portion 54 Sheet 55 Optical substrate precursor 60 Patterning mask 60a Exposed region 60b Non-exposed region 102 Cathode electrode 103 N-type semiconductor layer 104 Light emitting layer 105 P-type semiconductor layer 106 Transparent conductive layer 108 Anode electrode 110 Multilayer Semiconductor Layer 200 Light Emitting Element

Claims (22)

An optical base material for forming a light emitting element, comprising: a base material; and a microstructure layer formed on a main surface of the base material,
A plurality of dots composed of a plurality of convex portions or concave portions are formed on the surface of the fine structure layer,
An optical base material, wherein the main surface side of the base material is provided with the fine structure layer and a flat surface that can be used as an electrode forming portion of a light emitting element.   The optical substrate according to claim 1, wherein the flat surface is a surface where a main surface of the substrate is exposed.   3. The optical substrate according to claim 1, wherein the main surface is a p-plane electrode side.   The optical substrate according to any one of claims 1 to 3, wherein the flat surface is a surface produced by photolithography.   The base material includes a base material body and a conductive layer formed on a surface of the base material body, and the surface of the conductive layer forms a main surface of the base material. The optical substrate according to any one of claims 1 to 4.   The microstructure layer contains a compound containing at least one of an aromatic group, a polycyclic group, or a heterocyclic group, or Al, Si, P, Ti, Ga, Ge, Zr, Nb, Ta, In, and The optical substrate according to any one of claims 1 to 5, comprising at least one element selected from Sn.   The photosensitive resin material for forming the microstructure layer includes at least one of an antioxidant, a polymerization inhibitor, an ultraviolet absorber, a radical scavenger, a sensitizer, and an adhesion assistant. The optical substrate according to any one of claims 1 to 6.   The optical substrate according to any one of claims 1 to 7, wherein the photosensitive resin material for forming the fine structure layer is a negative resist.   The optical substrate according to any one of claims 1 to 8, wherein the photosensitive resin material for forming the fine structure layer is an alkali developable resin.   The optical substrate according to any one of claims 1 to 9, wherein the sensitive resin material for forming the microstructure layer contains a compound having a carboxylic acid group. A light emitting device formed using the optical substrate according to any one of claims 1 to 10,
A light-emitting element, wherein a multilayer semiconductor layer including a semiconductor layer and a light-emitting layer is formed on a surface of the microstructure layer, and an electrode layer is formed on the flat surface. A mold in which a plurality of dots composed of a plurality of convex portions or concave portions are formed on the surface; a base material; a photosensitive resin material interposed between the surface of the mold and the main surface of the base material; A step of forming an optical substrate precursor obtained by laminating
Exposing the optical substrate precursor through a mask, and at this time, exposing the exposure area to a range smaller than the formation area of the dots formed on the mold;
The mold is peeled off and the exposed photosensitive resin material is left on a part of the main surface as a fine structure layer having the dots formed on the surface, and an unexposed portion of the photosensitive resin material is developed by development. Removing and forming the microstructure layer and a flat surface on the main surface;
The manufacturing method of the optical base material characterized by having.   13. The method for producing an optical substrate according to claim 12, further comprising a step of heating the optical substrate precursor after the development.   The method for producing an optical substrate according to claim 12 or 13, wherein a part of the main surface is exposed by removing an unexposed portion of the photosensitive resin material.   The method for producing an optical substrate according to any one of claims 12 to 14, wherein an unexposed portion of the photosensitive resin material is removed with a solvent.   16. The method for producing an optical substrate according to claim 15, wherein the unexposed portion of the photosensitive resin material is removed with a solvent and then rinsed with water.   16. The method for producing an optical substrate according to claim 15, wherein an unexposed portion of the photosensitive resin material is removed with an aqueous alkaline solution and then rinsed with water.   The method for producing an optical substrate according to any one of claims 12 to 17, wherein an ultrasonic wave is used when removing an unexposed portion of the photosensitive resin material.   The optical base material precursor is formed by bonding the base material to the photosensitive resin material side of the sheet filled with the photosensitive resin material on the surface of the mold, or the main surface of the base material 13. The optical base material precursor is formed by applying a photosensitive resin material and adhering the photosensitive resin material to the photosensitive resin material while pressing the surface of the mold on which the dots are formed. The method for producing an optical substrate according to any one of claims 18 to 18.   The method for manufacturing an optical substrate according to any one of claims 12 to 19, further comprising a step of heating the optical substrate precursor after the exposure.   The optical substrate according to any one of claims 12 to 20, wherein a pressure is applied between the substrate and the mold at the time of bonding in the step of forming the optical substrate precursor. Method. The method for producing an optical substrate according to any one of claims 12 to 21, wherein heat is applied at the time of bonding in the step of forming the optical substrate precursor.

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