JP2005010230A - Rugged pattern forming material, rugged pattern receiving body, rugged pattern forming method, transfer foil, and optical component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a rugged pattern forming material which is little taken off, is excellent in a shaping property and shape retaining characteristic, and permits the exact duplication of a surface structure having a rugged pattern with good accuracy, more particularly a rugged pattern forming material which permits the exact duplication of even the recent intricate and fine rugged pattern, a rugged pattern receiving body, rugged pattern transfer foil, a rugged pattern forming method and optical components. <P>SOLUTION: The rugged pattern forming material consists of a photosetting resin composition in which epoxy acrylate including ≥2 ethylenically unsaturated bonds within one molecule and a cyclic structure and having a viscosity of ≥50,000 mPa s at 25°C is included at ≥50mass% of the entire part of the solid content and which is ≥20,000 mPa s in the viscosity at 25°C. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【発明の効果】
以上に述べたように、本発明の凹凸パターン形成材料は、常温では高粘度又は固体状の流動しない凹凸パターン形成層を形成することが可能であり、エンボス加工の際に加熱すると粘度が低下してスタンパーのキャビティ内に容易に流れ込んで正確に賦型され、スタンパーからは版取られを起こさずにきれいに剥離することができる。更に、硬化させる前にスタンパーを取り除いても、瞬時の冷却で固化されるためパターン崩れを起こし難い。このため、非常に複雑な凹凸パターンでも非常に精度良く複製することができる。また、スタンパーを取り除いた後で凹凸パターン形成層の前面から光照射して硬化させることも可能である。従って、充分に硬化させることが可能である上、両面に一括して凹凸を形成することも可能である。更に、支持体は透明だけでなく不透明なものも用いることができ、取り除いたスタンパーはエンボス工程で連続使用できるので連続生産性に優れている。
【０１５５】
また、本発明の凹凸パターン形成材料は少ない加熱で低粘度化するため、エンボス時に短時間の加熱ですみ、高速で凹凸パターンを形成することができる。エンボス加工の高速化が図れるため、生産性が向上する。
【０１５６】
更に、上記エポキシアクリレートは加熱により容易に低粘度化するため、組成物中に溶剤を含まなくても塗布することが可能であり、この場合には、作業時の安全性が向上し、残留溶剤が後工程に及ぼす蒸着阻害等の不具合が低減される。
【０１５７】
また、上記エポキシアクリレートは１分子内にエチレン性不飽和結合を２つ以上有するため、本発明の凹凸パターン形成材料は光硬化性を有する。従って、本発明の凹凸パターン形成材料は、エンボス加工のプロセス温度よりも低い温度で硬化させることができ、硬化工程でのパターン崩れも起こし難く、エンボス加工により形成した凹凸パターンを充分に固定化できると共に、強度等の充分な皮膜物性を得ることができる。
【０１５８】
また、本発明に係る凹凸パターン形成方法によれば、凹凸パターン形成層からスタンパーを取り除いた後で硬化させることができるため、凹凸パターンを連続大量生産することが可能である。
【０１５９】
また、上記本発明に係る凹凸パターン形成材料は、支持体上に常温では高粘度又は固体状の流動しない凹凸パターン形成層を形成することができるため、凹凸パターン転写箔を形成することも可能である。凹凸パターン転写箔を利用する場合には、生産性をさらに向上させることができる。
【０１６０】
本発明によれば、レリーフホログラムや回折格子の凹凸パターンを複製できることは言うまでもなく、サイズが比較的大きい１００μｍ以上のようなフレネルレンズ等の光学物品の他、より高度な光学的機能を有する複雑な凹凸パターン、例えば、全光線及び／又は特定の波長の光の反射、透過、散乱、偏光、集光又は干渉の少なくとも一つを制御する光学素子や、情報記録素子等の凹凸パターンであっても精度良く且つエンボス加工により大量連続生産することが可能である。
【図面の簡単な説明】
【図１】凹凸パターン転写箔の一例についての模式的断面図である。
【図２】凹凸パターン作成方法の一例を説明するための図である。
【図３】凹凸パターン作成方法の一例を説明するための図である。
【図４】凹凸パターンの一例を示す図である。
【符号の説明】
１…転写箔
２…支持体
３…剥離層
４…凹凸パターン形成層
４’…凹凸パターン
５…反射層
６…接着層
７…支持ローラー
８…スタンパー
９…エンボスローラー
９ａ…金属ローラー
９ｂ…ペーパーローラー
９ｃ…圧接ローラー
９ｄ…圧接ローラー
１０…照射源
１１…照射源（予備硬化）[0001]
BACKGROUND OF THE INVENTION
The present invention is excellent in moldability and moldability maintenance, and in particular, a concavo-convex pattern forming material suitable for forming a fine concavo-convex surface structure of an optical article, a method for forming a concavo-convex pattern using the same, and these The present invention relates to a transfer foil obtained by using an optical article and an optical article.
[0002]
[Prior art]
Conventionally, for example, a photocurable resin composition is applied onto a support to form a photocurable resin layer, and an uneven pattern is applied to the surface of the photocurable resin layer, and then ultraviolet rays, electron beams, etc. An optical article such as a diffraction grating or a relief hologram is formed by curing the resin layer by exposure to active energy rays and laminating layers having different refractive indexes on the formed uneven pattern surface. .
[0003]
As a general forming method, a method of forming by a photocuring reaction using a liquid photocurable resin composition is used. For example, a liquid photocurable resin composition is applied onto a transparent support such as a polyester film to form a liquid photocurable resin layer, and a stamper having fine irregularities is pressed onto the support side. After removing the stamper after curing by light irradiation, pouring a liquid photocurable resin onto the stamper, pressing the support to expand the resin layer, and then curing by applying light from the support side Thereafter, there are a method of removing the stamper, a method of filling the stamper with resin, a method of transferring the resin to the support by removing the stamper after the support is stacked and irradiated with light from the support side and cured. However, in the method of forming using these liquid photocurable resin compositions, since the light is irradiated from the back side of the support, there is a restriction that it must be transparent to the light irradiated by the support. If the body is light-absorbing, curing will be insufficient, the process will take time because the stamper cannot be removed until curing is complete, and the photocurable resin layer is liquid, so bubbles will enter between the pressed stamper and defects Or when the stamper is peeled off from the cured resin layer, the surface of the resin layer becomes rough, cracks are formed, the pattern is chipped, or the substrate and the resin layer are peeled off. is there.
[0004]
Patent Document 1 is a compound having a so-called soft segment and a hard segment, which is composed of a cross-linked polymer formed by radiation polymerization of an oligomer composition that may contain an epoxy acrylate having a cyclic structure, An optical article having a surface carrying a structure is disclosed. However, since the oligomer composition is a liquid composition used to be cured by being injected or filled into a matrix, there is a problem associated with the method of forming using the liquid photocurable resin composition described above. In addition, there is a problem that the surface hardness of the resulting cured product is lowered due to the introduction of the soft segment and the weather resistance is lowered.
[0005]
Patent Document 2 discloses an ionizing radiation curable resin composition for optical sheets containing an epoxy acrylate having a cyclic structure. However, since this resin composition has a low viscosity at 25 ° C. of 1000 to 12000 cps and is a liquid composition, the above-mentioned liquid photocurable resin is not suitable for the process because it takes time to remove the stamper until the curing is completed. Problems associated with the method of forming with the composition arise.
[0006]
On the other hand, as another method of forming an optical article such as a diffraction grating or a relief hologram, a photocurable resin composition having a high viscosity or a solid is applied on a support at room temperature to form a photocurable resin layer, On top of that, there is a method in which a stamper is pressed and peeled off and then cured by light irradiation (Patent Documents 3 and 4). According to this method, the photocurable resin layer is directly irradiated with light so that it can be sufficiently cured. Since the photocurable resin composition is highly viscous or solid, coating and replication can be performed in separate steps. The stamper can be peeled off and light can be irradiated, so the stamper can be pressed and cured in separate steps. The light can be irradiated from the resin layer surface, so the support can be opaque to the light. However, since there is no need to irradiate light, there is an advantage that double-sided batch molding can be performed. Further, there are advantages that bubbles are difficult to enter between the photocurable resin layer and the stamper, so that the pattern can be formed accurately, and when the stamper is peeled off from the photocurable resin layer, the surface of the resin layer is less likely to be stringed.
[0007]
However, in the method using a photocurable resin composition having a high viscosity or a solid at room temperature, a part of the photocurable resin composition is adhered in the cavity of the stamper in order to peel off the stamper from the uncured resin layer. The stamper is peeled off from the uncured resin layer, which tends to remain (the phenomenon of plate-cutting), and the harder the photocurable resin composition flows into the cavity of the stamper as the uneven pattern to be replicated becomes finer. Then, since light is irradiated, there is a problem that pattern collapse is likely to occur until the curing is completed.
[0008]
Patent Document 5 describes a photocurable resin composition containing a urethane-modified acrylic resin having a bulky group and a release agent as essential components. The resin composition could solve the above problems.
[0009]
However, even with the resin composition described in Patent Document 5, it is very difficult to form a concavo-convex pattern at a high speed because it is necessary to sufficiently heat during embossing. In addition, a very complicated optical uneven pattern in recent years can be taken even with the resin composition described in Patent Document 5 and accurately replicated without causing problems of resin moldability and pattern collapse. It is very difficult.
[0010]
Furthermore, since the conventional resin composition contains a solvent as an essential component, problems such as a safety problem during work and a hindrance to deposition caused by a residual solvent on a subsequent process have occurred.
[0011]
[Patent Document 1]
Japanese Examined Patent Publication No. 4-5681
[Patent Document 2]
Japanese Patent Laid-Open No. 7-233227
[Patent Document 3]
JP-A-60-254174
[Patent Document 4]
JP 61-156273 A
[Patent Document 5]
JP 2000-63459 A
[0012]
[Problems to be solved by the invention]
The present invention has been accomplished in view of the above-mentioned actual situation, and the first object thereof is that the plate structure is small, the moldability and the mold maintenance are excellent, the surface structure having the concavo-convex pattern with high accuracy and high speed. An object of the present invention is to provide a concavo-convex pattern forming material that can be replicated on the surface, in particular, a concavo-convex pattern forming material that can accurately replicate a very complex fine uneven pattern in recent years.
[0013]
The second object of the present invention is to provide a concavo-convex pattern receptor and a concavo-convex pattern forming method using the above materials.
[0014]
The third object of the present invention is to provide a concavo-convex pattern transfer foil using the concavo-convex pattern forming material and the forming method, and an optical article having the concavo-convex pattern.
[0015]
[Means for Solving the Problems]
The concavo-convex pattern-forming material according to the present invention provided to achieve the above object includes two or more ethylenically unsaturated bonds and a cyclic structure in one molecule, and has a viscosity at 25 ° C. of 50000 mPa · s or more. The epoxy acrylate is a photocurable resin composition containing 50% by mass or more of the entire solid content and having a viscosity at 25 ° C. of 20000 mPa · s or more.
[0016]
An epoxy acrylate that contains two or more ethylenically unsaturated bonds in one molecule and a cyclic structure, and has a viscosity of 50000 mPa · s or more at 25 ° C., is used at the uneven pattern forming material of the present invention. Although it is a viscous material or solid, it softens easily when heated to the embossing or coating process temperature, and the viscosity is lowered. When it is returned to room temperature, which is the use environment temperature of the product, it instantly solidifies. Therefore, the concavo-convex pattern forming material of the present invention containing the epoxy acrylate in an amount of 50% by mass or more based on the total solid content can form a concavo-convex pattern forming layer that does not flow at a high viscosity or a solid state at room temperature. When heated at this time, the viscosity is lowered and it flows easily into the cavity of the stamper to be accurately shaped, and can be peeled cleanly from the stamper without causing plate removal. Furthermore, even if it is removed from the stamper before being cured, it is hard to cause pattern collapse because it is solidified by instantaneous cooling. For this reason, even a very complicated concavo-convex pattern can be reproduced with very high accuracy. In addition, since the photocuring can be performed after the stamper is removed, the support can be not only transparent but also opaque, and unevenness can be formed on both sides at once.
[0017]
Moreover, since the uneven pattern forming material of the present invention lowers the viscosity with a small amount of heating, the uneven pattern can be formed at a high speed by heating for a short time during embossing. Productivity is improved because the embossing speed can be increased.
[0018]
Furthermore, since the uneven pattern forming material of the present invention is easily reduced in viscosity by heating, it can be applied without containing a solvent in the composition. In this case, safety during operation is improved. In addition, problems such as deposition hindrance that the residual solvent exerts on the post-process are reduced.
[0019]
Moreover, since the said epoxy acrylate has two or more ethylenically unsaturated bonds in 1 molecule, the uneven | corrugated pattern formation material of this invention has photocurability. Therefore, the concavo-convex pattern forming material of the present invention can be cured at a temperature lower than the process temperature of embossing, hardly cause pattern collapse in the curing process, and can sufficiently fix the concavo-convex pattern formed by embossing. Sufficient film properties such as strength can be obtained.
[0020]
The uneven pattern forming material of the present invention further includes a monomer having two or more ethylenically unsaturated bonds in one molecule and having a viscosity of 20000 mPa · s or less at 25 ° C. It is preferable that an oligomer is included.
[0021]
The epoxy acrylate cyclic structure is one or more selected from bisphenol type, hydrogenated bisphenol type, biphenol type, novolac type, and naphthalene type, and maintains the uneven shape when peeled from the stamper in an uncured state. From the point of view, it is preferable.
[0022]
Moreover, in order to apply without a solvent, it is preferable that a viscosity will be 10000 mPa * s or less in any temperature of 30-120 degreeC.
[0023]
The inclusion of a solvent or a proportion of 3% by mass or less of the entire composition is preferable from the viewpoint of reducing safety during work and hindering vapor deposition.
[0024]
When the contact angle of water on the surface of the coating film formed by applying the concavo-convex pattern forming material on the support is 90 ° or more before and after curing, the release property from the stamper becomes good, and the plate is removed. This is preferable because it is difficult to occur.
[0025]
Next, the concavo-convex pattern receptor according to the present invention is formed using at least the concavo-convex pattern forming material according to the present invention.
[0026]
The concavo-convex pattern receptor according to the present invention does not contain a solvent or contains the concavo-convex pattern-forming material according to the present invention, which is contained in a proportion of 3% by mass or less of the whole composition, on the support by heating and melting. It may be formed by coating.
[0027]
Next, the method for forming a concavo-convex pattern according to the present invention includes a stamper provided with a concavo-convex shape on the surface of a concavo-convex pattern receptor having at least a concavo-convex pattern forming layer formed using the concavo-convex pattern forming material according to the present invention. A concavo-convex pattern is formed by pressure contact.
[0028]
In order to sufficiently fix the concavo-convex pattern and to ensure film properties such as strength, the concavo-convex pattern forming layer is usually cured by further light irradiation.
[0029]
In order to sufficiently cure the concavo-convex pattern or improve productivity, after removing the stamper from the concavo-convex pattern formation layer, light irradiation is performed to cure the concavo-convex pattern formation layer and fix the concavo-convex pattern. It is preferable. Further, before removing from the stamper, the concavo-convex pattern may be fixed by irradiating with light to cure the concavo-convex pattern forming layer.
[0030]
According to the present invention, a concavo-convex pattern transfer foil comprising at least the concavo-convex pattern forming material and provided with a concavo-convex pattern forming layer on which a concavo-convex pattern is formed can be formed on a first support. Is possible. When using concavo-convex pattern transfer foil, it is difficult to carry out direct embossing, such as articles with complex surface shapes, and supports glass, plastic, metal plates, etc. that cannot be rolled up An uneven pattern can be formed on the body by continuous transfer.
[0031]
In addition, according to the present invention, it is needless to say that a relief hologram or a concavo-convex pattern of a diffraction grating can be duplicated. In addition to a relatively large optical article such as a Fresnel lens having a relatively large size of 100 μm or more, it has a more advanced optical function. Complex concavo-convex patterns, such as concavo-convex patterns such as optical elements that control at least one of reflection, transmission, scattering, polarization, condensing, or interference of all rays and / or light of a specific wavelength, and information recording elements. However, it is possible to carry out mass production with high accuracy and embossing.
[0032]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below. The concavo-convex pattern-forming material according to the present invention contains 50 mass% of the total solid content of epoxy acrylate containing two or more ethylenically unsaturated bonds and a cyclic structure in one molecule and having a viscosity at 25 ° C of 50000 mPa · s or more. It is contained above and consists of a photocurable resin composition having a viscosity at 25 ° C. of 20000 mPa · s or more.
[0033]
The solid content of the composition includes all components except the solvent, for example, a liquid monomer component. In the present invention, light includes all wavelengths in the visible and non-visible regions that can cause a photoreactive functional group to cause a photoreaction, and includes all ionizing radiation such as radiation. For example, microwaves, infrared rays, visible light, ultraviolet rays, X-rays, α rays, electron beams and the like are all included, but ultraviolet rays, electron beams and the like are mainly used.
[0034]
In the present invention, the viscosity refers to a value obtained by a rotational viscometer shown in JIS-K7117. However, the viscosity cannot be measured with the above rotational viscometer capable of measuring a resin having a viscosity of 50000 mPa · s. The resin can be regarded as having a viscosity of 50000 mPa · s or more. The high viscosity material can be measured for dynamic viscosity using a rheometer (visco-viscoelasticity measuring device), a dynamic viscoelasticity measuring device, or the like. As for the dynamic viscosity, the measured value in the lower frequency region matches the value of the viscosity. In the present invention, the viscosity of a high-viscosity material of 50000 mPa · s or higher is measured using a dynamic viscoelasticity measuring device (for example, Rheogel-E4000 manufactured by UBM Co., Ltd.), using a liquid shearing jig, and a fundamental frequency. The dynamic viscosity is calculated from the viscoelastic data when a sine wave is applied at 10 Hz. The high-viscosity material used in the present invention has a dynamic viscosity that does not change depending on the measurement frequency or becomes higher in the low frequency region. Therefore, if the measured value of the dynamic viscosity at 10 Hz is sufficiently higher than 50000 mPa · s, the viscosity Can be considered to be sufficiently higher than 50000 mPa · s.
[0035]
An epoxy acrylate that contains two or more ethylenically unsaturated bonds in one molecule and a cyclic structure, and has a viscosity of 50000 mPa · s or more at 25 ° C., is used at the uneven pattern forming material of the present invention. Although it is a viscous material or solid, it softens easily when heated to the embossing or coating process temperature, and the viscosity is lowered. When it is returned to room temperature, which is the use environment temperature of the product, it instantly solidifies. It is presumed that the cyclic structure contained in the epoxy acrylate is easy to arrange due to its rigidity and has a regular structure, so that the viscosity suddenly decreases or the viscosity increases reversibly in a narrow temperature range. .
[0036]
Therefore, the concavo-convex pattern forming material of the present invention containing the epoxy acrylate in an amount of 50% by mass or more based on the total solid content can form a concavo-convex pattern forming layer that does not flow at a high viscosity or a solid state at room temperature. When heated at this time, the viscosity is lowered and it flows easily into the cavity of the stamper to be accurately shaped, and can be peeled cleanly from the stamper without causing plate removal. Furthermore, even if it is removed from the stamper before being cured, it is hard to cause pattern collapse because it is solidified by instantaneous cooling. For this reason, even a very complicated concavo-convex pattern can be reproduced with very high accuracy. In addition, since the photocuring can be performed after the stamper is taken out, the support can be not only transparent but also opaque, and unevenness can be collectively formed on both sides.
[0037]
Moreover, since the uneven pattern forming material of the present invention lowers the viscosity with a small amount of heating, the uneven pattern can be formed at a high speed by heating for a short time during embossing. Productivity is improved because the embossing speed can be increased.
[0038]
Furthermore, since the above-mentioned epoxy acrylate is easily reduced in viscosity by heating, it can be applied even without a solvent in the composition. In this case, the safety during operation is improved, and the residual solvent Inconveniences such as deposition hindrance affecting the subsequent processes are reduced.
[0039]
Moreover, since the said epoxy acrylate has two or more ethylenically unsaturated bonds in 1 molecule, the uneven | corrugated pattern formation material of this invention has photocurability. Therefore, the concavo-convex pattern forming material of the present invention can be cured at a temperature lower than the process temperature of embossing, hardly cause pattern collapse in the curing process, and can sufficiently fix the concavo-convex pattern formed by embossing. Sufficient film properties such as strength can be obtained.
[0040]
The concavo-convex pattern forming material of the present invention has a viscosity at 25 ° C. of 20000 mPa · s or more in order to form a concavo-convex pattern that does not flow at room temperature, and the concavo-convex pattern does not collapse even after the stamper is pressed and removed. For this purpose, a high-viscosity material is preferable, the viscosity at 25 ° C. is preferably 50000 mPa · s or more, and the viscosity at 25 ° C. is particularly preferably 80000 mPa · s or more or a solid.
[0041]
Moreover, since the uneven | corrugated pattern formation material of this invention has a lower softening temperature from the point that embossing is possible with little heat, since the suitable resin temperature at the time of embossing is 60-80 degreeC, softening temperature is It is preferably 80 ° C. or lower, and more preferably 60 ° C. or lower. The softening temperature in this case is Rheogel-E4000 manufactured by UBM Co., Ltd., a material having a high viscosity is once heated at 25 ° C., and packed in a liquid shearing jig. The dynamic viscoelasticity of the temperature rising process is measured while applying a sine wave under the condition of a frequency of 10 Hz. The value of the dynamic storage elastic modulus obtained is almost constant below the softening temperature, but rapidly decreases when the softening starts. Therefore, the inflection point of the dynamic storage elastic modulus plot is referred to herein as the softening temperature.
[0042]
The epoxy acrylate having two or more ethylenically unsaturated bonds and a cyclic structure in one molecule used in the present invention is combined with an ethylenically unsaturated bond to a compound having two or more epoxy groups and a cyclic structure in one molecule. It is obtained by reacting a compound having a carboxylic acid with a ring-opening addition reaction of the epoxy group with a carboxylic acid. Epoxy acrylate is characterized by having an epoxy residue containing a hydroxyl group by ring opening of the epoxy group.
[0043]
As a compound having two or more epoxy groups and a cyclic structure in one molecule, a glycidyl ether compound having two or more epoxy groups and a cyclic structure in one molecule is preferably used. As such a glycidyl ether compound, Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin; hydrogenated bisphenol type epoxy resin; biphenol type epoxy resin; bixylenol type epoxy resin; phenol novolac type epoxy resin , Cresol novolac type epoxy resin, xylenol novolak type epoxy resin, etc. novolac type epoxy resin; naphthalene skeleton epoxy resin; alicyclic skeleton epoxy resin; isocyanurate skeleton, fluoro Epoxy resins having a down skeleton and the like; and the like. Among these, the cyclic structure of the epoxy acrylate is selected from bisphenol type, hydrogenated bisphenol type, biphenol type, novolac type, and naphthalene type from the viewpoint of maintaining the uneven shape after removing the stamper when forming the uneven pattern. One or more of these are preferably used.
[0044]
As the compound having an ethylenically unsaturated bond and a carboxylic acid, a molecule having one or more ethylenically unsaturated bonds and a carboxyl group in one molecule can be used. Examples of the compound having an ethylenically unsaturated bond and a carboxylic acid include (meth) acrylic acid. In addition, one or more ethylenically unsaturated bonds and a molecule having a hydroxyl group and an acid anhydride are included in one molecule. Can be synthesized by reacting.
[0045]
Examples of the molecule having one or more ethylenically unsaturated bonds and a hydroxyl group include hydroxyalkyl such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxycyclohexyl meta (acrylate). (Meth) acrylates; trimethylolpropane mono (meth) acrylate, trimethylolpropane diacrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol di ( (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol pen Data (meth) acrylate.
[0046]
Examples of the acid anhydride include maleic anhydride, phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, 4-methyl-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like.
[0047]
The above epoxy acrylates may be used alone or in combination of two or more. The viscosity at 25 ° C. is 50000 mPa · s or more, preferably 80000 mPa · s or more, or a solid epoxy acrylate is used in the concavo-convex pattern forming material according to the present invention so that the solid content is 50% by mass or more. The concavo-convex pattern forming material according to the present invention may be blended with an epoxy acrylate having a viscosity at 25 ° C. of less than 50000 mPa · s. In a range not exceeding 50% by mass, the composition is blended so that the viscosity at 25 ° C. of the entire composition is 20000 mPa · s or more.
[0048]
The uneven pattern forming material according to the present invention contains two or more ethylenically unsaturated bonds in one molecule from the viewpoint of decreasing the viscosity of the composition and improving the crosslinking density, and has a viscosity of 20000 mPa · s or less at 25 ° C. A certain reactive monomer and / or oligomer may be blended.
[0049]
Examples of such reactive monomers include triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di ( Bifunctional monomers such as (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol-based di (meth) acrylate, ethylene oxide (hereinafter referred to as EO) modified phthalic acid di (meth) acrylate; trimethylolpropane tri ( (Meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter referred to as PO) -modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) ) Trifunctional monomers such as acrylate; tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate and ditrimethylolpropane tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like 5 or more functional monomers.
[0050]
Examples of the reactive oligomer include urethane acrylates, polyester acrylates, polybutadiene acrylates, polyether acrylates, epoxy acrylates, etc. Among them, the viscosity at 25 ° C. is 20000 mPa · s or less. Those can be preferably used.
[0051]
As urethane acrylates, an isocyanate compound having two or more isocyanate groups, a compound having two or more hydroxyl groups, and a compound having one or more hydroxyl groups and one or more (meth) acryloyl groups are reacted. Urethane acrylate obtained by reacting the obtained urethane acrylate or an isocyanate compound having two or more isocyanate groups with a compound having two or more hydroxyl groups and one or more (meth) acryloyl groups is preferred.
[0052]
Examples of the isocyanate compound having two or more isocyanate groups used for the synthesis of urethane acrylate include hexamethylene diisocyanate, 2,4-tolylene diisocyanate, isophorone diisocyanate, and hydrogenated xylylene diisocyanate. Examples of the compound having two or more hydroxyl groups used for the synthesis of urethane acrylate include 1,3-butanediol, trimethylolpropane, pentaerythritol, and glycerin. Examples of the compound having one or more hydroxyl groups and one or more (meth) acryloyl groups used for the synthesis of urethane acrylate include 2-hydroxyethyl (meth) acrylate, trimethylolpropane diacrylate, and pentaerythritol triacrylate. , Dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate and the like.
[0053]
The polyester acrylate is preferably a polyester acrylate obtained by reacting a compound having two or more hydroxyl groups or a polyester compound synthesized from a cyclic ester compound and a polybasic acid with a compound having a (meth) acryloyl group.
[0054]
As the compound having two or more hydroxyl groups used for the synthesis of the polyester acrylate, for example, the same compounds as those used for the synthesis of the urethane acrylate can be used. Examples of the cyclic ester compound used for the synthesis of the polyester acrylate include a lactone compound such as ε-caprolactone, a derivative thereof, or an addition reaction product of the lactone compound and an epoxy compound such as glycidyl methacrylate. Examples of the polybasic acid used for the synthesis of the polyester acrylate include saturated polybasic acids such as adipic acid, unsaturated polybasic acids such as maleic acid, and aromatic polybasic acids such as phthalic acid.
[0055]
Examples of polyether acrylates include polyether compounds obtained by reacting alkylene oxides such as ethylene oxide and propylene oxide with compounds having two or more hydroxyl groups in the molecule, and reactions such as alkyl (meth) acrylates. Those obtained by reacting an ester having a functional functional group and synthesizing by an ester exchange method or the like are preferred.
[0056]
As the epoxy acrylates, those having a viscosity of 20000 mPa · s or less at 25 ° C. among the above-mentioned epoxy acrylates can be preferably used.
[0057]
When the above monomers and / or oligomers are not used or when the amount used is too small, the strength, heat resistance, scratch resistance, water resistance, chemical resistance, and adhesion to the substrate of the resulting cured resin layer are poor. May be sufficient. On the other hand, if the amount of monomer or oligomer used is too large, the plate may be taken at the time of replication, and the uneven shape may not be maintained when the stamper is removed in an uncured state. From this viewpoint, it is preferable that the monomer and / or oligomer is blended in a proportion of 5 to 45% by mass and further 10 to 40% by mass in the total solid content of the uneven pattern forming material according to the present invention.
[0058]
If necessary, the concavo-convex pattern forming material according to the present invention may contain other components such as a photopolymerization initiator, a polymerization inhibitor, a mold release agent, and an organometallic coupling agent.
[0059]
As the photopolymerization initiator, a photopolymerization initiator that generates an appropriate active species according to the difference in the reaction mode of the epoxy acrylate and the reactive monomer and / or oligomer (for example, radical polymerization or cationic polymerization) is used. Since the ethylenic double bond contained in the epoxy acrylate is radical polymerization, it is particularly preferable to use a photo radical initiator.
[0060]
Examples of the photo radical initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, anthraquinone, methylanthraquinone, acetophenone, 2,2-diethoxyacetophenone, 2, 2-dimethoxy-2-phenylacetone, benzyldiacetylacetophenone, benzophenone, p-chlorobenzophenone, 2-hydroxy-2-methylpropiophenone, diphenyldisulfide, tetramethylthiuram sulfide, α-chloromethylnaphthalene, anthracene, hexachlorobutadiene, Pentachlorobutadiene, Michler's ketone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzyldimethylket Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, and the like.
[0061]
The photopolymerization initiator is preferably blended at a ratio of 0.5 to 10% by mass with respect to the total solid content of the uneven pattern forming material according to the present invention. A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.
[0062]
In order to improve the storage stability, the uneven pattern forming material of the present invention may contain a polymerization inhibitor. As a polymerization inhibitor, for example, phenols such as hydroquinone, t-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines; coppers and the like can be used. The polymerization inhibitor is preferably blended at a ratio of 0.1 to 10% by mass with respect to the total solid content of the uneven pattern forming material.
[0063]
Moreover, it is preferable that the uneven | corrugated pattern formation material of this invention mix | blends a mold release agent. By adding a mold release agent, when removing the stamper pressed against the concavo-convex pattern forming layer, the plate of the concavo-convex pattern forming material can be prevented and the stamper can be used continuously for a long time (repetitive embossing). become.
[0064]
As the release agent, conventionally known release agents, for example, waxes such as polyethylene wax, paraffin wax, microcrystalline wax, amide wax, montanic acid wax, oil-based wax; fluorine-based and phosphate-based surface activity Any of the following agents can be used: silicone release agents such as silicone oils and silicone resins; fluorine release agents such as fluorine compounds and fluorine resins such as vinylidene fluoride;
[0065]
In particular, a silicone release agent is preferable from the viewpoint of compatibility with the resin. Examples of the silicone release agent include polysiloxane, modified silicone oil, polysiloxane containing trimethylsiloxysilicic acid, and silicone acrylic resin.
[0066]
The modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, for example, amino modification, epoxy modification, carboxyl modification, carbinol modification, (meth) acryl modification, mercapto modification, phenol modification, polyether modification. , Methylstyryl modification, alkyl modification, fluorine modification and the like. Two or more of the above-described modification methods can be performed on one polysiloxane molecule.
[0067]
As the silicone-based acrylic resin, (meth) acryloyl-modified silicone oil or acrylic resin copolymerized or grafted with a monomer containing silicon is used.
[0068]
The silicone release agent can be added alone or in combination of two or more.
[0069]
The release agent is preferably blended at a ratio of 0.1 to 10% by mass in the total solid content of the uneven pattern forming material of the present invention. When the ratio of the release agent is less than the above range, the release property between the stamper and the uneven pattern forming layer tends to be insufficient. On the other hand, if the ratio of the release agent exceeds the above range, the surface of the coating film may be rough due to repelling during coating of the composition, or the substrate itself and the adjacent layer in the product, for example, the adhesion of the vapor deposition layer It is not preferable from the viewpoint of inhibiting the properties and causing film breakage or the like during transfer (film strength becomes too weak).
[0070]
An organic metal coupling agent may be blended with the concavo-convex pattern forming material of the present invention in order to improve the heat resistance, strength, or adhesion of the surface structure having the concavo-convex pattern to the metal vapor deposition layer. As the organometallic coupling agent, for example, various coupling agents such as a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a tin coupling agent can be used.
[0071]
The organometallic coupling agent is 0% in the total solid content of the concavo-convex pattern forming material of the present invention from the viewpoints of heat resistance, strength, effect of imparting adhesion to the deposited layer, stability of the composition, and film formability. It is preferable to mix | blend in the ratio of 1-10 mass%.
[0072]
The concavo-convex pattern forming material of the present invention is made of inorganic fine particles to maintain the plastic deformation characteristics during the formation of the concavo-convex pattern, and to adjust the viscosity to a desired value and to improve the shape maintenance after removing the stamper before uncured. May be blended.
[0073]
As the inorganic fine particles, those that can be uniformly dispersed in the composition, such as a colloidal form in a diluted monomer, are used.
[0074]
In addition, inorganic fine particles having a so-called ultrafine particle size are used in order to ensure sufficient transparency of the coating film. Here, “ultrafine particles” are particles of submicron order, and generally mean particles having a particle diameter smaller than particles having a particle diameter of several μm to several hundred μm, which are generally called “fine particles”. ing. The specific size of the inorganic fine particles used in the present invention varies depending on the use and grade of the optical article to which the uneven pattern forming material is applied, but generally the primary particle diameter is in the range of 1 nm to 300 nm. It is preferable to use it. If the primary particle diameter is less than 1 nm, it becomes difficult to sufficiently improve the plastic deformation characteristics of the uneven pattern forming material and the sustainability of the uneven shape before uncured, while if the primary particle diameter exceeds 300 nm, it is transparent. And the transparency may be insufficient depending on the use of the optical article.
[0075]
Specific examples of inorganic fine particles include SiO ₂ TiO ₂ , ZrO ₂ , SnO ₂ , Al ₂ O ₃ Among these, it is preferable to select and use a colloidal dispersible particle having a particle size on the order of submicron as described above, particularly colloidal silica (SiO 2). ₂ It is preferable to use fine particles.
[0076]
In addition, in order to form a chemical bond such as a covalent bond between fine particles or with a curable component such as epoxy acrylate, use inorganic fine particles having a reactive functional group such as a (meth) acryloyl group introduced on the surface. Can do.
[0077]
The inorganic fine particles are 0.1 to 30 mass in the total solid content of the concavo-convex pattern forming material of the present invention from the viewpoints of plastic deformation characteristics, improvement of ruggedness shape maintenance properties before uncured and sufficient strength and surface hardness. It is preferable to mix | blend in the ratio of%, and it is especially preferable to mix | blend in the ratio of 1-20 mass%.
[0078]
In order to adjust the uneven pattern forming material of the present invention to the desired viscosity, polymers may be blended in the range of 0.1 to 10% by mass.
[0079]
As the polymers, any of those having curable properties per se and those not having them may be used, or two or more kinds of polymers may be used in combination. Examples of polymers include acrylic resin, polyester, epoxy resin, polyolefin, styrene resin, polyamide, polyimide, polyamideimide, polyurethane, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polycarbonate, melamine resin, urea resin, alkyd resin, Examples include, but are not limited to, phenolic resins, cellulose resins, diallyl phthalate resins, silicone resins, polyarylate resins, polyacetal resins, and the like.
[0080]
In addition, when the contact angle of water on the surface of the coating film formed by applying the concavo-convex pattern forming material according to the present invention on the support is 90 ° or more before and after photocuring, the releasability from the stamper is This is preferable because it is good and the phenomenon of taking a plate is less likely to occur. The contact angle of water is obtained by observing the angle formed between the water droplet and the film surface with a contact angle meter.
[0081]
The epoxy acrylate used in the present invention is a high-viscosity or solid at 25 ° C., but softens easily when heated to lower the viscosity, and instantly solidifies when returned to room temperature, which is the use environment temperature of the product. Therefore, the concavo-convex pattern forming material of the present invention containing the epoxy acrylate in an amount of 50% by mass or more based on the total solid content is highly viscous or solid at room temperature and does not flow, but particularly preferably at any temperature of 30 to 120 ° C. When the viscosity is reduced to 10000 mPa · s or less, preferably 8000 mPa · s or less when the temperature is set to 80 to 120 ° C., the solvent is not contained, or only 3% by mass or less of the whole composition is heated. Then, it can be applied on the support by melting. By not using or reducing the amount of the solvent, problems such as safety problems at the time of work and vapor deposition inhibition that the residual solvent exerts on the post-process are improved.
[0082]
The concavo-convex pattern forming material of the present invention can be prepared in the state of a coating solution using a diluting solvent as in the prior art, and can also be used for forming a concavo-convex pattern. In this case, the coating solution is usually adjusted so that the solid content concentration is about 10 to 60% by mass.
[0083]
Solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, benzene, toluene, xylene, chlorobenzene, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, 1,4-dioxane, 1, 2-Dichloroethane, dichloromethane, chloroform, methanol, ethanol, isopropanol, or a mixed solvent thereof can be used.
[0084]
The concavo-convex pattern forming material is applied to the surface of a support such as a base film, and dried as necessary to form a concavo-convex pattern forming material layer (concavo-convex pattern forming layer) to produce a concavo-convex pattern receptor. Then, a concavo-convex pattern having an optical function is formed by pressing a stamper on the surface of the concavo-convex pattern forming layer of the concavo-convex pattern receptor to perform embossing and curing the concavo-convex pattern forming layer by an appropriate method such as exposure. It can be used as an optical article or stamper.
[0085]
The concavo-convex pattern receptor according to the present invention is formed using at least the concavo-convex pattern forming material according to the present invention. The concavo-convex pattern receptor is formed, for example, by applying the concavo-convex pattern forming material to the surface of a support such as a base film and drying it as necessary to form a concavo-convex pattern forming material layer (concave pattern forming layer). Manufactured.
[0086]
When the concavo-convex pattern forming material does not contain a solvent or contains a solvent at a ratio of 3% by mass or less of the whole composition, the concavo-convex pattern forming material is heated and melted on the support. Is applied to produce an uneven pattern receptor.
[0087]
The concavo-convex pattern forming layer may be formed on one side of the support or on both sides. Even if the concavo-convex pattern forming material according to the present invention used for the concavo-convex pattern receptor of the present invention is removed from the stamper before being cured, it is hard to cause pattern collapse due to instantaneous cooling, so after removing the stamper It is also possible to cure by irradiating light from the front surface of the concavo-convex pattern forming layer. The concavo-convex pattern receptor of the present invention does not necessarily have to be cured in a state where the stamper is in pressure contact, and is therefore suitable as a concavo-convex pattern receptor for forming concavo-convex on both sides at once.
[0088]
The concavo-convex pattern forming layer is produced, for example, by applying using a gravure coater and then drying the organic solvent contained in the composition as necessary. As a coating machine other than the gravure coater, for example, a roll coater, a curtain coater, a flow coater, a lip coater, a doctor blade coater and the like can be used. The thickness of the concavo-convex pattern forming layer is appropriately adjusted, but is usually about 0.1 to 5.0 μm.
[0089]
Before applying the uneven pattern forming layer to the support, other layers such as an anchor layer, a release layer, a metal thin film layer, and an overcoat layer may be formed as necessary. Although the support etc. which are used for an uneven | corrugated pattern receptor can use a well-known thing suitably, the thing similar to what is used for the transfer foil mentioned later is used preferably for a support body, a peeling layer, a metal thin film layer, etc.
[0090]
The concavo-convex pattern forming method according to the present invention includes a concavo-convex pattern forming layer formed using the concavo-convex pattern forming material according to the present invention, and a concavo-convex shape is provided on the surface of the concavo-convex pattern receptor according to the present invention. An uneven pattern is formed by pressing the stamper.
[0091]
Usually, after embossing by pressing a stamper on the surface of the concavo-convex pattern receiving layer of the concavo-convex pattern receiver, the concavo-convex pattern is fixed by fixing the concavo-convex pattern by further irradiating light to cure the concavo-convex pattern forming layer. Form. In this case, the uneven pattern formed by embossing can be sufficiently fixed and sufficient film properties such as strength can be obtained.
[0092]
In the step of curing the concavo-convex pattern forming layer, the stamper may be cured in pressure contact before removing the stamper. However, the concavo-convex pattern forming material according to the present invention may be instantaneously removed from the stamper before curing. It is hard to cause pattern collapse due to solidification by cooling, so that it is possible to cure by removing light from the front surface of the concavo-convex pattern forming layer after removing the stamper. When curing with the stamper in pressure contact, light is irradiated from the back side of the support, so that the support must be transparent, and if the support has light absorption, curing is insufficient. Since the stamper cannot be removed until the curing is completed, there is a problem that the process takes time. On the other hand, when the stamper is removed and then cured by light irradiation from the front surface of the concavo-convex pattern forming layer, there is no restriction on the support and it can be cured sufficiently, and the removed stamper can be embossed. Because it can be used continuously, it has excellent continuous productivity. Furthermore, it is also suitable for forming unevenness on both sides at once. On the other hand, in the case where the stamper is cured while being pressed, there is an advantage that the unevenness can be fixed more accurately and the plate is not easily taken off.
[0093]
Moreover, after forming an uneven | corrugated pattern in an uneven | corrugated pattern formation layer, you may form other layers, such as a metal thin film layer, an overcoat layer, a pressure-sensitive or heat-sensitive adhesive layer, as needed.
[0094]
The concavo-convex pattern receptor may be a final product to which the surface structure of the concavo-convex pattern is to be imparted, but may be an intermediate transfer medium. That is, in the present invention, the concavo-convex pattern forming material is applied to a first support to form a concavo-convex pattern forming layer, and a concavo-convex pattern is formed on the concavo-convex pattern forming layer to produce a transfer foil. After the patterning layer is cured, it can be transferred onto a second support (final product). When using a transfer foil, there is an advantage that it is not necessary to directly emboss the surface of the final product, or a large number of uneven patterns can be formed in advance on the transfer foil. It is also possible to form an uneven pattern by continuous transfer on the surface of an article that is difficult to directly emboss, such as a shaped article, or on a support such as glass, plastic, or metal plate that cannot be rolled up. It is.
[0095]
In the present invention, the concavo-convex pattern transfer foil is made of at least the concavo-convex pattern forming material on the first support, and can be peeled off from the first support and transferred to the second support. Is a laminate in which a concavo-convex pattern forming layer is provided and a concavo-convex pattern is formed on the concavo-convex pattern forming layer, and if necessary, in addition to the concavo-convex pattern forming layer, a release layer, a reflective layer, an adhesive layer or One or more of the other layers can be provided. For example, as shown in FIG. 1, the transfer foil 1 may have a configuration in which a peeling layer 3, an uneven pattern forming layer 4, a reflective layer 5, and an adhesive layer 6 are sequentially laminated on a support 2.
[0096]
As a support for producing a concavo-convex pattern receptor and a transfer foil, a flexible base film is usually used, and a plastic film such as polyethylene terephthalate is suitable in terms of strength and heat resistance. The material is not limited to a plastic film, and may not be flexible, and other materials such as a metal plate and paper may be used as a support. In the case of using an impregnated support such as paper, it may be formed in a state in which the concavo-convex pattern forming layer is impregnated in the support structure, and even in such a state, it is provided on the support. It is included in one form of the uneven pattern forming layer. In addition, a continuous film may be used as the substrate film in consideration of mass productivity of a concavo-convex pattern such as a hologram, but a sheet-like substrate film may be used.
[0097]
The release layer is provided as needed on the lower layer of the concavo-convex pattern forming layer for the purpose of improving the peelability of the transfer foil and the foil cutting property, and the concavo-convex pattern is formed on the transfer surface (second support) from the transfer foil. It is the layer that becomes the outermost surface after being transferred together with the layer. As the release layer, for example, only one kind selected from acrylic resin, polyester resin, polyvinyl chloride resin, cellulose resin, silicone resin, chlorinated rubber, casein, various surfactants, metal oxides, etc., alone or 2 More than seeds can be selected and mixed for use. Or what added these as an additive to the uneven | corrugated pattern formation material of this invention used for an uneven | corrugated pattern formation layer can also be used as a peeling layer.
[0098]
The reflective layer is provided on the concavo-convex pattern when forming a relief hologram, for example. When an opaque metal thin film that reflects light is used as the reflective layer, an opaque type hologram is obtained. When a reflective layer having a refractive index difference from the hologram layer is provided with a transparent material, the transparent type is used. The reflective layer can be formed using a transparent material having a refractive index different from that of the resin of the uneven pattern forming layer. The refractive index in this case may be larger or smaller than the refractive index of the resin of the concavo-convex pattern forming layer, but the difference in refractive index is preferably 0.1 or more, more preferably 0.5 or more. Zero or more is optimal.
[0099]
The metal thin film is, for example, a metal such as Cr, Ti, Fe, Co, Ni, Cu, Ag, Au, Ge, Al, Mg, Sb, Pb, Pd, Cd, Bi, Sn, Se, In, Ga, and Rb. And a mixture of oxides, nitrides, sulfides, etc., alone or in combination of two or more thereof, such as vacuum deposition such as chemical vapor deposition and physical vapor deposition, sublimation, sputtering, reactive sputtering, ion plating, electroplating, etc. The method can be used. Among the metal thin films, Al, Cr, Ni, Ag, Au and the like are particularly preferable, and the film thickness is in the range of 1 to 10,000 nm, desirably 20 to 200 nm.
[0100]
Titanium oxide (TiO ₂ ), A metal compound having a relatively high refractive index, such as zinc sulfide (ZnS), can be used as a transparent reflective layer because it can provide transparency when the particle size is small.
[0101]
The high refractive index film can be formed using a coating liquid of a high refractive index material, for example, coating of a coating liquid in which a high refractive index filler is dispersed, coating of a colloidal solution of gold or silver, sol gel It can be formed by forming a coating film by hydrolysis polycondensation reaction of an organometallic compound represented by the reaction.
[0102]
The adhesive layer is used for the purpose of improving the transferability of the concavo-convex pattern forming layer and the adhesion to the transferred surface after transfer, or the surface of the concavo-convex pattern forming layer after embossing is used as a reflective film or a protective film. Is coated on the outermost surface of the concavo-convex pattern forming layer for the purpose of improving the adhesion to these layers, and is the lowermost layer after being transferred together with the concavo-convex pattern forming layer.
[0103]
As the adhesive layer, a known heat-sensitive adhesive resin can be used. For example, rubber systems such as polyisoprene rubber, polyisobutylene rubber, styrene butadiene rubber; poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, poly (meth) acrylate, (Meth) acrylic acid esters such as poly (meth) acrylic acid-2-ethylhexyl; polyvinyl ethers such as polyisobutyl ether; polyvinyl chlorides such as polyvinyl acetate and vinyl chloride-vinyl acetate copolymer; polyacrylamide Polyamides such as polymethylolacrylamide; Vinyl chlorides such as polyvinyl chloride; Other vinyls such as polyvinyl butyral, vinyl acetate / octyl acrylate, vinyl acetate / butyl acrylate, vinylidene chloride / butyl acrylate; polystyrene, etc. An aromatic vinyl system of; and Li chloride olefin and the like, can be used alone or in combination of two or more select only one among these.
[0104]
The method for forming a concavo-convex pattern according to the present invention will be specifically described by taking a transfer foil of a relief hologram as an example and dividing it into each stage of preparation of the transfer foil, duplication of the concavo-convex pattern, and transfer. In addition, the code | symbol used is for referring FIGS. 1-3.
[0105]
<Production of transfer foil>
First, the base film 2 made of continuous plastic such as polyethylene terephthalate is fed out from the roll stock. A coating solution of a release agent was applied onto the unrolled base film using a gravure coater, and then set to a temperature at which the organic solvent contained in the coating solution was scattered, for example, l00 to 165 ° C. The release layer 3 is formed by introducing the powder into a heating furnace for about 0.1 to 1 minute and drying it. On the release layer 3, the concavo-convex pattern forming material according to the present invention is subsequently applied using a gravure coater. Moreover, when the uneven | corrugated pattern formation material which concerns on this invention is a solvent-free, it heat-melts and apply | coats at 80-120 degreeC with a coating unit with a heater. When the concavo-convex pattern forming material contains a solvent, the material is then led to a temperature at which the organic solvent contained in the composition scatters, for example, in a heating furnace set at 100 to 165 ° C. for about 0.1 to 1 minute. dry. When the concavo-convex pattern forming material is solvent-free, a drying step is unnecessary. As described above, the concavo-convex pattern forming layer 4 is formed to produce the transfer foil 1. As a coating machine other than the gravure coater, for example, a roll coater, a curtain coater, a flow coater, a lip coater, a doctor blade coater, a die coater and the like can be used. The thickness of the concavo-convex pattern forming layer is usually about 0.1 to 5.0 μm. The produced transfer foil 1 is conveyed from the coating unit of the apparatus to the duplication unit.
[0106]
<Reproduction of uneven pattern>
Next, the relief foil stamper is pressed onto the surface of the concavo-convex pattern forming layer and embossed on the transfer foil 1 conveyed to the duplication unit to form a concavo-convex pattern.
[0107]
FIG. 2 is a diagram illustrating an example of a method for continuously producing a concavo-convex pattern using a continuous sheet-like transfer foil. In FIG. 2, the continuous sheet-like transfer foil 1 is conveyed to a duplication unit by a support roller 7 and supplied to an embossing process. On the conveyance path in the embossing process, for example, a pair of embossing composed of a metal roll 9a and a paper roll 9b on which a stamper 8 continuously created from a mother die made using a laser beam or an electron beam is mounted on the peripheral surface. A roller 9 is installed. In addition, as an embossing roller of the duplicating apparatus, a duplication hologram created from a master hologram by resin plate making and pasted on a cylinder can be used.
[0108]
When the transfer foil 1 passes between the embossing rollers, the stamper is pressed against the concavo-convex pattern forming layer to form the concavo-convex pattern 4 ′. The embossing of the hologram pattern is, for example, a hot roll temperature of 100 to 200 ° C. and a press pressure of 5 × 10. ³ ~ 5x10 ⁶ Perform at Pa. When embossing is performed under the pressing conditions in this range, the resin temperature of the concavo-convex pattern forming layer is adjusted to a temperature within or near the temperature range of 60 to 80 ° C., and the viscosity becomes suitable for embossing. When the hot roll temperature is higher than the above range, embossing can be performed at a high speed, but the damage to the base film is increased. Moreover, since it will take time to raise resin temperature when a hot roll temperature is made lower than the said range, an embossing process becomes slow.
[0109]
The embossing illustrated above is single-sided embossing, but double-sided embossing may be used. In embossing, it is important to set the temperature of the embossing roll. From the viewpoint of reproducing the embossing shape, it is preferable to emboss at a relatively high temperature and relatively high pressure, but in order to prevent adhesion to the embossing plate. It is preferable to emboss at a relatively low pressure, which is exactly the opposite relationship. Further, when considering the heat capacity that acts effectively, the conveyance speed of the film to be duplicated is also important. In order to reduce the adhesion of the concavo-convex pattern forming material to the embossing roll, the selection of the release agent described above is also important.
[0110]
When the continuous sheet-like transfer foil 1 passes between the embossing rollers, the embossing roller rotates in accordance with the supply speed of the transfer foil, and the embossing is repeated on the uneven pattern forming layer 4 so that the uneven pattern 4 ′ is continuous. Shaped.
[0111]
When the transfer foil 1 passes between the embossing rollers, the portion of the concavo-convex pattern forming layer where the concavo-convex pattern is shaped is peeled off from the stamper, and a curing process is performed. In this example, the uneven pattern forming layer is photocured using the irradiation source 10. Curing of the concavo-convex pattern forming layer by light irradiation may be performed with the stamper kept in pressure contact, but by performing the curing after removing the stamper, the pressure contact process and the curing process can be performed independently and in parallel. preferable. By separating the pressure welding process and the curing process, the working rate of the stamper is increased, and the efficiency of the curing work is increased by direct and uniform light irradiation on the surface of the concavo-convex pattern forming layer, resulting in high productivity. .
[0112]
Examples of the light used for curing include high energy ionizing radiation and ultraviolet rays. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, radiation such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes or nuclear reactors can also be used. Examples of the ultraviolet ray source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a solar lamp.
[0113]
After forming the concavo-convex pattern and curing, on the concavo-convex pattern forming layer, if necessary, a reflective layer 5 such as a metal vapor deposition layer, or a transparent protective film for enhancing scratch resistance and stain resistance May be formed. For example, the reflective layer can be formed by vacuum-depositing aluminum to a thickness of 600 mm.
[0114]
In addition, when a layer such as a reflective layer or a protective film is added on the concavo-convex pattern forming layer, an adhesive layer 6 may be further added thereon. For example, an acrylic heat-sensitive sealant is applied with a gravure coat, dried at 100 ° C., and a dry film thickness of 3 g / m ² The adhesive layer can be formed.
[0115]
The continuous sheet-like transfer foil 1 produced in this way is cut into sheets. Alternatively, the continuous sheet-shaped transfer foil 1 may be wound again after the formation of the concavo-convex pattern to form a roll stock, which may be stored or transported.
[0116]
FIG. 3 is a diagram showing another method for continuously producing a concavo-convex pattern using a continuous sheet-like transfer foil. In FIG. 3, the continuous sheet-like transfer foil 1 is conveyed by the support roller 7 and supplied to the embossing process.
[0117]
On the conveyance path in the embossing step, a metal roller 9a having a cavity shape in which a concavo-convex pattern to be fabricated is inverted is mounted over 360 degrees, and the transfer foil 1 is in close contact with the metal roller 9a. Pressure roller 9c that presses the transfer foil 1 against the metal roller 9a at the position of the first half (preferably immediately after the start of close contact), and the second half of the stage where the transfer foil 1 is in close contact with the metal roller 9a (preferably immediately before the end of close contact). A set of embossing rollers 9 composed of a pressing roller 9d that presses the transfer foil 1 against the metal roller 9a is provided.
[0118]
The rotation axis of the metal roller 9 a is offset from the height of the transfer path of the transfer foil 1. Therefore, the transfer foil 1 is not in line contact with the peripheral surface of the metal roller, but is in surface contact and can be sufficiently shaped by the stamper 8. The height difference between the transfer path of the transfer foil 1 and the metal roller 9a is preferably adjusted so that the transfer foil 1 can contact the peripheral surface of the metal roller 9a over a wide area.
[0119]
The concavo-convex pattern forming layer can be softened by a heat roller that heats the metal roller 9a, the pressure roller 9c in the first half, or both. In this case, the conditions such as the hot roll temperature, the pressing pressure, and the resin temperature of the concavo-convex pattern forming layer are the same as those in FIG.
[0120]
Moreover, the softened uneven | corrugated pattern formation layer can be cooled by making the press roller 9d of a latter half part into a cooling roll as needed, and the shape maintainability after embossing can be improved.
[0121]
The concavo-convex pattern forming layer of the transfer foil 1 may be pre-cured by the irradiation source 11 while being pressed against the stamper. Preliminarily semi-curing by light irradiation with the concavo-convex pattern forming layer pressed against the stamper, it becomes difficult to lose shape until the main curing is performed after the stamper is peeled off, improving the shape maintenance property be able to.
[0122]
When the transfer foil 1 passes between the metal roller 9a and the latter pressure roller 9d, the portion of the concavo-convex pattern forming layer where the concavo-convex pattern 4 ′ is shaped is peeled off from the stamper, and the irradiation source 10 is used in the curing process. The concavo-convex pattern forming layer is photocured.
[0123]
<Transfer of uneven pattern>
Next, on the uneven pattern forming layer of the transfer foil on which the uneven pattern is formed, the transfer surface of the second support is faced and superimposed, and the portion of the transfer foil where the hologram is to be transferred is placed on the base film side. Then, the film is heated and pressed with a pressure roller or a pressure plate to melt and bond it, and then the transfer foil is peeled off, whereby the concavo-convex pattern forming layer having the concavo-convex pattern is transferred onto the second support. The temperature and pressure at the time of transfer are factors related to the pressure method (roll type, stamping type) and pressure method, as well as the material and melting temperature of the support, the melting temperature of the heat-sensitive adhesive, and the heat-sensitive adhesive. Since the conditions vary greatly depending on factors such as the adhesion between the agent and the support material, the conditions are adjusted accordingly.
[0124]
In this way, the transfer process is completed, and an optical article comprising a cured resin layer having a surface structure on which a relief hologram relief pattern is formed, which is made of a cured product of the relief pattern forming material, is obtained.
[0125]
According to the present invention, the unevenness having various optical functions, comprising the cured product of the uneven pattern forming material according to the present invention, by the same method as the relief hologram or by modifying the method as necessary. It is possible to produce an optical article provided with a cured resin layer having a surface structure on which a pattern is formed.
[0126]
The concavo-convex pattern forming material according to the present invention can form concavo-convex patterns of various sizes. Specifically, for example, a concavo-convex pattern having a concavo-convex pattern width (pitch) of 100 nm to 500 μm can be formed. it can.
[0127]
Conventionally, the concavo-convex pattern of a hologram replicated by embossing generally has a width (pitch) of about 500 to 1500 nm and a depth (depth / width) with respect to the width of about 1/3 or less. According to the present invention, it is needless to say that such a concavo-convex pattern can be duplicated, and a complex concavo-convex pattern having a more advanced optical function, for example, the width (pitch) of the concavo-convex pattern is about 200 nm or less, or Even when a pattern with a ratio of depth to depth (depth / width) of 1 or more is replicated, the concave / convex pattern forming material can be sufficiently poured into the cavity when the stamper is pressed, and the plate is removed when the stamper is peeled off. Therefore, it is difficult to cause pattern collapse after the stamper is removed. Therefore, it is possible to mass-produce a concavo-convex pattern with high accuracy by embossing.
[0128]
As an optical article produced by embossing using the concavo-convex pattern forming material of the present invention, at least one of reflection, transmission, scattering, polarization, condensing or interference of all light rays and / or light of a specific wavelength is controlled. An optical element is mentioned. As an element (subwavelength structure element) which consists of a periodic uneven | corrugated pattern below the wavelength of light, the structure (Math-eye) which has antireflection performance, a polarizing plate, and a phase difference plate are mentioned, for example.
[0129]
Examples of the optical element include those having a concavo-convex pattern of 100 μm to several hundred μm. For example, a backlight member of a liquid crystal display, a Fresnel lens used as a member of a projection screen, a lenticular lens, a light diffusion plate, etc. Other examples include a light guide plate or a prism sheet.
[0130]
Furthermore, examples of the optical article produced by embossing using the concavo-convex pattern forming material of the present invention include, for example, a relief hologram or a diffraction grating in which concavo-convex portions having a width of about 1 μm are usually engraved. Relief holograms and diffraction gratings can be used for relief holograms and diffraction gratings used in graphic arts and design applications, such as amusement products such as so-called photo clubs, gifts, packaging, postcards / sealings, novelty goods, etc. For example, credit cards, ID cards, gift certificates, banknotes and the like are used for security applications and forgery prevention applications, using attached symbols and complex patterns.
[0131]
In addition, a computer generated hologram (Computer Generated Hologram) in which a concavo-convex pattern having a wavelength equal to or smaller than the wavelength of light is formed. This is a technique (for example, refer to Japanese Patent Application Laid-Open No. 2002-40219) that can synthesize a concavo-convex pattern for controlling the wavelength of light by a computer. A plate, a holographic image can be made. With this technique, an image having high security and an optical element such as a light reflector can be produced.
[0132]
As an optical article, there is an information recording element for recording information by forming concave and convex pits. The size of the concavo-convex pattern of the information recording element is, for example, 0.2 μm to 0.8 μm, although it depends on the recording amount. Examples of the information recording element include an information recording hologram, an optical card, and an optical disk.
[0133]
The present invention can be applied to applications that control light more complicatedly or more precisely than relief holograms and diffraction gratings. However, when applied to relief holograms and diffraction gratings, the present invention is not limited to simply obtaining bright holograms. Relief holograms and diffraction gratings with simple designs can be formed.
[0134]
In addition, the present invention continuously forms fine wiring patterns, patterns used for optical waveguides, micro-sized and nano-sized fine grooves and channels used for lab-on-a-chip, etc. It can also be applied.
[0135]
Furthermore, the present invention is capable of replicating not only fine patterns but also sizes of 100 μm or more, and it is easy to form irregularities on opaque substrates by the production method of the present invention. It can also be applied to.
[0136]
In addition, according to the present invention, a concavo-convex pattern can be formed with very high accuracy, so that a complementary concavo-convex pattern can be duplicated using a concavo-convex pattern to be applied to an optical article as a mold, and this can be used as a stamper. It is.
[0137]
【Example】
(Example 1)
An uneven pattern forming material 1 was prepared with the following composition. Since it was solid at 25 ° C., the viscosity was measured when a dynamic viscoelasticity measurement method (Rheogel-E4000 manufactured by UBM Co., Ltd. was used and a sine wave was applied at a fundamental frequency of 10 Hz using a liquid shearing jig. The dynamic viscosity was calculated from the elasticity data by the calculation of the dynamic viscosity from the elasticity data. ⁹ mPa · s.
<Rough pattern forming material 1>
Epoxy acrylate (25 ° C. solid) (trade name: Lipoxy VR-60, manufactured by Showa Polymer): 60 parts by weight
-Reactive oligomer (urethane acrylate; viscosity at 25 ° C. 20000 mPa · s) (trade name: Murasaki UV-1700B, manufactured by Nippon Synthetic Chemical Industry): 30 parts by weight
Bifunctional monomer (neopentyl glycol diacrylate; 25 ° C. viscosity 5 mPa · s) (trade name: NPGDA, Nippon Kayaku): 5 parts by weight
Photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals): 5 parts by weight.
[0138]
(Example 2)
An uneven pattern forming material 2 was prepared with the following composition. It was a solid at 25 ° C. According to the same dynamic viscoelasticity measurement as above, the dynamic viscosity is 9 × 10. ⁸ mPa · s.
<Rough pattern forming material 2>
・ Epoxy acrylate (solid at 25 ° C.) (Brand name: Lipoxy VR-90, manufactured by Showa Polymer): 70 parts by weight
-Reactive oligomer (urethane acrylate; viscosity at 25 ° C. 20000 mPa · s) (trade name: Murasaki UV-1700B, manufactured by Nippon Synthetic Chemical Industry): 15 parts by weight
Bifunctional monomer (hexanediol diacrylate; 25 ° C. viscosity 5 mPa · s) (trade name: HDDA, Nippon Kayaku): 10 parts by weight
Photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals): 5 parts by weight.
[0139]
(Comparative Example 1)
An uneven pattern forming material C1 was prepared with the following composition. It was a solid at 25 ° C. According to the same dynamic viscoelasticity measurement as described above, the dynamic viscosity is 1 × 10 ⁹ mPa · s.
<Rough pattern forming material C1>
Polymethylmethacrylate (25 ° C. solid) (trade name: BR-85, manufactured by Mitsubishi Rayon): 30 parts by weight
-Urethane acrylate (trade name: Purple light UV-1700B, manufactured by Nippon Synthetic Chemical Industry): 65 parts by weight
Photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals): 5 parts by weight.
[0140]
(Comparative Example 2)
An uneven pattern forming material C2 was prepared with the following composition. The viscosity at 25 ° C. was 10,000 mPa · s.
<Rough pattern forming material C2>
Epoxy acrylate (25 ° C viscosity 10000 mPa · s) (trade name: Lipoxy VR-77, Showa High Polymer): 95 parts by weight
Photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals): 5 parts by weight.
[0141]
(Evaluation)
(1) Production of uneven pattern receptor
The compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were dissolved in methyl ethyl ketone to form a 20% solid solution. 1 mass% of silicone oil (trade name X-24-8201, manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto and stirred well. Thereafter, a support (polyethylene terephthalate film; trade name Diafoil T-600E, manufactured by Mitsubishi Polyester Film) is coated with a bar coater, dried in an oven at 100 ° C. for 30 seconds, and an uneven pattern forming layer having a thickness of about 2 μm. A concavo-convex pattern receptor having the above was prepared.
[0142]
(2) Water contact angle measurement
The integrated exposure amount is 600 mJ / cm on the concavo-convex pattern receptor obtained in (1). ² The resin coating surface was irradiated with ultraviolet rays so as to be cured. The contact angle of water on the film surface before and after curing was measured with a contact angle meter.
[0143]
(3) Concavity and convexity pattern formation test 1
A nickel stamper having a line and space pattern with a pitch of 0.5 μm and a height of 0.3 μm was used as the stamper. The concavo-convex pattern surface of the stamper and the concavo-convex pattern forming layer of the concavo-convex pattern receiver obtained in (1) are overlapped, and a pressure of 3 MPa is applied with a heat roll heated to about 130 ° C. and pressed at a speed of 15 m / min. It was. Thereafter, the film was peeled off through a cooling roll at about 30 ° C. The time from pressure bonding to peeling was about 1 second. The peeled film was held at room temperature for about 1 minute, and then irradiated with ultraviolet rays so that the integrated exposure amount was 600 mJ / cm 2 to obtain a film with a diffraction grating engraved.
[0144]
The glossiness of the obtained film was visually observed to evaluate the brightness of the diffraction grating. Depending on the brightness of the diffraction grating, the performance of the diffraction grating and the reproducibility of the uneven shape can be evaluated. A bright diffraction grating was evaluated as good (◯), and a dark diffraction grating was determined as poor (×).
[0145]
Further, the surface of the obtained film was observed with an AFM (atomic force microscope), and the depth of the diffraction grating was measured. As the AFM, Nano Scope III type AFM (manufactured by Digital Instruments) was used, and the scanning mode was a tapping mode. A nickel stamper with a depth reproducibility of 90% or more was evaluated as good (◯), and a sample with less than 90% as defective (×).
[0146]
Moreover, the shape after embossing was observed, and the thing without a string-like roughness was evaluated as good (◯), and a certain one was evaluated as defective (×). In addition, the presence or absence of the plate was observed, and the case where no resin remained on the nickel stamper was evaluated as good (◯). The evaluation results are shown in Table 1.
[0147]
(4) Concavity and convexity pattern formation test 2
The compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were dissolved in methyl ethyl ketone to form a 20% solid solution. 3 mass% of silicone oil (trade name X-24-8201, manufactured by Shin-Etsu Chemical Co., Ltd.) was added thereto and stirred well. Thereafter, a support (polyethylene terephthalate film; trade name Diafoil T-600E, manufactured by Mitsubishi Polyester Film) is coated with a bar coater, dried in an oven at 100 ° C. for 30 seconds, and an uneven pattern forming layer having a thickness of about 2 μm. A concavo-convex pattern receptor having the above was prepared. As the stamper, a stamper made of a nickel plating plate having convex and concave portions having a pitch of 300 nm and a height of 250 nm regularly arranged in a square lattice shape in the vertical and horizontal directions and having a fine uneven shape in which the valley side is pointed from the mountain side was used. . This is a shape called Moth-eye having antireflection performance. The concavo-convex pattern surface of the stamper and the concavo-convex pattern forming layer were overlapped, and a pressure of 3 MPa was applied with a heat roll heated to about 130 ° C., and the pressure was pressed at a speed of 15 m / min. Thereafter, the film was peeled off through a cooling roll at about 30 ° C. The time from pressure bonding to peeling was about 1 second. The peeled film is held at room temperature for about 1 minute, and then the integrated exposure is 600 mJ / cm. ² The film was engraved with a diffraction grating.
[0148]
The back surface of the obtained fine uneven pattern film was shielded from light, visible light was incident from an incident angle of 5 °, and the reflectance (wavelength 650 nm) of the opposite light was measured. The smaller the reflectance, the higher the antireflection performance, that is, the fine concavo-convex pattern is accurately engraved. In a film that does not form a fine uneven pattern, the reflectance measured under these conditions is 3% or more. The evaluation results are shown in Table 1.
[0149]
(5) Concavity and convexity pattern formation test 3
The compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were melted by heating in an oven at 110 ° C. Thereto, 1% by mass of silicone oil (trade name BYK-307, manufactured by Big Chemie) was added to prepare a 130 ° C. hot plate, on which a support (polyethylene terephthalate film; trade name Diafoil T-600E) was prepared. , Manufactured by Mitsubishi Polyester Film) and coated with a molten resin to prepare a pattern receptor having an uneven pattern forming layer.
[0150]
The concavo-convex pattern formation conditions and evaluation were performed in the same manner as the concavo-convex pattern formation test 1.
[0151]
In addition, evaluation of coating property evaluated that what can form a thin film in the range of 2-10 micrometers was coatable ((circle)), and the thing which has a high viscosity and cannot be coated was evaluated as uncoating (x). The evaluation results are shown in Table 1.
[0152]
(6) Concavity and convexity pattern formation test 4
Pattern acceptance having a concavo-convex pattern forming layer having a thickness of about 200 μm, coated with a molten resin on the support under the same conditions as the concavo-convex pattern formation test 2 except that a 100 ° C. hot plate was used instead of the 130 ° C. hot plate The body was made.
[0153]
As the stamper, a metal mold having a pattern as shown in FIG. 4 having a pitch of 200 μm and a height of 100 μm was used. The concavo-convex pattern surface of the stamper and the concavo-convex pattern forming layer were overlapped, and a pressure of 6 MPa was applied with a heat roll heated to about 130 ° C., and pressure-bonded at a speed of 15 m / min. Thereafter, the film was peeled off through a cooling roll at about 30 ° C. The time from pressure bonding to peeling was about 1 second. The peeled film is held at room temperature for about 1 minute, and then the integrated exposure is 600 mJ / cm. ² The film was engraved with a diffraction grating. The evaluation was performed in the same manner as the above-described uneven pattern formation tests 1 and 3 except for the glossiness. The evaluation results are shown in Table 1.
[0154]
[Table 1]

【The invention's effect】
As described above, the concavo-convex pattern forming material of the present invention can form a high-viscosity or solid non-flowing concavo-convex pattern forming layer at room temperature, and the viscosity decreases when heated during embossing. Thus, it can easily flow into the cavity of the stamper and be accurately shaped, and can be peeled cleanly from the stamper without causing plate removal. Furthermore, even if the stamper is removed before curing, the pattern is not easily broken because it is solidified by instantaneous cooling. For this reason, even a very complicated concavo-convex pattern can be reproduced with very high accuracy. Further, after removing the stamper, it is also possible to cure by irradiating light from the front surface of the concavo-convex pattern forming layer. Therefore, it is possible to sufficiently cure, and it is also possible to form unevenness on both sides at once. Furthermore, the support can be not only transparent but also opaque, and the removed stamper can be used continuously in the embossing process, so it has excellent continuous productivity.
[0155]
Moreover, since the uneven pattern forming material of the present invention lowers the viscosity with a small amount of heating, the uneven pattern can be formed at a high speed by heating for a short time during embossing. Productivity is improved because the embossing speed can be increased.
[0156]
Furthermore, since the above-mentioned epoxy acrylate is easily reduced in viscosity by heating, it can be applied even without a solvent in the composition. In this case, the safety during operation is improved, and the residual solvent Inconveniences such as deposition hindrance affecting the subsequent processes are reduced.
[0157]
Moreover, since the said epoxy acrylate has two or more ethylenically unsaturated bonds in 1 molecule, the uneven | corrugated pattern formation material of this invention has photocurability. Therefore, the concavo-convex pattern forming material of the present invention can be cured at a temperature lower than the process temperature of the embossing process, hardly cause pattern collapse in the curing process, and can sufficiently fix the concavo-convex pattern formed by the embossing process. In addition, sufficient film properties such as strength can be obtained.
[0158]
Moreover, according to the uneven | corrugated pattern formation method which concerns on this invention, since it can harden | cure after removing a stamper from an uneven | corrugated pattern formation layer, it is possible to mass-produce a concavo-convex pattern continuously.
[0159]
In addition, since the uneven pattern forming material according to the present invention can form an uneven pattern forming layer that does not flow at high temperature or solid at room temperature on a support, it is also possible to form an uneven pattern transfer foil. is there. When the uneven pattern transfer foil is used, productivity can be further improved.
[0160]
According to the present invention, it is needless to say that a relief hologram or a concavo-convex pattern of a diffraction grating can be duplicated. In addition to a relatively large optical article such as a Fresnel lens having a relatively large size of 100 μm or more, a complex having a more advanced optical function An uneven pattern, for example, an optical element that controls at least one of reflection, transmission, scattering, polarization, condensing, or interference of all light rays and / or light of a specific wavelength, and an uneven pattern such as an information recording element Mass production is possible with high accuracy and embossing.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of an example of an uneven pattern transfer foil.
FIG. 2 is a diagram for explaining an example of a method for creating an uneven pattern.
FIG. 3 is a diagram for explaining an example of a method for creating an uneven pattern.
FIG. 4 is a diagram illustrating an example of an uneven pattern.
[Explanation of symbols]
1. Transfer foil
2 ... Support
3 ... release layer
4 ... Uneven pattern forming layer
4 '... Uneven pattern
5 ... Reflective layer
6 ... Adhesive layer
7 ... Support roller
8 ... Stamper
9 ... Embossed roller
9a ... Metal roller
9b ... Paper roller
9c ... Pressure contact roller
9d ... Pressure contact roller
10 ... Irradiation source
11 ... Irradiation source (pre-curing)

Claims (21)

One molecule contains two or more ethylenically unsaturated bonds and a cyclic structure, and an epoxy acrylate having a viscosity at 25 ° C. of 50000 mPa · s or more is contained by 50% by mass or more of the entire solid content, and the viscosity at 25 ° C. is 20000 mPa. An uneven pattern forming material comprising a photocurable resin composition of s or more. Furthermore, the uneven | corrugated pattern formation material of Claim 1 containing the monomer and / or oligomer which contain two or more ethylenically unsaturated bonds in 1 molecule, and whose viscosity is 20000 mPa * s or less in 25 degreeC. The concavo-convex pattern forming material according to claim 1 or 2, wherein the viscosity is 10,000 mPa · s or less at any temperature of 30 to 120 ° C. The uneven | corrugated pattern formation material in any one of Claims 1 thru | or 3 whose cyclic structure of the said epoxy acrylate is 1 or more types selected from the bisphenol type | mold, hydrogenated bisphenol type | mold, a biphenol type | mold, a novolak type | mold, and a naphthalene type | mold. The uneven | corrugated pattern formation material in any one of Claims 1 thru | or 4 which does not contain a solvent or contains in the ratio of 3 mass% or less of the whole composition. The uneven pattern forming material according to any one of claims 1 to 5, wherein a contact angle of water on a coating film surface formed by applying the uneven pattern forming material on a support is 90 ° or more before and after photocuring. . A concavo-convex pattern receptor formed using at least the concavo-convex pattern forming material according to any one of claims 1 to 6. The concavo-convex pattern receptor according to claim 7, wherein the concavo-convex pattern-forming material according to claim 5 is formed by coating on a support by heating and melting. A method for producing a concavo-convex pattern receptor, comprising the step of applying the concavo-convex pattern forming material according to claim 5 on a support by heating and melting the material. A concavo-convex pattern is formed by press-contacting a stamper provided with a concavo-convex shape on the surface of a concavo-convex pattern receptor having a concavo-convex pattern forming layer formed using at least the concavo-convex pattern forming material according to claim 1. A method for forming an uneven pattern. The concavo-convex pattern formation method according to claim 10, wherein the concavo-convex pattern receptor is the concavo-convex pattern receptor according to claim 8. Furthermore, the uneven | corrugated pattern formation method of Claim 10 or 11 which hardens the said uneven | corrugated pattern formation layer by light irradiation. The uneven | corrugated pattern formation method of Claim 12 which light-irradiates after removing a stamper from the said uneven | corrugated pattern formation layer, and hardens the said uneven | corrugated pattern formation layer. The uneven | corrugated pattern formation method of Claim 12 which light-irradiates before removing a stamper from the said uneven | corrugated pattern formation layer, and hardens the said uneven | corrugated pattern formation layer. A concavo-convex pattern transfer in which a concavo-convex pattern forming layer made of at least the concavo-convex pattern forming material according to any one of claims 1 to 6 is provided on a support so as to be transferable, and the concavo-convex pattern is formed on the concavo-convex pattern forming layer. Foil. An optical article comprising a surface structure made of a cured product of the concavo-convex pattern forming material according to claim 1 and having a concavo-convex pattern formed thereon. The optical article according to claim 16, wherein the concavo-convex pattern is an optical element that controls at least one of reflection, transmission, scattering, polarization, light collection, and interference of all light rays and / or light of a specific wavelength. The optical article according to claim 16, wherein the uneven pattern is a relief hologram, a diffraction grating, or a computer generated hologram. The optical article according to claim 17, wherein the optical element is a structure having antireflection performance, a polarizing plate, or a retardation plate. The optical article according to claim 17, wherein the optical element is a Fresnel lens, a lenticular lens, a light guide plate, a light diffusion plate, or a prism sheet. The optical article according to claim 16, wherein the uneven pattern has a structure for recording information.

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