JP2011178155A - Resin mold, molded object, and method for manufacturing molded object - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin mold which is a mold for imprinting, made of a resin, and easily releasable and of which the surface has good fine shape precision even in a case that the surface is subjected to hydrophilizing processing. <P>SOLUTION: The resin mold comprises a material containing a resin component (a). The resin component (a) is applied to the smooth surface of a base material having the smooth surface and dried to form a resin layer (A) having a smooth surface to thereby obtain the resin mold of which the static contact angle (X1) measured according to JIS R3257 when 3 μL of water is arranged on the smooth surface of the formed resin layer (A) satisfies a condition (1). The resin component (b) in a material constituting a transfer object is applied to the smooth surface of the base material having the smooth surface and dried to form a resin layer 11 having the smooth surface and, after 3 μL of water 13 is arranged on the smooth surface of the formed resin layer 11, the absolute value θ of the difference between the static contact angle (Y1) and static contact angle (X1) of the resin mold measured according to JIS R3257 is 20-60°. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin mold, a molded body, and a method for manufacturing the molded body. More specifically, the present invention relates to a resin nanoimprint mold used in a microstructure molding technique, and can be easily released from a transfer target. The present invention also relates to a resin mold, a molded body, and a method for manufacturing the molded body, which have a fine surface shape with good accuracy even when the surface is subjected to a hydrophilic treatment.

  Conventionally, in the field of manufacturing semiconductors such as LSIs and memories, a lithography technique is used as a method for forming a fine pattern. However, the lithography technique has a problem that the process is complicated, the area that can be processed at one time is small, and the equipment cost is very high. Therefore, recently, a nanoimprint method has attracted attention because it has a simple process, a large area that can be processed at one time (that is, a large area can be transferred collectively), and a low equipment cost, as compared with lithography technology. Specifically, the nanoimprint method is a method capable of achieving nano-order microfabrication by pressing a mold on which a nanometer-order fine shape is formed against a resin. And according to such a nanoimprint method, as mentioned above, a fine pattern can be replicated with a simple process and low cost. As the mold, a mold made of silicon, quartz, metal, resin or the like is used.

  As the nanoimprint method, a thermal nanoimprint method, an optical (UV) nanoimprint method, and the like have been reported, and the thermal nanoimprint method is performed by pressing a mold heated above the glass transition temperature of a resin transfer target against the transfer target. This is a method of transferring a micrometer or nanometer-order fine shape to a transfer target (see, for example, Non-Patent Document 1 and Patent Document 1). In the optical nanoimprint method, a mold such as quartz that transmits light is pressed against a transfer target made of a photocurable resin, and then the transfer target is cured by irradiating the mold with light such as ultraviolet rays. This is a method of transferring a micrometer or nanometer order fine shape to a transfer target (see, for example, Non-Patent Document 2, Non-Patent Document 3, and Patent Document 2).

  As a mold used in the thermal nanoimprint method, a mold mainly made of silicon or nickel is mainly used, and as a mold used in the optical nanoimprint method, a mold mainly made of quartz or the like is used.

  However, molds made of silicon, nickel, and quartz are expensive and have a high risk of contamination and breakage. Therefore, recently, resin molds (resin molds) have been used. Specifically, resin molds made of a material containing a cyclic olefin copolymer (COC) (see, for example, Patent Document 3), oil A resin mold containing a thermoplastic resin containing a cyclic structure and a fatty acid ester compound containing a hydroxyl group, having a predetermined glass transition temperature (Tg) and a predetermined melt flow rate (MFR) (for example, see Patent Document 4) ) Has been proposed.

International Publication No. 04/062886 Pamphlet JP 2007-84625 A JP 2007-55235 A JP 2006-35823 A

S. Y. Chou, P.A. R. Krauss, P.M. J. et al. Renstrom: Appl. Phys. Lett. 67 (1995) p. 3114 T.A. Bailey, B.M. J. et al. Chooi, M .; Colburn, M.M. Meissi, S .; Shaya, J .; G. Ekerdt, S .; V. Screenivasan, C.I. G. Willson: J.M. Vac. Sci. Technol. B18 (2000) p. 3572 A. Kumar, G .; M.M. Whitesides: Appl. Phys. Lett. 63 (1993) p. 2002

  However, since the resin component constituting the resin mold described in Patent Documents 3 and 4 is similar in properties to the resin component in the material constituting the transfer object, the affinity between the resin mold and the transfer object is very high. There is a problem that when the resin mold is pressed against the transfer target, the resin mold and the transfer target are in close contact with or welded to each other. In such a case, the resin mold cannot be released from the transfer target, or even if it can be released, there is a problem that the transferred fine shape is damaged. Moreover, although the resin type | mold described in patent document 4 has reduced the affinity with the transcription | transfer object by mix | blending an additive (hydroxyl group containing fatty acid ester compound), the compounding ratio of an additive becomes non-uniform | heterogenous. There is. For this reason, there is a possibility that a difference in releasability may occur due to a difference in surface properties (specifically, a difference in contact angle) between resin mold production lots. Also, even in the same resin mold, the surface properties may vary (partially) depending on the location (specifically, the contact angle may be different). There could be a difference. Therefore, development of a resin mold that can be easily released from the transfer object is eagerly desired.

  In addition, when the properties of the resin component constituting the resin mold and the resin component constituting the transfer target are similar, the contact angle is reduced by hydrophilizing the surface having the fine shape of the resin mold, and the resin mold Can be reduced in affinity with the transcription target. However, there has been a problem that the surface shape is deteriorated (that is, the fine shape is scraped) by the hydrophilic treatment. Therefore, the development of a resin mold in which the fine shape is difficult to be cut by the hydrophilization treatment (that is, the accuracy of the fine shape of the surface is good) is eagerly desired.

  The present invention has been made in order to solve the above-described problems of the prior art, and can be easily released from a transfer target. Even when the surface is hydrophilized, the surface has a fine shape. It is an object to provide a resin mold, a molded body, and a method for manufacturing the molded body with good accuracy.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors paid attention to the relationship between the surface property of the resin component in the material constituting the resin mold and the surface property of the resin component in the material constituting the transfer target, The absolute value of the difference between the static contact angle with respect to 3 μL of water of the resin component in the material constituting the resin mold and the static contact angle with respect to 3 μL of water of the resin component in the material constituting the transfer object is 20 It has been found that the above-described problems can be achieved by setting the angle to 60 ° to 60 °, and the present invention has been completed.

  The present invention provides the following resin mold, molded body, and method for producing the molded body.

[1] A nanoimprint for forming a fine shape for pattern formation on the surface, which is made of a material containing the resin component (a), and transferring the fine shape to a transfer object made of a material containing the resin component (b) A resin layer having a smooth surface by applying the resin component (a) on the smooth surface of a substrate having a smooth surface and drying or irradiating light. After forming (A), 3 μL of water is placed on the smooth surface of the formed resin layer (A), and the static contact angle (X1) measured in accordance with JIS R 3257 is as follows: Resin mold that satisfies condition (1).
Condition (1): Applying the resin component (b) of the material constituting the transfer object onto the smooth surface of a substrate having a smooth surface and drying or irradiating light. After forming a resin layer (B) having a smooth surface with 3 μL of water on the smooth surface of the formed resin layer (B), static contact measured according to JIS R 3257 The absolute value of the difference between the angle (Y1) and the static contact angle (X1) is 20 ° to 60 °.

[2] The resin mold according to [1], which is obtained by hydrophilizing the surface on which a fine shape is formed.

[3] After forming the resin layer (A), the smooth surface of the formed resin layer (A) is hydrophilized, and 3 μL of water is disposed on the hydrophilized smooth surface, and JIS The resin mold according to [2], wherein the static contact angle (X2) measured in accordance with R 3257 satisfies the following condition (2).
Condition (2): The difference ((Y1) − (X2)) between the static contact angle (Y1) and the static contact angle (X2) is 20 ° to 60 °.

[4] The resin mold according to [2] or [3], in which UV ozone treatment is performed as the hydrophilic treatment.

[5] The resin mold according to [2] or [3], wherein a corona discharge treatment is performed as the hydrophilic treatment.

[6] The resin mold according to [2] or [3], in which plasma discharge treatment is performed as the hydrophilic treatment.

[7] The resin mold according to any one of [1] to [6], wherein the surface is obtained by a release agent treatment.

[8] The resin mold according to any one of [1] to [7], wherein the resin component (a) includes a thermoplastic resin, and a fine shape on the surface is formed by thermal nanoimprint.

[9] The thermoplastic resin according to [8], wherein the thermoplastic resin is at least one selected from the group consisting of a cyclic olefin resin, a polyolefin resin, an acrylic resin, a polycarbonate resin, a polyvinyl ether resin, and a polystyrene resin. Resin mold.

[10] The resin mold according to any one of [1] to [7], wherein the resin component (a) includes a photocurable resin, and a fine shape on the surface is formed by optical nanoimprinting. .

[11] Structural unit derived from at least one curable compound selected from the group consisting of a linear vinyl ether compound, an alicyclic vinyl ether compound, an epoxy compound, an oxetane compound, and an acrylic compound. The resin mold as described in [10] above, which contains

[12] The resin mold according to any one of [1] to [11], which is for thermal nanoimprinting.

[13] The resin mold according to any one of [1] to [11], which is for optical nanoimprint.

[14] A molded product obtained by transferring a fine shape formed on the surface of the resin mold according to any one of [1] to [13].

[15] Using a resin mold made of a material containing a resin component (a) and having a fine shape for pattern formation formed on the surface, the fine shape of the resin mold is made from a material containing a resin component (b) A method for producing a molded body that obtains a molded body in which the inverted shape of the fine shape of the resin mold is formed on the surface thereof by transferring to a transfer target, wherein the resin component (a) Is applied on the smooth surface of the substrate having a smooth surface and dried, or the resin layer (A) having a smooth surface is formed by irradiating light, and then the resin layer ( Production of a molded body using a resin mold in which 3 μL of water is placed on the smooth surface of A) and the static contact angle (X1) measured in accordance with JIS R 3257 satisfies the following condition (1) Method.
Condition (1): Applying the resin component (b) of the material constituting the transfer object onto the smooth surface of a substrate having a smooth surface and drying or irradiating light. After forming a resin layer (B) having a smooth surface with 3 μL of water on the smooth surface of the formed resin layer (B), static contact measured according to JIS R 3257 The absolute value of the difference between the angle (Y1) and the static contact angle (X1) is 20 ° to 60 °.

[16] As the resin mold, the smooth surface of the formed resin layer (A) is obtained by hydrophilizing the surface on which a fine shape is formed, and after forming the resin layer (A). The surface is hydrophilized, 3 μL of water is placed on the hydrophilized smooth surface, and the static contact angle (X2) measured according to JIS R 3257 satisfies the following condition (2) The method for producing a molded article according to [15], wherein a resin mold is used.
Condition (2): The difference ((Y1) − (X2)) between the static contact angle (Y1) and the static contact angle (X2) is 20 ° to 60 °.

  The resin mold of the present invention is a resin-made nanoimprint mold used in the molding technology for fine structures, and can be easily released from the transfer target. Even when the surface is hydrophilized, the surface mold is fine. There is an effect that the accuracy of the shape is good.

  The molded product of the present invention can be easily released from the transfer target, and even when the surface is subjected to a hydrophilic treatment, the molded product is formed using a resin mold with good precision of the surface fine shape. This has the effect of having a good fine pattern.

  The method for producing a molded article according to the present invention can be easily released from a transfer target, and is formed using a resin mold having a fine surface with a good precision even when the surface is hydrophilized. Therefore, there is an effect that a molded body having a good fine pattern can be manufactured.

It is explanatory drawing which shows typically the measurement state of the contact angle in this invention. It is sectional drawing which shows typically the manufacturing process of one Embodiment of the resin mold | type of this invention. It is sectional drawing which shows typically the manufacturing process of one Embodiment of the resin mold | type of this invention. It is sectional drawing which shows typically the manufacturing process of one Embodiment of the resin mold | type of this invention. It is sectional drawing which shows typically one Embodiment of the resin type | mold of this invention. 6 is a SEM (scanning electron microscope) photograph of a resin mold after UV ozone treatment obtained in Example 5. FIG.

  Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to the following embodiment. That is, it is understood that modifications and improvements as appropriate to the following embodiments are also within the scope of the present invention based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. Should be.

[1] Resin mold:
The resin mold of the present invention is made of a material containing a resin component (a), a fine shape for pattern formation is formed on the surface, and the fine shape is transferred to a transfer object made of a material containing the resin component (b). A resin having a smooth surface by applying the resin component (a) on the smooth surface of a substrate having a smooth surface and drying or irradiating light. After forming the layer (A), 3 μL of water is placed on the smooth surface of the formed resin layer (A), and the static contact angle (X1) measured according to JIS R 3257 is as follows: It satisfies (1).
Condition (1): The resin component (b) of the material constituting the transfer object is applied on the smooth surface of the substrate having a smooth surface and dried, or smoothed by light irradiation. After forming the resin layer (B) having a surface, 3 μL of water is disposed on the smooth surface of the formed resin layer (B), and the static contact angle (Y1) measured according to JIS R 3257 And the absolute value of the difference between the static contact angle (X1) is 20 ° to 60 °.

  Such a resin mold is a resin-made nanoimprint mold used in the molding technology for fine structures, and can be easily released from the transfer target. Even when the surface is hydrophilized, the surface is fine. Good shape accuracy. That is, when the absolute value is 20 ° to 60 °, the above-described effects can be obtained. However, when the absolute value is less than 20 °, the releasability is deteriorated. The accuracy is good, but the fine shape accuracy is poor.

  As described above, the absolute value needs to be 20 ° to 60 °, preferably 20 ° to 58 °, and more preferably 20 ° to 55 °. When the absolute value is within the above preferred range, there is an advantage that the mold can be more easily released from the transfer target, and the accuracy of the fine shape of the surface is excellent even when the surface is hydrophilized.

  The resin component (a) preferably contains a thermoplastic resin. Examples of the thermoplastic resin include cyclic olefin resins, polyolefin resins, acrylic resins, polycarbonate resins, polyvinyl ether resins, polystyrene resins, polyethylene terephthalate resins, vinyl chloride resins, and the like. Among these, at least one selected from the group consisting of a cyclic olefin resin, a polyolefin resin, an acrylic resin, a polycarbonate resin, a polyvinyl ether resin, and a polystyrene resin is preferable, and a cyclic olefin resin is preferable. Further preferred. Examples of the cyclic olefin-based resin include cyclic olefin ring-opening polymerization / hydrogenated product (COP resin) and cyclic olefin copolymer (COC resin).

  When the resin component (a) contains a thermoplastic resin, it is preferable that the resin mold has a fine shape on the surface formed by thermal nanoimprint. This is because a fine shape can be efficiently formed by forming the fine shape by thermal nanoimprint.

  The resin component (a) preferably contains a photocurable resin. This photocurable resin contains a structural unit derived from a curable compound. Examples of the curable compound include a linear vinyl ether compound, an alicyclic vinyl ether compound, an epoxy compound, an oxetane compound, an acrylic compound, and an anhydrous compound. And maleic acid. Among these, a linear vinyl ether compound, an alicyclic vinyl ether compound, an epoxy compound, an oxetane compound, and an acrylic compound are preferable. These compounds can be used alone or in combination of two or more. That is, it preferably includes a structural unit derived from at least one curable compound selected from the group consisting of a linear vinyl ether compound, an alicyclic vinyl ether compound, an epoxy compound, an oxetane compound, and an acrylic compound.

  When the resin component (a) contains a photocurable resin, it is preferable that the resin mold has a fine shape formed on the surface by optical nanoimprinting. This is because a fine shape can be efficiently formed by forming a fine shape by optical nanoimprint.

  Examples of the resin component (a) include thermosetting resins in addition to the thermoplastic resin and the photocurable resin.

  The resin mold of the present invention is not particularly limited as long as it is made of a material containing the resin component (a), and may be made only of the resin component (a), or may be a lubricant, antioxidant, antistatic agent. It may further contain other components (additives) such as an agent, an ultraviolet stabilizer, a leveling agent (surface adjusting agent), a viscosity adjusting agent, a polymerization initiator, and a sensitizer.

  In the resin mold of the present invention, the surface on which the fine shape is formed is preferably subjected to a hydrophilic treatment. By hydrophilizing the surface, the static contact angle on the surface of the resin layer can be easily reduced, and a resin mold having good releasability can be obtained. In addition, when the surface properties are changed by hydrophilization treatment after the resin mold is manufactured, in the resin mold manufacturing process, good releasability from a metal mold can be secured. After the hydrophilic treatment, the affinity between the resin mold and the transfer target can be reduced by this hydrophilic treatment, and a resin mold having good releasability from the transfer target can be obtained.

Furthermore, when hydrophilizing, it is preferable to process so that the following static contact angle (X2) may satisfy the following conditions (2). The static contact angle (X2) is obtained by applying the resin component (a) on the smooth surface of the substrate having a smooth surface and drying or irradiating light with the resin layer (A ), The smooth surface of the formed resin layer (A) is hydrophilized, 3 μL of water is placed on the hydrophilized smooth surface, and a value measured in accordance with JIS R 3257. is there.
Condition (2): The difference ((Y1) − (X2)) between the static contact angle (Y1) and the static contact angle (X2) is 20 ° to 60 °.

  In the resin mold of the present invention, as described above, the difference between the static contact angle (Y1) and the static contact angle (X2) is preferably 20 ° to 60 °, and 20 ° to 58 °. More preferably, it is particularly preferably 20 ° to 55 °. When the difference between the static contact angle (Y1) and the static contact angle (X2) is within the above range, it is particularly easy to release from the transfer target, and even when the surface is hydrophilized It is possible to obtain a resin mold with excellent accuracy of the fine shape.

  Examples of the hydrophilization treatment include UV ozone treatment, corona discharge treatment, plasma discharge treatment, and metal sodium treatment. Among these, UV ozone treatment, corona discharge treatment, and plasma discharge treatment are preferable.

  In the case of hydrophilization by UV ozone treatment, there is an advantage that the surface treatment can be performed in the atmosphere and the damage to the resin is small. The conditions for the UV ozone treatment are not particularly limited, and conventionally known conditions can be appropriately employed. Specifically, UV irradiation is performed using a low-pressure mercury lamp in the air at an irradiation distance of 10 to 30 mm. Processing can be exemplified. In addition to the low-pressure mercury lamp, a xenon excimer lamp can be used.

  In the case of hydrophilization by corona discharge treatment, there is an advantage that surface treatment can be performed in the atmosphere as in the case of UV ozone treatment and the treatment speed is high. The conditions for the corona discharge treatment are not particularly limited, and conventionally known conditions can be appropriately employed. Specifically, in the air, a discharge gap of 0.5 to 20 mm and a high frequency of 10 kHz to 100 kHz, A process of applying a high voltage can be exemplified.

  In the case of hydrophilization by plasma discharge treatment, since only the very surface of the resin mold can be modified, there is an advantage that the bulk characteristics of the resin component (a) are not affected. The conditions for the plasma discharge treatment are not particularly limited, and conventionally known conditions can be appropriately employed. Specifically, RIE (reactive ion etching) treatment in the presence of oxygen gas or nitrogen gas can be used. The reverse sputtering treatment in the presence can be exemplified.

  The resin mold of the present invention is preferably obtained by treating the surface with a release agent. By performing such a release agent treatment, there is an advantage that the releasability is further improved. As the release agent treatment, for example, a release agent can be applied to the surface of the resin mold by dip coating, spin coating, spray coating or the like. Examples of the release agent include a fluorine-based solvent and a silicon-based release agent. The release agent treatment may be performed before the hydrophilic treatment or after the hydrophilic treatment when the surface of the resin mold is subjected to the hydrophilic treatment. Preferably it is done.

[2] Manufacturing method of resin mold:
When the resin component (a) of the constituent material is made of a thermoplastic resin (that is, when a fine shape on the surface is formed by thermal nanoimprinting), the resin mold of the present invention is as follows. Can be manufactured as follows. First, a mold on which a desired uneven pattern is formed is prepared (see FIG. 2A). Examples of the mold material include metals such as silicon, quartz, SiC, nickel, and tantalum, and glassy carbon. Next, a resin film made of a thermoplastic resin is prepared. Examples of the thermoplastic resin include the above-described cyclic olefin resin, polyolefin resin, acrylic resin, polycarbonate resin, polyvinyl ether resin, polystyrene resin, and the like. FIG. 2A is a cross-sectional view schematically showing the mold 1 on which the uneven pattern 15 is formed.

  Next, as shown in FIG. 2B, the mold 1 is arranged on the resin film 3 so that the surface on which the desired uneven pattern 15 is formed contacts the resin film 3. Thereafter, the mold is pressed against the resin film while applying heat using a conventionally known press machine or the like (see FIG. 2C). Thereafter, the resin film is released from the mold, and a resin mold 5 on which a desired uneven pattern 17 (inverted shape of the uneven pattern 15 of the mold 1) as shown in FIG. 2D is formed can be obtained. 2C is a cross-sectional view showing a state in which the mold 1 is pressed against the resin film 3, and FIG. 2D is a cross-sectional view showing the resin mold 5 on which a desired uneven pattern 17 is formed.

  Next, the resin mold of the present invention can be manufactured as follows when the resin component (a) of the constituent materials is made of a photocurable resin. First, a mold on which a desired uneven pattern is formed is prepared. Examples of the mold material include quartz. Next, a photocurable resin is applied onto the substrate to form a coating film on the substrate. Examples of the photocurable resin include those containing a structural unit derived from a curable compound composed of a linear vinyl ether compound, an alicyclic vinyl ether compound, an epoxy compound, an oxetane compound, an acrylic compound, and the like. Examples of the substrate include resin films such as PET films and cyclic olefin resin films, and semiconductor substrates such as silicon wafers. As a method for forming the coating film, a conventionally known method can be adopted, and examples thereof include a method using a bar coater and the like, and a spin coating method.

  Next, a metal mold | die is arrange | positioned so that the surface in which the desired uneven | corrugated pattern was formed contacts the said coating film on the formed coating film. A mold is pressed against the coating film using a conventionally known press machine or the like. Thereafter, the coating film is cured by irradiating predetermined light to obtain a cured resin film. Then, the cured resin film and the PET film are released from the mold, and a resin mold on which a desired uneven pattern is formed can be obtained. The wavelength of the irradiated light can be appropriately selected according to the photocurable resin.

[3] Application of resin mold:
The resin mold of the present invention can be used to obtain a molded product having an uneven shape on the surface (resin surface) to be transferred by thermal nanoimprint or optical nanoimprint. Specifically, as this molded body, an optical disk molded body, an optical fiber, a camera lens, an overhead projector lens, an LBP Fθ lens, a prism, a liquid crystal display element (LCD), a light diffusion plate, a light guide plate, a polarizing film, Optically molded products such as retardation films, brightness enhancement films, condensing films; various clean containers such as liquid chemical containers, ampoules, infusion bags, eye drops containers, semiconductor wafer storage containers; syringes, medical infusion tubes, etc. Medical equipment; resist masks for substrate processing such as silicon and sapphire.

  The resin mold of the present invention may be used for thermal nanoimprinting or optical nanoimprinting. That is, it may be used for a thermal nanoimprint method or an optical nanoimprint method.

  When it is for thermal nanoimprinting, the resin mold may be formed by thermal nanoimprinting, or a fine shape on the surface may be formed by thermal nanoimprinting, but may be formed by thermal nanoimprinting. It is preferable that If it is formed by optical nanoimprinting, the heat resistance of the resin mold is not sufficient, and the resin mold may be deformed by heat when transferred to a transfer target. Moreover, when it is for optical nanoimprinting, the resin mold may be one in which the fine shape on the surface is formed by thermal nanoimprinting, or may be formed by optical nanoimprinting. It is preferable that it is formed. When formed by optical nanoimprinting, in addition to the short manufacturing time of the resin mold, the transfer time for the transfer object may be short, so that there is an advantage that the molded body can be manufactured in a short time.

  Moreover, it is preferable that the resin mold | type of this invention is an object for optical nanoimprints. That is, when a photocurable resin is included as the resin component (b) of the material constituting the transfer object, the fine shape of the resin mold is transferred to the transfer object by the optical nanoimprint method. The resin mold is preferably used for the optical nanoimprint method as described above. Thus, when used as a resin mold for optical nanoimprinting, the optical nanoimprinting method has the advantage that the desired molded article can be produced in a shorter time than the thermal nanoimprinting method.

[4] Molded body:
The molded body of the present invention is obtained by transferring a fine shape formed on the surface of the resin mold of the present invention. That is, it consists of a transfer object onto which a fine shape formed on the surface of the resin mold of the present invention is transferred. Such a molded body is formed using a “resin mold that can be easily released from a transfer target and has a fine surface shape with excellent accuracy even when the surface is hydrophilized”. Therefore, it has a good fine pattern.

  Specifically, as the molded body, the above-described optical disk molded body, optical fiber, camera lens, overhead projector lens, LBP Fθ lens, prism, liquid crystal display element (LCD), light diffusion plate, light guide plate, polarization Optical molded products such as films, retardation films, brightness enhancement films, and light-collecting films; various clean containers such as liquid chemical containers, ampoules, infusion bags, eye drops containers, semiconductor wafer storage containers; syringes, medical infusion tubes Medical device materials such as: resist masks for substrate processing such as silicon and sapphire.

[5] Manufacturing method of molded article:
The method for producing a molded body of the present invention uses a resin mold made of a material containing the resin component (a) and having a fine shape for pattern formation formed on the surface, and the resin mold (b) ) Is transferred to a transfer target made of a material containing a resin mold, and a molded body manufacturing method for obtaining a molded body having a reversal shape of the resin mold formed on the surface thereof. ) Is applied on a smooth surface of a substrate having a smooth surface and dried, or the resin layer (A) having a smooth surface is formed by irradiating light, and then the formed resin layer (A ), 3 μL of water is placed on the smooth surface, and the static contact angle (X1) measured according to JIS R 3257 is a method using a resin mold that satisfies the following condition (1).
Condition (1): The resin component (b) of the material constituting the transfer object is applied on a smooth surface of a substrate having a smooth surface and dried or irradiated with light to obtain a smooth surface. After forming the resin layer (B) having 3 μL of water on the smooth surface of the formed resin layer (B), the static contact angle (Y1) measured according to JIS R 3257 and The absolute value of the difference from the static contact angle (X1) is 20 ° to 60 °.

  According to such a manufacturing method, a molded article can be formed using a “resin mold that can be easily released from a transfer target and has a fine surface shape with good accuracy even when the surface is hydrophilized”. Since it is formed, a molded body having a good fine pattern can be produced.

  As a material containing the resin component (a) which comprises a resin type | mold, the material similar to the material containing the resin component (a) mentioned above can be used. Examples of the resin component (b) constituting the transfer target include thermoplastic resins and photo-curable resins. Specific examples of the thermoplastic resin include a cyclic olefin resin, a polyolefin resin, an acrylic resin, a polyvinyl ether resin, and a polystyrene resin. Specific examples of the photocurable resin include linear vinyl ether compounds, alicyclic vinyl ether compounds, epoxy compounds, oxetane compounds, acrylic compounds, and the like.

  The transfer target varies depending on the application, for example, a film or plate having a thickness of 40 μm to 3 mm, or a thin film having a thickness of nano to micron formed on a substrate. Can be mentioned. When it consists only of a resin component, it is often in the form of a film or plate. Moreover, in the case of a thin film, it can obtain by apply | coating and drying the material containing the resin component which comprises the said transcription | transfer object on flat base materials, such as PET film and a silicon wafer. In addition, when transferring the fine shape of the resin mold by the thermal nanoimprint method, it is preferable to heat the transfer target to make it flexible. Conventionally known conditions can be appropriately employed as the transfer conditions.

The method for producing a molded body of the present invention is obtained by hydrophilizing the surface on which a fine shape is formed as a resin mold, and after forming the resin layer (A), the formed resin layer (A) When the smooth surface is hydrophilized, 3 μL of water is placed on the hydrophilized smooth surface, and the static contact angle (X2) measured according to JIS R 3257 satisfies the following condition (2): It is preferable to use a filling resin mold.
Condition (2): The difference ((Y1) − (X2)) between the static contact angle (Y1) and the static contact angle (X2) is 20 ° to 60 °.

  Examples of the hydrophilization treatment include the UV ozone treatment, corona discharge treatment, plasma discharge treatment, and metallic sodium treatment already described above.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to these Examples and a comparative example.

  Tables 1 and 2 show a resin (resin component (a)) used as a resin-type material and a resin (resin component (b)) used as a material to be transferred. In Table 1, “ethylene-methylphenylnorbornene copolymer” is an ethylene / methylphenylnorbornene copolymer described in JP-A-2005-239975 (hereinafter referred to as “Et-MePhNB”). There). In Table 2, “TCDVE / 1-AdVE = 70/30” means that tricyclodecane vinyl ether (TCDVE) / 1-adamantyl vinyl ether (1-AdVE) is mixed at a mass ratio of 70:30 to obtain a mixture. 5.0 parts by weight of a polymerization initiator (trade name “WPI113” manufactured by Wako Pure Chemical Industries, Ltd.) and 1.0 part by weight of a leveling agent (trade name manufactured by Enomoto Kasei Co., Ltd.) with respect to 100 parts by weight of the resulting mixture. “Dispalon 1761”), 1.5 parts by mass of a sensitizer (trade name “UVS-1221” manufactured by Kawasaki Kasei Co., Ltd.), and 1.0 part by mass of a viscosity modifier (ethylene / methylphenylnorbornene copolymer, (Described in JP-A-2005-239975). “PAK equivalent” means 53.2% by mass of tripropylene glycol diacrylate, 9.9% by mass of trimethylolpropane triacrylate, 27.0% by mass of N-vinyl-2-pyrrolidone as a curable monomer, As an initiator, 9.0% by mass of a trade name “IRGACURE651” manufactured by Ciba Japan Co., Ltd. and 0.9% by mass of a trade name “Disparon 1761” manufactured by Enomoto Kasei Co., Ltd. as a leveling agent are mixed.

  Next, methods for measuring various physical property values and methods for evaluating various properties are shown below.

[Static contact angle]:
The static contact angle was measured by the following method in accordance with “Static Drop Method” in JIS R 3257 “Test Method for Wetting of Substrate Glass Surface”. The static contact angle was measured using “AUTO SLIDING ANGLE SA-30DM” manufactured by Kyowa Interface Science Co., Ltd. First, a method for measuring the static contact angle of a thermoplastic resin will be described.

  First, the following resin layer having a smooth surface was prepared. Then, the angle θ (see FIG. 1) between the resin layer surface and the tangent to the water droplet surface when 3 μL of water was disposed on the surface (smooth surface) of the resin layer was measured. For the thermoplastic resins (1) and (2), trade names “ZF-16” and trade names “ZF-14” manufactured by Optis (both are sheets of length 100 mm × width 100 mm × thickness 0.1 mm) are used as they are. Used as a resin layer. After the thermoplastic resins (3) and (4) are dissolved in a solvent (decalin), the resin dissolved in the solvent is smoothly applied onto a substrate (glass plate) by a bar coater, and then, in a vacuum oven By drying, a resin layer having a smooth surface (having a smooth surface) was obtained. As the thermoplastic resin (5), a trade name “HC-31” (sheet of 100 mm length × 100 mm width × 0.1 mm thickness) manufactured by Shikoku Kako Co., Ltd. was used as it was as a resin layer. The thermoplastic resin (6) was thermoformed into a sheet having a length of 100 mm, a width of 100 mm and a thickness of 1 mm to obtain a resin having a smooth surface (having a smooth surface). After the thermoplastic resin (7) is dissolved in a solvent (diethylbenzene), the resin dissolved in the solvent is smoothly applied onto a substrate (glass plate) by a bar coater, and then dried in a vacuum oven. A resin layer having a smooth surface (having a smooth surface) was obtained.

  Next, a method for measuring the static contact angle of the photocurable resin will be described. First, a photocurable resin is applied onto a smooth surface of a substrate by a bar coater to form a coating film, and the coating film is irradiated with light to cure the coating film so that the surface has a smooth surface. A resin layer was obtained. Then, the angle θ (see FIG. 1) between the resin layer surface and the tangent to the water droplet surface when 3 μL of water was placed on the surface (smooth surface) of the obtained resin layer was measured. The measurement results are simply indicated as “contact angle (°)” in Tables 1 to 3, and indicated as “contact angle X (°)” or “contact angle Y (°)” in Tables 5 and 6.

[Static contact angle after hydrophilization]:
The static contact angle after hydrophilization treatment is the same as the evaluation method of [Static contact angle] above, after forming a resin layer, the surface (smooth surface) of this resin layer is hydrophilized to make it hydrophilic. Droplets were placed on the surface of the treated resin layer, and the angle θ was measured (measured). Table 3 shows the static contact angle (°) of the resins used in the examples and comparative examples after UV ozone treatment or plasma treatment. The static contact angle was reduced by the hydrophilization treatment.

  As the hydrophilization treatment, UV ozone treatment and plasma treatment were performed. The UV ozone treatment was performed using a UV ozone cleaning device “OC-2506 (with ozone decomposing device OCA-150L-D)” manufactured by Eye Graphics Co., Ltd., under the conditions of a low-pressure mercury lamp and an irradiation distance of 10 mm. The exhaust time in the UV ozone cleaning apparatus was 2 minutes. When UV ozone treatment is performed, Table 3 shows treatment time (seconds).

As the plasma treatment, two types of plasma treatments, a first plasma treatment and a second plasma treatment, were performed. As the first plasma treatment, a plasma etching apparatus “EXAM” manufactured by Shinko Seiki Co., Ltd. was used, and the conditions were oxygen gas (pressure 15 Pa), power 20 W, and treatment time 1 minute. As the second plasma treatment, reverse sputtering was performed using a sputtering apparatus “CFS-4ES” manufactured by Shibaura Mechatronics Co., Ltd. under the conditions of nitrogen gas (pressure 0.5 Pa), power 50 W, and treatment time 1 minute. When the plasma treatment is performed, in Table 3, “O ₂ , under 15 Pa, 20 W, 1 minute RIE” or “N ₂ , under 15 Pa, 50 W, 1 minute reverse sputtering” is shown.

  Hereinafter, a method for measuring the angle θ will be specifically described. First, the resin layer was placed on a sample table of “AUTO SLIDING ANGLE SA-30DM” with its smooth surface facing upward. This sample stage is movable vertically and horizontally. Thereafter, distilled water was sucked into the syringe barrel, and this syringe barrel was fixed to the “AUTO SLIDING ANGLE SA-30DM”. Then, 3 μL of droplet-shaped distilled water (droplet) is formed at the tip of the syringe barrel, and the sample stage is slowly moved so that the droplet does not fall from the tip of the syringe barrel. Were slowly brought into contact with the surface (smooth surface) of the resin layer to place the droplets on the smooth surface of the resin layer (see FIG. 1). Thereafter, an image of the droplet placed on the surface of the resin layer is read by an optical reader attached to the “AUTO SLIDING ANGLE SA-30DM”, and the surface of the resin layer 11 and water droplets ( The tangent angle θ of the surface of the (droplet) 13 was measured. The angle θ was measured by “FACE measurement / analysis integrated system FAMAS version 2.1.0” attached to “AUTO SLIDING ANGLE SA-30DM”. The reason why the droplets are arranged on the smooth surface is to eliminate the influence of the water repellent effect due to the fine shape. That is, it is possible to measure the “angle θ” in a state where the droplets are arranged on the fine shape portion (on the surface on which the fine shape is formed) of the resin layer after the fine shape is formed. The water-repellent effect may be different depending on the shape. Therefore, in order not to cause a difference in water repellency effect due to a difference in fine shape, droplets were placed on a smooth surface and the “angle θ” was measured.

  As described above, the static contact angles of the resin used as the resin mold material and the resin used as the material to be transferred were respectively measured, and the “difference in static contact angle” was calculated from the measured static contact angles. . Specifically, the “difference in static contact angle” is calculated from the formula: (static contact angle of the resin used as the material to be transferred) − (static contact angle of the resin used as the resin mold material). did. In Tables 5 and 6, the difference is indicated by “difference in static contact angle (Z = Y−X)”.

[Glass transition temperature (Tg) or softening temperature (Tm)]:
The glass transition temperature (Tg) was determined from an endothermic peak when the temperature was raised from room temperature to 200 ° C. using a differential scanning calorimeter (models “EXSTAR6000” and “DSC6200”) manufactured by Seiko Denshi Kogyo. The softening temperature (Tm) is a state in which the tip of the quartz probe is pressed against the resin with a constant load using a thermal mechanical analyzer with a stress strain measurement function (models “EXSTAR6000” and “TMA / SS6000”) manufactured by Seiko Denshi Kogyo. In the heating furnace of the model “TMA / SS6000”, the temperature of the quartz probe and the resin was increased, and the behavior of the resin softening and the quartz probe tip was observed was obtained. In the case of a thermoplastic resin, the glass transition temperature (Tg) or softening temperature (Tm) was measured. In the case of a photocurable resin, the glass transition temperature (Tg) in the resin after curing was measured.

[Releasability]:
As in the examples and comparative examples, a resin mold having a fine shape formed on the surface and a transfer object were prepared. Next, the transfer object and the surface (finely shaped surface) of the resin mold were brought into contact with each other, and then the resin mold was pressed against the transfer object, and then the resin mold was separated from the transfer object. Imprinting was performed in this way. The peelability when the resin mold was separated from the transfer object was evaluated. The evaluation standard is “B” when the resin mold cannot be removed from the transfer target or when the fine shape of the transfer target is damaged even if it is peeled off, and the resin mold can be released from the transfer target. In addition, the case where no damage was observed in the fine shape of the transfer object was determined as good “G”. Table 4 shows the imprint conditions for each resin used in the examples and comparative examples. When the resin to be transferred is a photo-curing resin (see Tables 5 and 6), the resin mold is pressed against the transfer object in the state of the coating before photocuring, and then the above-mentioned coating is applied. The resin was cured by irradiation with light under the conditions shown in Table 4, and then the resin mold was separated from the transfer target. In addition, when the resin to be transferred is a thermoplastic resin (see Tables 5 and 6), the transfer target that is a film after the coating film is vacuum dried is heated under the conditions shown in Table 4. The resin mold was pressed away from the object to be transferred by pressing the resin mold through the steps of pressurization, pressure holding, and cooling. In Table 5, when UV ozone treatment is performed, the treatment time (seconds) is shown. When the plasma treatment is performed, “O ₂ , 15 Pa, 20 W, 1 minute” or “N ₂ , 15 Pa, 50 W, 1 minute, reverse sputtering” is indicated.

[Fine shape accuracy]:
The accuracy of the resin mold fine shape was evaluated by measuring the height (depth) of the resin mold fine shape before and after the hydrophilization treatment by using a field emission scanning electron microscope (FE-SEM) (model “ JSM-6700F ”) was used to obtain an image with an observation magnification of 100,000 times, and the height (depth) of the fine shape in the obtained image was measured. Specifically, the ratio (%) of the “difference between the height of the fine shape before the hydrophilic treatment and the height of the fine shape after the hydrophilic treatment” to the height of the fine shape before the hydrophilic treatment exceeds 20%. The case of “B” was judged as “B”, and the case of 20% or less was judged as “G”. Hereinafter, this ratio may be referred to as “fine shape change rate”. In Tables 5 and 6, “−” is shown when the hydrophilic treatment is not performed. This evaluation is shown as “resin mold fine shape accuracy” in Tables 5 and 6.

  FIG. 3 is a SEM photograph of the surface of the resin mold after UV ozone treatment obtained in Example 5. The height (depth) of the fine shape is indicated by “D”.

Example 1
Cyclic olefin resin (cycloolefin polymer (COP)) by a thermal nanoimprint method using a silicon mold in which a hole-shaped pattern having a diameter of 220 nm (accuracy ± 10%) and a depth of 200 nm (accuracy ± 5%) is formed. The above pattern was transferred to a film “ZF-16” manufactured by Optitis. Specifically, first, a silicon mold 1 was prepared as shown in FIG. 2A. Next, as shown in FIG. 2B, the silicon mold 1 was arranged on the resin film 3 so that the surface on which the hole-shaped pattern was formed was in contact with the resin film 3. Then, it set to the press stage of thermal nanoimprint apparatus "VX-2000" made from SCIVAX. Thereafter, on the resin film (thermoplastic resin (1) (ZF-16)) under the conditions of a press plate temperature of 195 ° C., a press stage temperature of 195 ° C., a pressure of 1.5 MPa, a pressure holding time of 60 seconds, and a cooling temperature of 100 ° C. Imprinting was performed (the mold was pressed against the resin film). Thereafter, the pressure was released, the sheet was taken out from the press stage (see FIG. 2C), and the resin film 3 (resin mold 5) was released from the mold 1. Thus, a film (resin mold 5 having a hole-shaped pattern with a diameter of 215 nm and a depth of 204 nm) on which the hole-shaped pattern of the mold was transferred was obtained (see FIG. 2D). Thereafter, a release agent “OPTOOL DSX” manufactured by Daikin Co., Ltd. was dropped onto the finely shaped surface (surface) of the obtained resin mold and applied to the entire surface. Then, it was air-dried and baked for 10 minutes on a 100 degreeC hotplate. After baking, the excess mold release agent was washed (washed off) with a fluorine-based solvent “DEMNUM Solvent (Daikin)” to obtain a resin mold. On the other hand, as a transfer object, a sheet (thermoplastic resin (6)) made of polymethyl methacrylate resin (PMMA) having a length of 100 mm, a width of 100 mm, and a thickness of 1 mm was used. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Example 2)
A resin mold was obtained in the same manner as in Example 1 except that the hydrophilic treatment was performed. The hydrophilic treatment was UV ozone treatment. Specifically, UV ozone treatment is performed by using a UV ozone cleaning device “OC-2506 (with ozone decomposing device OCA-150L-D)” manufactured by Eye Graphics Co., Ltd., using a low-pressure mercury lamp in the presence of ozone. The resin mold was irradiated with UV under the conditions of a distance of 10 mm and a UV ozone treatment time of 60 seconds. The exhaust time in the UV ozone cleaning apparatus was 2 minutes. After the hydrophilization treatment, a mold release agent “OPTOOL DSX” manufactured by Daikin Co., Ltd. was dropped onto the finely shaped surface (UV irradiated surface) which is the surface of the resin mold and applied to the entire surface. Then, it was air-dried and baked for 10 minutes on a 100 degreeC hotplate. After baking, the excess mold release agent was washed (washed off) with a fluorine-based solvent “DEMNUM Solvent (Daikin)” to obtain a resin mold.

  On the other hand, a sheet obtained as follows was prepared as a transfer target. First, on a polyethylene terephthalate (PET) film having a length of 100 mm × width of 100 mm × thickness of 0.1 mm, a solution obtained by dissolving the resin (Et-MePhNB) shown in Table 5 in decalin is applied by a bar coater to form a coating film. Formed. Thereafter, the formed coating film was vacuum-dried to prepare a sheet having a resin (Et-MePhNB) film formed on the surface of the PET. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Examples 3 and 5)
Each resin mold and each sheet as a transfer object were obtained in the same manner as in Example 2 except that the resin shown in Table 5 was used and the UV ozone treatment was performed for the treatment time shown in Table 5. And the said evaluation was performed using these (resin type | mold, sheet | seat).

Example 4
The resin shown in Table 5 was used, the UV ozone treatment was performed for the treatment time shown in Table 5, and the product name “HC-31” (length 100 mm × width 100 mm × thickness) manufactured by Shikoku Kako Co., Ltd. as a transfer target. A resin mold and a sheet as a transfer target were obtained in the same manner as in Example 2 except that a 0.1 mm sheet) was used. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Example 6)
Using a quartz mold with a hole-shaped pattern with a diameter of 220 nm (accuracy ± 10%) and depth 200 nm (accuracy ± 5%), the hole-shaped pattern is transferred to a photo-curing resin by UV nanoimprinting. Got the mold.

Specifically, first, a photocurable resin (TCDVE / 1-AdVE = 70/30) was applied on a PET film with a bar coater to form a coating film. On the coating film, the mold was placed so that the surface on which the hole-shaped pattern of the quartz mold was formed was in contact with the coating film, and then a hot press “AH-1T” (manufactured by ASONE) Set on the press stage. Next, imprinting was performed on the photocurable resin (1) (UNP-β) under the conditions of the press plate temperature normal temperature, the press stage temperature normal temperature, the pressure 1.0 MPa, and the pressure holding time 10 seconds (see Table 4). (The mold was pressed against the coating film). Thereafter, the pressure was released, and these were taken out of the press stage. Then, the above-mentioned coating film was irradiated with UV under the conditions of a UV irradiation amount of 20 mW / cm ² and a UV irradiation time of 38 seconds using an LED light source (“EXECURE-H-1VC” manufactured by HOYA, wavelength 365 nm). The coating film was cured to obtain a cured resin film. Then, the cured resin film and the PET film were released from the mold. In this manner, a pre-hydrophilic resin mold (resin mold on which a hole-shaped pattern having a diameter of 210 nm and a depth of 201 nm was formed) having a fine hole-shaped pattern transferred (formed) on the surface was obtained.

  Next, UV ozone treatment (hydrophilization treatment) was performed on the obtained resin mold before hydrophilization treatment. The UV ozone treatment uses a UV ozone cleaning device “OC-2506 (with ozone decomposing device OCA-150L-D)” manufactured by Eye Graphics Co., Ltd., using a low-pressure mercury lamp, under the condition of an irradiation distance of 10 mm in the presence of ozone. The resin mold before hydrophilization treatment was irradiated with UV. The exhaust time in the UV ozone cleaning apparatus was 2 minutes. After the hydrophilization treatment, a release agent “OPTOOL DSX” manufactured by Daikin Co., Ltd. was dropped onto the finely shaped surface (UV-irradiated surface) which is the surface of the resin mold, and applied to the entire surface. Then, it was air-dried and baked for 10 minutes on a 100 degreeC hotplate. After baking, the excess mold release agent was washed (washed off) with a fluorine-based solvent “DEMNUM Solvent (Daikin)” to obtain a resin mold.

  On the other hand, a sheet obtained as follows was prepared as a transfer target. First, on a PET film having a length of 100 mm, a width of 100 mm, and a thickness of 0.1 mm, a solution obtained by dissolving the thermoplastic resin (4) (Topas 8007) in decalin was applied by a bar coater to form a coating film. Thereafter, the formed coating film was vacuum-dried to prepare a sheet having a resin (Topas 8007) film formed on the surface of the PET. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Examples 7, 8, and 11)
Photoresin is used on a PET film having a length of 100 mm, a width of 100 mm, and a thickness of 0.1 mm as a transfer object, using the resin shown in Table 5 and performing the UV ozone treatment for the treatment time shown in Table 5. Each resin mold and transfer object was the same as in Example 2 except that a sheet (sheet before photocuring the above-mentioned coating film) in which (1) was applied by a bar coater to form a coating film was used. Each sheet was obtained. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Examples 9 and 10)
Using the resin shown in Table 5 and, as a transfer target, a photocoating resin shown in Table 5 was coated on a PET film having a length of 100 mm × width of 100 mm × thickness of 0.1 mm by a bar coater. A resin mold was obtained in the same manner as in Example 1 except that the formed sheet (sheet before photocuring the coating film) was used. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Examples 12 and 13)
A resin mold was obtained in the same manner as in Example 6 except that the resin shown in Table 5 was used. Further, a sheet as a transfer target was obtained in the same manner as in Example 7. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Examples 14 and 15)
A resin mold was obtained in the same manner as in Example 2 except that plasma treatment (hydrophilization treatment) was performed. The plasma treatment was performed by using a plasma etching apparatus “EXAM” manufactured by Shinko Seiki Co., Ltd. and performing RIE treatment under the conditions of oxygen gas (pressure 15 Pa), power 20 W, and treatment time 1 minute. This condition is shown in Table 5 as “O ₂ , under 15 Pa, 20 W, 1 minute”.

  On the other hand, for the transfer object, in Example 14, a sheet as the transfer object was obtained in the same manner as in Example 5. In Example 15, a sheet as a transfer target was obtained in the same manner as Example 7. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Examples 16 and 17)
Except for using a sputtering apparatus “CFS-4ES” manufactured by Shibaura Mechatronics Co., Ltd., except that plasma treatment was performed by reverse sputtering under conditions of nitrogen gas (pressure 0.5 Pa), power 50 W, and treatment time 1 minute. In the same manner as in No. 2, a resin mold was obtained. This condition is shown as “N ₂ , 0.5 Pa, 50 W, 1 minute reverse sputtering” in Table 5.

  On the other hand, for the transfer object, in Example 16, a sheet as the transfer object was obtained in the same manner as in Example 5. In Example 17, a sheet as a transfer target was obtained in the same manner as Example 7. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Comparative Examples 1, 6, 7, 10, 11, 15, 16)
A resin mold was obtained in the same manner as in Example 1 except that the resins shown in Table 6 were used. On the other hand, regarding the transfer target, in Comparative Example 1, a sheet as a transfer target was obtained in the same manner as in Example 2. In Comparative Example 6, a sheet as a transfer target was obtained in the same manner as in Example 4. In Comparative Example 7, a sheet as a transfer target was obtained in the same manner as in Example 6. In Comparative Examples 10, 11, 15, and 16, sheets as transfer targets were obtained in the same manner as in Example 7. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Comparative Examples 2-5, 12, 13)
A resin mold was obtained in the same manner as in Example 2 except that the UV ozone treatment time was changed to the time shown in Table 6 and the resin shown in Table 6 was used. On the other hand, regarding the transfer target, in Comparative Examples 2 to 5, a sheet as the transfer target was obtained in the same manner as in Example 2. In Comparative Examples 12 and 13, sheets as transfer targets were obtained in the same manner as in Example 7 except that the resins shown in Table 6 were used. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Comparative Example 8)
Using a quartz mold with a hole-shaped pattern with a diameter of 220 nm (accuracy ± 10%) and depth 200 nm (accuracy ± 5%), the hole-shaped pattern is transferred to a photo-curing resin by UV nanoimprinting. Got the mold.

  Specifically, first, a photocurable resin (TCDVE / 1-AdVE = 70/30) was applied on a PET film with a bar coater to form a coating film. On the coating film, the mold is placed so that the surface on which the hole pattern of the quartz mold is formed is in contact with the coating film, and then set on the press stage of the hot press “AH-1T”. did.

Next, imprinting was performed on the photocurable resin (1) (UNP-β) under the conditions of the press plate temperature normal temperature, the press stage temperature normal temperature, the pressure 1.0 MPa, and the pressure holding time 10 seconds (see Table 4). (The mold was pressed against the coating film). Thereafter, the pressure was released, and these were taken out of the press stage. Then, the above-mentioned coating film was irradiated with UV under the conditions of a UV irradiation amount of 20 mW / cm ² and a UV irradiation time of 38 seconds using an LED light source (“EXECURE-H-1VC” manufactured by HOYA, wavelength 365 nm). The coating film was cured to obtain a cured resin film. Then, the cured resin film and the PET film were released from the mold. Thus, a resin mold (a resin mold on which a hole-shaped pattern having a diameter of 206 nm and a depth of 197 nm was formed) onto which a hole-shaped pattern was transferred was obtained. A release agent “OPTOOL DSX” manufactured by Daikin Co., Ltd. was dropped onto the finely shaped surface, which is the surface of the obtained resin mold, and applied to the entire surface. Then, it was air-dried and baked for 10 minutes on a 100 degreeC hotplate. After baking, the excess mold release agent was washed (washed off) with a fluorine-based solvent “DEMNUM Solvent (Daikin)” to obtain a resin mold. On the other hand, as a transfer target, a sheet as a transfer target was obtained in the same manner as in Example 6. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Comparative Example 9)
A resin mold was obtained in the same manner as in Comparative Example 8. On the other hand, as a transfer target, a sheet as a transfer target was obtained in the same manner as in Example 7. And the said evaluation was performed using these (resin type | mold, sheet | seat).

(Comparative Example 14)
A resin mold was obtained in the same manner as in Comparative Example 8 except that the resins shown in Table 6 were used. On the other hand, as a transfer target, a sheet as a transfer target was obtained in the same manner as in Example 7. And the said evaluation was performed using these (resin type | mold, sheet | seat).

  As is clear from Tables 5 and 6, the resin molds of Examples 1 to 17 can be easily released from the transfer target as compared with the resin molds of Comparative Examples 1 to 16 (the mold release property is good). It was confirmed that the precision of the fine shape of the surface was good even when the surface was hydrophilized.

  In the case of the resin molds of Comparative Examples 4 and 5, the releasability was good, but the precision of the fine shape of the resin mold was poor. Specifically, in Comparative Example 4, the fine shape change rate was 21%, and in Comparative Example 5, the fine shape change rate was 64%.

  The resin mold of the present invention can be suitably used as a resin mold for nanoimprinting. The shaping | molding die of this invention can be used suitably as optical shaping | molding articles, such as a condensing film. The manufacturing method of the shaping | molding die of this invention can manufacture the shaping | molding die which can be used as optical shaping | molding articles, such as a condensing film.

1: Mold, 3: Resin film, 5: Resin mold, 11: Resin layer, 13: Water droplets, 15, 17: Concave and convex pattern.

Claims (16)

A resin for nanoimprint, which is made of a material containing a resin component (a), has a fine shape for pattern formation formed on the surface, and transfers the fine shape to a transfer object made of a material containing a resin component (b) Resin layer (A) having a smooth surface by applying the resin component (a) on the smooth surface of a substrate having a smooth surface and drying or irradiating light. After forming 3 μL of water on the smooth surface of the formed resin layer (A), the static contact angle (X1) measured in accordance with JIS R 3257 is the following condition (1 Resin mold that satisfies).
Condition (1): Applying the resin component (b) of the material constituting the transfer object onto the smooth surface of a substrate having a smooth surface and drying or irradiating light. After forming a resin layer (B) having a smooth surface with 3 μL of water on the smooth surface of the formed resin layer (B), static contact measured according to JIS R 3257 The absolute value of the difference between the angle (Y1) and the static contact angle (X1) is 20 ° to 60 °.   The resin mold according to claim 1, wherein the surface on which the fine shape is formed is obtained by hydrophilization treatment. After the resin layer (A) is formed, the smooth surface of the formed resin layer (A) is hydrophilized, and 3 μL of water is disposed on the hydrophilized smooth surface to JIS R 3257. The resin mold according to claim 2, wherein the static contact angle (X2) measured in accordance with the condition satisfies the following condition (2).
Condition (2): The difference ((Y1) − (X2)) between the static contact angle (Y1) and the static contact angle (X2) is 20 ° to 60 °.   The resin mold according to claim 2, wherein UV ozone treatment is performed as the hydrophilic treatment.   The resin mold according to claim 2 or 3, wherein a corona discharge treatment is performed as the hydrophilic treatment.   The resin mold according to claim 2 or 3, wherein a plasma discharge treatment is performed as the hydrophilization treatment.   The resin mold according to claim 1, wherein the surface is obtained by a release agent treatment. The resin component (a) contains a thermoplastic resin,
The resin mold according to any one of claims 1 to 7, wherein a fine shape on the surface is formed by thermal nanoimprint.   The resin mold according to claim 8, wherein the thermoplastic resin is at least one selected from the group consisting of a cyclic olefin resin, a polyolefin resin, an acrylic resin, a polycarbonate resin, a polyvinyl ether resin, and a polystyrene resin. The resin component (a) contains a photocurable resin,
The resin mold according to any one of claims 1 to 7, wherein a fine shape on the surface is formed by optical nanoimprint.   The photo-curable resin includes a structural unit derived from at least one curable compound selected from the group consisting of a linear vinyl ether compound, an alicyclic vinyl ether compound, an epoxy compound, an oxetane compound, and an acrylic compound. The resin mold according to claim 10.   The resin mold according to any one of claims 1 to 11, which is for thermal nanoimprinting.   The resin mold according to any one of claims 1 to 11, which is for optical nanoimprint.   The molded object obtained by transferring the fine shape formed on the surface of the resin mold as described in any one of Claims 1-13. Using a resin mold made of a material containing the resin component (a) and having a fine pattern forming pattern formed on the surface, the fine shape of the resin mold is made of a material containing the resin component (b) Is a method of manufacturing a molded body to obtain a molded body in which the inverted shape of the fine shape of the resin mold is formed on the surface thereof,
As the resin mold, the resin component (a) is applied on the smooth surface of a substrate having a smooth surface and dried or irradiated with light to form a resin layer (A) having a smooth surface. After forming 3 μL of water on the smooth surface of the formed resin layer (A), the static contact angle (X1) measured in accordance with JIS R 3257 is the following condition (1 The manufacturing method of the molded object using the resin type | mold which satisfy | fills.
Condition (1): Applying the resin component (b) of the material constituting the transfer object onto the smooth surface of a substrate having a smooth surface and drying or irradiating light. After forming a resin layer (B) having a smooth surface with 3 μL of water on the smooth surface of the formed resin layer (B), static contact measured according to JIS R 3257 The absolute value of the difference between the angle (Y1) and the static contact angle (X1) is 20 ° to 60 °. As the resin mold, the surface on which the fine shape is formed is obtained by hydrophilic treatment, and after the resin layer (A) is formed, the smooth surface of the formed resin layer (A) is made hydrophilic. A resin mold in which 3 μL of water is disposed on the smooth surface that has been subjected to a hydrophilization treatment and the static contact angle (X2) measured in accordance with JIS R 3257 satisfies the following condition (2): The manufacturing method of the molded object of Claim 15 used.
Condition (2): The difference ((Y1) − (X2)) between the static contact angle (Y1) and the static contact angle (X2) is 20 ° to 60 °.