Double-sided molding method and molded product

Abstract

The purpose of the present invention is to provide: a double-sided molding method using a protective film that, during processing, does not detach from a resin pattern to be protected, does not cause any defects, and does not generate any adhesive residues when the protective film is detached; and a molded product obtained thereby.　A double-sided molding method for forming a first resin pattern 110 on a first surface 11 of a substrate 1 and forming a second resin pattern 120 on a second surface 12 of the substrate 1 comprises: a protective film pasting step for pasting a silicone rubber layer side of a protective film 2 having the silicone rubber layer on the first resin pattern 110; and a second resin pattern molding step for forming a second resin pattern 120 on the second surface 12 after the protective film pasting step.

Description

Double-sided molding method and molded product

[0001] The present invention relates to a double-sided molding method for forming patterns on both sides of a molded object, and to a molded product.

[0002] Conventionally, nanoimprinting technology has been used as a method for forming micro- or nano-order fine patterns. This involves pressing a mold having a fine molding pattern onto a molding target such as a resin, and transferring the pattern to the molding target using heat or light. In recent years, there has been a demand for transferring fine patterns to both sides of a substrate in order to improve the performance of optical components such as optical lenses and waveguides for AR glasses. To this end, double-sided imprinting devices (see, for example, Patent Document 1) and double-sided imprinting methods (see, for example, Patent Document 2) have been developed in which a water-soluble protective film or the like is applied to protect the fine pattern, and the protective film is then removed after double-sided imprinting.

[0003] International Publication No. WO2014 / 034576 International Publication No. WO2019 / 159969

[0004] However, double-sided imprinting equipment is a special device and has the problem of high initial installation costs, while those that form a water-soluble protective film have the problem of taking time to apply and remove the protective film.

[0005] One possible solution is to apply a protective film coated with an adhesive to the fine pattern. However, while typical protective films are designed for semiconductor processes and are suitable for protecting non-resin semiconductor elements, they have a strong adhesion to resin fine patterns, which can lead to adhesive residue. In particular, the nanoimprint process uses pressure during molding, which means the adhesive of the protective film penetrates into the fine pattern, making it more likely to adhere than in typical semiconductor processes. Therefore, typical protective films cannot be applied directly. Furthermore, the protective film must not peel off from the target during processing and must not cause defects in the target's fine pattern.

[0006] Therefore, the present invention aims to provide a double-sided molding method and a molded product using a protective film that does not peel off from the resin pattern to be protected during the process, does not cause defects, and does not leave any adhesive residue when the protective film is peeled off.

[0007] Here, the term "micropattern" as used herein refers to a pattern of a size that can be molded by an imprinting process, particularly a pattern of a size that can be molded by a nanoimprinting process. Specifically, the micropattern is a pattern having a region in which the depth of the concave structure or the height of the convex structure of the molded concave-convex structure is on the order of 1 nm (1 nm to 9 nm) to 100 μm (100 μm to 999 μm). In the case of a nanoimprinting process, the concave-convex structure may have a region in which the depth of the concave structure or the height of the convex structure is on the order of 1 nm (1 nm to 9 nm) to 100 nm (100 nm to 999 nm). The bottom width of the concave structure or the top width of the convex structure of the molded concave-convex structure may also be the above-mentioned size. Note that the combination of the depth of the concave structure (or the height of the convex structure) and the bottom width of the concave structure (or the top width of the convex structure) may be such that one is on the order of 1 nm to 100 μm and the other is on the order of 1 nm to 100 nm, or vice versa. The bottom width of the concave structure or the top width of the convex structure may be larger than the above sizes depending on the application, for example, on the order of 1 mm. The cross-sectional shape of the concave-convex structure depends on the mold, but examples include polygonal shapes such as rectangles, shapes with curves such as semicircles, and shapes combining curves and straight lines. These may also be shapes that have been subjected to various chamfering or tapering processes.

[0008] In order to achieve the above-mentioned object, the double-sided molding method of the present invention is a double-sided molding method for forming a first resin pattern on a first surface of a substrate and forming a second resin pattern on a second surface of the substrate, and is characterized by having a protective film attachment process in which the silicone rubber layer side of a protective film having a silicone rubber layer is attached to the first resin pattern, and a second resin pattern molding process in which a second resin pattern is formed on the second surface after the protective film attachment process.

[0009] In this case, it is preferable that the tensile strength of the silicone rubber layer is greater than the adhesive strength of the silicone rubber layer. The tensile strength of the silicone rubber layer can be 1.0 MPa or more. The adhesive strength of the silicone rubber layer can be 10 kPa or more and 1500 kPa or less.

[0010] The elastic modulus of the silicone rubber layer is preferably smaller than that of the first resin constituting the first resin pattern. The elastic modulus of the silicone rubber layer may be less than 200 MPa. The elastic modulus of the first resin may be 200 MPa or greater.

[0011] The thickness of the silicone rubber layer is preferably 1 μm or more and 1 mm or less.

[0012] It is also preferable to have a protective film peeling step of peeling off the protective film attached to the first surface after the second resin pattern molding step.

[0013] The silicone rubber layer may be formed by curing an addition-curable silicone pressure-sensitive adhesive composition that contains: (A) 100 parts by mass of an organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and having a viscosity of 0.01 to 1,000 Pa s at 25°C; (B) 5 to 500 parts by mass of an organopolysiloxane resin having alkenyl groups; (C) an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms per molecule, in an amount such that the number of silicon-bonded hydrogen atoms in component (C) is 0.1 to 5.0 times the molar ratio of all silicon-bonded alkenyl groups in the composition; and (D) a platinum group metal catalyst, but does not contain a non-crosslinkable organopolysiloxane resin.

[0014] The molded product of the present invention is characterized by comprising a substrate having a first surface and a second surface, a first resin pattern formed on the first surface, and a protective film having a silicone rubber layer attached onto the first resin pattern.

[0015] In this case, it is preferable that the tensile strength of the silicone rubber layer is greater than the adhesive strength of the silicone rubber layer. The tensile strength of the silicone rubber layer can be 1.0 MPa or more. The adhesive strength of the silicone rubber layer can be 10 kPa or more and 1500 kPa or less.

[0016] The elastic modulus of the silicone rubber layer is preferably smaller than that of the first resin constituting the first resin pattern. The elastic modulus of the silicone rubber layer may be less than 200 MPa. The elastic modulus of the first resin may be 200 MPa or greater.

[0017] The thickness of the silicone rubber layer is preferably 1 μm or more and 1 mm or less.

[0018] The device may also include a second resin pattern formed on the second surface.

[0019] The silicone rubber layer may be formed by curing an addition-curable silicone pressure-sensitive adhesive composition that contains: (A) 100 parts by mass of an organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and having a viscosity of 0.01 to 1,000 Pa s at 25°C; (B) 5 to 500 parts by mass of an organopolysiloxane resin having alkenyl groups; (C) an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms per molecule, in an amount such that the number of silicon-bonded hydrogen atoms in component (C) is 0.1 to 5.0 times the molar ratio of all silicon-bonded alkenyl groups in the composition; and (D) a platinum group metal catalyst, but does not contain a non-crosslinkable organopolysiloxane resin.

[0020] In the double-sided molding method of the present invention, damage to the pattern is prevented by using a protective film, so that the pattern can be transferred by imprinting to both sides of the molding target using a conventional imprinting device.

[0021] 1 is a cross-sectional view showing a double-sided molding method of the present invention.

[0022] The double-sided molding method of the present invention is a double-sided molding method for forming a first resin pattern 110 (sometimes referred to as a first pattern) on a first surface 11 of a substrate 1 and a second resin pattern 120 (sometimes referred to as a second pattern) on a second surface 12 of the substrate 1, and is mainly composed of a protective film attachment step and, after the protective film attachment step, a second resin pattern molding step for forming the second resin pattern 120 on the second surface 12. Here, the first surface 11 and the second surface 12 refer to substantially opposing main surfaces of the substrate, and are surfaces having a much larger area than the other surfaces.

[0023] The substrate 1 is used to form a first resin pattern 110 on a first surface 11 and a second resin pattern 120 on a second surface 12 of the substrate 1. The substrate 1 may have any shape as long as the first resin pattern 110 and the second resin pattern 120 can be formed on both surfaces by an imprinting method. For example, the substrate 1 may be shaped like a plate, a flexible film, or a lens. Therefore, the first surface 11 and the second surface 12 may be flat, curved, or a combination thereof. From these facts, it can be seen that the substrate can also be expressed as a base material having two main surfaces. If this substrate (base material) is not rigid but flexible, the attachment of a protective film can be expected to improve the handleability of the substrate (base material).

[0024] Furthermore, the material of the substrate 1 can be any material as long as it allows a first resin pattern 110 to be formed on the first surface 11 and a second resin pattern 120 to be formed on the second surface 12 of the substrate 1, and inorganic materials such as glass and silicone, metal materials such as aluminum, and resin materials such as silicone-based resins, epoxy-based resins, and acrylic-based resins can be used.

[0025] The first resin pattern 110 and the second resin pattern 120 have a fine uneven structure and are intended to impart a desired function to the surface of the substrate 1. The uneven structure may be any structure that can impart a desired function to the surface of the substrate 1, and examples of such structures include a structure for diffracting light such as an AR waveguide, a structure for suppressing reflection such as a moth eye, and a structure for polarizing light such as a wire grid. The first resin pattern 110 and the second resin pattern 120 may have different functions or structures.

[0026] The first resin 31 used for the first resin pattern 110 and the second resin 32 used for the second resin pattern 120 may be any material capable of forming the first resin pattern 110 or the second resin pattern 120, such as a photocurable resin capable of photoimprinting, or a thermoplastic or thermosetting resin capable of thermal imprinting. An intermediate layer may be formed between the substrate 1 and the first resin 31 or the second resin 32 to improve adhesion between the substrate 1 and the first resin 31 or the second resin 32. The substrate 1 itself may be made of a resin capable of forming the first resin pattern 110 or the second resin pattern 120. In this case, the substrate 1 may be made of, for example, a photocurable resin capable of photoimprinting, or a thermoplastic or thermosetting resin capable of thermal imprinting. The state of the resin in the first resin pattern 110 or the second resin pattern 120 is not particularly limited, and may be an uncured state, a B-stage state, or a C-stage state of the curable resin.

[0027] The first resin pattern 110 is formed on the first surface 11 of the substrate 1 in a first resin pattern molding process prior to the protective film attachment process. The first resin pattern 110 may be formed in any manner. For example, a substrate 1 as shown in FIG. 1( a) is prepared and a primer 4 is applied as shown in FIG. 1( b). The primer 4 is used to improve the wettability between the substrate 1 and the resin to be applied thereon. Resin is then applied to the first surface 11 of the substrate 1 as shown in FIG. 1( c), and the first resin pattern 110 may be formed on the first surface 11 of the substrate 1 using a well-known imprinting method such as photoimprinting or thermal imprinting as shown in FIGS. 1( d) and 1( e). Alternatively, a mask onto which a pattern is transferred by an imprinting method may be created on the substrate 1, and the first resin pattern 110 may be formed on the substrate 1 by etching using the mask. Alternatively, a resist pattern may be formed on the substrate 1 by an imprinting method or the like, and the first pattern may be formed by etching the substrate surface using the resist. After the first pattern is formed, the resist pattern may be removed, or it may remain as part of the first pattern. This means that the first resin pattern does not necessarily have to be formed by the imprint method.

[0028] 1(f), the protective film attachment step is a step of attaching the silicone rubber layer side of protective film 2 having a silicone rubber layer onto first resin pattern 110. It is sufficient that at least a part of the silicone rubber layer of protective film 2 is attached to the convex portions of first resin pattern 110. An existing film attachment device such as a laminating device can be used to attach protective film 2.

[0029] Here, the protective film 2 is attached to the first resin pattern 110 of the substrate 1 to protect the first resin pattern 110 from damage, etc. The protective film 2 has a film layer and a silicone rubber layer. The film layer and the silicone rubber layer preferably have a laminated structure, and an intermediate layer, such as an adhesion-imparting layer, may be provided between the film layer and the silicone rubber layer to improve their mutual adhesion. The protective film can also be obtained, for example, by forming a film layer by coating silicone rubber on the film layer. If the silicone rubber film can be formed independently, the protective film can also be obtained by laminating the silicone rubber layer and the film layer together. Here, if the silicone rubber layer can be handled independently, the film layer is not necessarily required. Such a silicone rubber layer can be obtained, for example, not only by forming the silicone rubber film independently, but also by peeling the film layer from the protective film.

[0030] Alternatively, a silicone rubber film may be formed directly on the first pattern including the first resin pattern. In such a case, it may be advantageous for subsequent peeling of the silicone rubber layer to form a film so that voids remain at the bottoms of the recesses, rather than forming a film so that the silicone rubber completely fills the recesses of the uneven structure.

[0031] The film layer may be any material as long as it is attached onto first resin pattern 110 and is not damaged after second resin pattern 120 is formed and before it is peeled off from first resin pattern 110. For example, the film layer may be made of a polymer film such as polyethylene terephthalate, polyolefin, polyvinyl chloride, or polyimide; a metal foil such as copper foil or aluminum foil; a nonwoven fabric; or a foam. The thickness of the film layer can be selected depending on the size and distribution of the pattern to be formed, the shape of the main surface of the substrate, and the handleability of the protective film, and may be, for example, 1 μm to 1 mm, or 30 to 500 μm.

[0032] The silicone rubber layer adheres to the surface of the substrate 1 on which the first resin pattern 110 is formed, protecting the first resin pattern 110 from scratches and other damage. In this case, if the tensile strength of the silicone rubber layer is smaller than the adhesive strength of the silicone rubber layer, adhesive residue may remain on the resin pattern when the protective film is peeled off. Therefore, the tensile strength of the silicone rubber layer should be greater than the adhesive strength of the silicone rubber layer. Furthermore, it is preferable that the silicone rubber layer has a tensile strength that is at least sufficient to prevent the silicone rubber layer from being damaged during the imprinting process. Therefore, the tensile strength of the silicone rubber layer is preferably 0.5 MPa or more, and more preferably 1.0 MPa or more. Although there are no particular limitations, the upper limit of the tensile strength may be approximately 20 MPa, considering factors such as availability.

[0033] <Method for Measuring the Tensile Strength of the Rubber Layer> A metal press plate was prepared with a PTFE sheet (manufactured by Nichias Corporation, product name TOMB No. 9001) placed on it, and a rectangular metal spacer (2 mm thick) was placed on top of the PTFE sheet. The silicone pressure-sensitive adhesive composition was then poured into the spacer, and a Teflon sheet and another metal press plate were placed on top of it, sandwiching the silicone pressure-sensitive adhesive composition between them. This was press-cured at 150°C for 10 minutes, heated in an oven at 150°C for 30 minutes, and then left to stand at room temperature for 14 hours to obtain a 2.0 mm thick sheet. These heating conditions can be adjusted as appropriate to match the degree of vulcanization required for use as a protective film, for example. The surfaces of the Teflon sheet, metal spacer, and metal press plate must be clean and smooth, with no irregularities that could affect the tensile strength of the sheet. If necessary, the Teflon sheet, metal spacer, and metal press plate can be polished. For details on the equipment and other conditions, JIS K 6299:2012 "Rubber - Preparation of Test Specimens" can be referenced as appropriate. The obtained sheet was punched using a punching tool specified in JIS K 6251:2017 "Vulcanized and Thermoplastic Rubber - Determination of Tensile Properties" to obtain dumbbell-shaped No. 2 test specimens. Using these test specimens, a tensile test was performed in accordance with JIS K 6251:2017 using a Shimadzu Autograph AGS-X at a tensile speed of 500 mm / min and a measurement temperature of 23°C (room temperature). For other measurement conditions, JIS K 6251:2017, JIS K 6249:2003 "Test Methods for Uncured and Cured Silicone Rubber" and JIS K 6250:2019 "Rubber - General Rules for Physical Testing Methods" can be referenced as appropriate.

[0034] In the present invention, the tensile strength is a value obtained by the above measurement. However, there are cases where only cured sheets having a thickness other than 2 mm are available. For example, this may be the case when the composition of the composition before curing is unknown and adjustment is not possible. In such cases, if the film layer of the protective film can be peeled off and peeling does not cause damage to the rubber layer that would affect the tensile strength, it is possible to estimate the tensile strength by measuring the rubber layer after peeling off the film layer. In this case, the measurement conditions other than the thickness are measured in the same manner as the measurement method described above, and the actual thickness is used in calculating the results, thereby estimating the tensile strength at a thickness of 2 mm. According to the inventor's findings, the tensile strength values ​​measured on a 1 mm thick sheet and those measured on a 200 μm thick sheet were equivalent.

[0035] Furthermore, the adhesive strength of the silicone rubber layer is preferably such that it can adhere to the first resin pattern 110 and does not peel off during the imprinting process. Therefore, the adhesive strength of the silicone rubber layer is preferably 10 kPa or more, and more preferably 20 kPa or more. Furthermore, it is desirable that the adhesive strength be such that the protective film can be easily peeled off without leaving any adhesive residue. Therefore, the adhesive strength of the silicone rubber layer is preferably, for example, 1500 kPa or less, and more preferably 1200 kPa or less.

[0036] <Method for Measuring the Adhesive Strength of a Rubber Layer (Silicone Rubber Layer)> A silicone pressure-sensitive adhesive composition is poured into an aluminum petri dish to a thickness of 1 mm. After leaving the surface to be approximately horizontal, the mixture is heated in an oven at 150°C for 30 minutes and then left to stand for 14 hours in an environment of 23°C and 50% RH (relative humidity) to obtain a rubber layer. These heating conditions can be adjusted as appropriate to match the degree of vulcanization required for use as a protective film, for example. Note that the surface texture of the rubber layer affects the adhesive strength, so it should be kept smooth without any residual air bubbles or significant unevenness or slopes. Furthermore, the surface (adhesive surface) of the rubber layer should be kept free of dust, and the adhesive surface should not be touched or have foreign matter adhered to it, including during measurement.

[0037] Next, under an environment of 23°C and 50% RH (relative humidity), double-sided adhesive tape (Nitto Denko Corporation, product name: General-purpose double-sided tape No. 501F) was applied to the back of an aluminum petri dish and firmly secured to the lower pressure plate, which serves as the sample stage of a Shimadzu Corporation EZ-SX compact benchtop testing machine. A 1 mm square SUS probe attached to the testing machine was pressed downward from above so as to be perpendicular to the surface (adhesive surface) of the rubber layer. This pressing was performed by bringing the probe into contact with the adhesive surface at a speed of 0.05 mm / sec, and then applying a contact load of 1 MPa for 15 seconds. The probe was then moved in the opposite direction to the pressing, from below to above so as to be perpendicular to the surface (adhesive surface) of the rubber layer at a speed of 200 mm / min, and the force required to peel the probe from the surface of the rubber layer was measured, and the maximum measured value was taken as the adhesive strength. Measurements were performed five times for each sample, and the average adhesive strength value from each measurement was taken as the adhesive strength in this invention.

[0038] In this measurement, the influence of the surface properties of the probe on the adhesive strength cannot be ignored, so it is preferable to use SUS304 as the material and limit the surface roughness to about 250 to 500 nm in root mean square roughness (Rq).

[0039] In the present invention, it is difficult to obtain accurate adhesive strength values ​​unless the sample is 1 mm or thick. Therefore, although the above measurement is performed using a sample with a thickness of 1 mm, there are cases where only cured sheets with a thickness of less than 1 mm are available. This may be the case when the composition of the composition before curing is unknown and adjustment is not possible. In such cases, if the film layer of the protective film can be peeled off and peeling does not cause damage to the rubber layer that would affect the adhesive strength, it is possible to estimate the adhesive strength by bonding multiple rubber layers from which the film layer has been peeled off and measuring a sheet with a thickness of at least 1 mm. In this case, the measurement surface of the rubber layer may become rough. The surface roughness of the measurement surface may affect the measured adhesive strength. Therefore, if the measurement surface is rough, it is preferable to smooth the measurement surface before measurement, for example by applying pressure through a Teflon sheet.

[0040] Furthermore, the elastic modulus of the silicone rubber layer is preferably flexible enough to protect the first resin pattern 110 of the substrate 1 from pressure, impact, and the like during processing. Therefore, the elastic modulus of the silicone rubber layer is preferably smaller than the elastic modulus of the first resin 31 constituting the first resin pattern 110. For example, the elastic modulus of the silicone rubber layer is preferably less than 200 MPa, more preferably less than 100 MPa. In this case, the elastic modulus of the first resin 31 is preferably 200 MPa or more, more preferably 500 MPa or more. While not particularly limited, the lower limit of the elastic modulus of the silicone rubber layer may be approximately 0.1 MPa or 3 MPa in terms of availability and ease of handling. Although not particularly limited, the upper limit of the elastic modulus of the first resin 31 may be approximately 50 GPa in terms of availability and ease of handling.

[0041] <Method for measuring the elastic modulus of the rubber layer (silicone rubber layer)> A metal press plate with a PTFE sheet (manufactured by Nichias Corporation, product name TOMB No. 9001) placed on it was prepared, and a metal rectangular frame-shaped spacer (2 mm thick) was placed on the PTFE sheet. Next, the silicone pressure-sensitive adhesive composition was poured into the spacer, and a Teflon sheet and another metal press plate were placed on top of it, sandwiching the silicone pressure-sensitive adhesive composition. This was press-cured under the conditions of 150 ° C x 10 minutes, further heated in an oven at 150 ° C for 30 minutes, and then left to stand at room temperature for 14 hours, after which a sheet with a thickness of 2.0 mm was obtained. The heating conditions can be appropriately adjusted, for example, to match the degree of vulcanization as much as possible when used as a protective film. The surfaces of the Teflon sheet, metal spacer, and metal press plate must be clean and smooth, with no irregularities that could affect the tensile strength of the sheet. If necessary, the Teflon sheet, metal spacer, and metal press plate may be polished. Regarding the equipment and other conditions, JIS K 6299:2012 "Rubber - Preparation of Test Specimens" may be referenced. The resulting sheet was cut into 5 mm x 30 mm samples. The elastic modulus of the resulting sample was then measured by dynamic mechanical analysis (DMA) in accordance with JIS K7244-4:1999 "Plastics - Test Methods for Dynamic Mechanical Properties - Part 4: Tensile Vibration - Non-Resonant Method." Specifically, both ends of the sample were attached to the chucks of a dynamic viscoelasticity measuring device (Rheogel-E4000 manufactured by UBM) so that the tensile direction was the longitudinal direction of the sample, and a tensile load was applied under the following measurement conditions to perform measurements using the tensile method. The measured value at 25°C in this measurement was taken as the modulus of elasticity. [Measuring conditions for modulus of elasticity] - Measurement sample: 5 mm x 30 mm rectangle - Chuck distance: 20 mm - Measurement mode: Tensile method (sinusoidal strain, tensile mode, strain amount: automatic strain) - Heating rate: 3°C / min - Temperature: -60°C or higher and 200°C or lower - Frequency: 10 Hz - Tensile load (static load): 20 g

[0042] In the present invention, the modulus of elasticity is a value obtained by the above measurement. However, there are cases where only cured sheets with thicknesses other than 2 mm are available. For example, this may be the case when the composition of the composition before curing is unknown and adjustment is not possible. In such cases, if the film layer of the protective film can be peeled off and peeling does not cause damage to the rubber layer that would affect the modulus of elasticity, it can be estimated by measuring the rubber layer after peeling off the film layer. In this case, the measurement conditions other than the thickness are measured in the same manner as the measurement method described above, and the actual thickness is used in calculating the results, thereby estimating the modulus of elasticity at a thickness of 2 mm. Furthermore, according to the findings of the inventors, when the modulus of elasticity was measured for multiple samples of silicone rubber with the same composition, ranging in thickness from 100 μm to 2 mm, the modulus of elasticity of samples thinner than 2 mm was equivalent to the modulus of elasticity of samples with a thickness of 2 mm.

[0043] Furthermore, the silicone rubber layer preferably has a thickness sufficient to protect the first resin pattern 110. Therefore, the thickness of the silicone rubber layer is preferably 1 μm or more, more preferably 5 μm or more. Furthermore, if the silicone rubber layer is too thick, it may hinder the formation of the second resin pattern 120. Therefore, the thickness of the silicone rubber layer is preferably 1 mm or less, more preferably 500 μm or less. Furthermore, depending on the protection form of the concave-convex structure of the micropattern, the thickness of the silicone rubber layer or protective film may be equal to or greater than the depth of the concave structures or the height of the convex structures of the concave-convex structure, or may be less than the depth of the concave structures or the height of the convex structures of the concave-convex structure. Examples of protection forms include a form in which at least a portion of the silicone rubber layer is protected by being embedded in at least a portion of the recesses, a form in which the silicone rubber layer and the film layer are protected by being embedded in at least a portion of the recesses, and a form in which the silicone rubber layer is protected by covering the opening of the recesses like a tent. These can be selected by, for example, appropriately adjusting the thickness, hardness such as elastic modulus, adhesive strength, etc. of the silicone rubber layer or film layer, and can be selected depending on the size and distribution of the pattern to be molded and the molding conditions.

[0044] Although a membranous material having a thickness of less than 250 μm is sometimes called a film, the term "film" in the present invention encompasses membranous materials or plate-like materials having a thickness of 250 μm or more. The protective film of the present invention can be provided, for example, in a roll form in which a long protective film is wound around a core, or in a sheet form in which the protective film is cut into a sheet of the required size.

[0045] The silicone rubber layer may be made of any material as long as it can adhere to the surface of the substrate 1 on which the first resin pattern 110 is formed and protect the first resin pattern 110 from scratches and the like. For example, it can be obtained from an addition-type or condensation-type silicone pressure-sensitive adhesive composition. Among these, an addition-type silicone pressure-sensitive adhesive composition is preferred from the viewpoint of film formation, as it has little cure shrinkage. Note that a condensation-type silicone pressure-sensitive adhesive composition can be used if the film layer has enough rigidity to withstand cure shrinkage during silicone rubber layer formation. Preferred examples of addition-type silicone pressure-sensitive adhesive compositions include compositions containing an organopolysiloxane, an organopolysiloxane resin, an organohydrogenpolysiloxane, and a metal catalyst. More specifically, a cured addition-curable silicone pressure-sensitive adhesive composition containing: (A) 100 parts by mass of an organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and having a viscosity of 0.01 to 1,000 Pa s at 25°C; (B) 5 to 500 parts by mass of an organopolysiloxane resin having alkenyl groups; (C) an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms per molecule, in an amount such that the number of silicon-bonded hydrogen atoms in component (C) is 0.1 to 5.0 times the molar ratio of all silicon-bonded alkenyl groups in the composition; and (D) a platinum group metal catalyst can be used.

[0046] (A) Organopolysiloxane Component (A) is the crosslinking component of the composition. It is an organopolysiloxane having a viscosity at 25°C of 0.01 to 1,000 Pa·s, preferably 0.05 to 500 Pa·s, and containing at least two alkenyl groups bonded to silicon atoms per molecule. If the viscosity at 25°C is less than 0.01 Pa·s, the adhesive strength of the cured product will be low, and if it exceeds 1,000 Pa·s, workability will be impaired. The viscosity is measured using a rotational viscometer (hereinafter the same). Such organopolysiloxane is not particularly limited as long as it satisfies the above viscosity and alkenyl group content requirements. Known organopolysiloxanes can be used, and their structures may be linear or branched. They may also be mixtures of two or more organopolysiloxanes with different viscosities.

[0047] The alkenyl group bonded to the silicon atom is not particularly limited, but is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms. Specific examples include vinyl, allyl, 1-butenyl, and 1-hexenyl groups. Of these, vinyl groups are preferred from the standpoints of ease of synthesis and cost. The alkenyl groups may be present either at the terminals or in the middle of the molecular chain of the organopolysiloxane, but from the standpoint of flexibility, it is preferable for them to be present only at both terminals.

[0048] The organic group other than the alkenyl group bonded to the silicon atom is not particularly limited, but is preferably a monovalent hydrocarbon group having 1 to 20 carbon atoms, and more preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms. Specific examples include alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-hexyl, and n-dodecyl; aryl groups such as phenyl; and aralkyl groups such as 2-phenylethyl and 2-phenylpropyl. Some or all of the hydrogen atoms in these hydrocarbon groups may be substituted with halogen atoms such as chlorine, fluorine, and bromine. Specific examples include halogen-substituted monovalent hydrocarbon groups such as fluoromethyl, bromoethyl, chloromethyl, and 3,3,3-trifluoropropyl. Among these, methyl groups are preferred in terms of ease of synthesis and cost. Therefore, a dimethylpolysiloxane in which both terminals are capped with dimethylvinylsilyl groups is particularly preferred as component (A). Component (A) may be used alone or in combination.

[0049] Specific examples of such component (A) include organopolysiloxanes represented by the following formula, but are not limited to these.

[0050] (In the formula, Me means a methyl group. The same applies hereinafter.)

[0051] (B) Organopolysiloxane Resin Component (B) is a cross-linkable resin containing alkenyl groups that improves the hardness and strength of the cured product while also imparting adhesive properties to the cured product. Conventional silicone adhesives impart adhesive properties by incorporating a non-cross-linkable resin. When such adhesives are used to protect a relief structure such as the first resin pattern 110, the non-cross-linkable resin that is not incorporated into the cross-linked structure migrates onto the relief structure. In contrast, component (B) used in the composition of the present invention contains alkenyl groups that are incorporated into the cross-linked structure upon curing, thereby significantly reducing material migration to devices when the cured product is used as a temporary fixing material.

[0052] The weight-average molecular weight of component (B) is preferably 500 to 30,000, more preferably 1,000 to 20,000. Within this range, the workability of the composition and the adhesive strength of the cured product are improved. The weight-average molecular weight is a value calculated using standard polystyrene standards in gel permeation chromatography (GPC).

[0053] The content of silicon-bonded alkenyl groups in component (B) is preferably 0.001 to 1.000 mol, and more preferably 0.010 to 0.500 mol, per 100 g of component (B). This range ensures good adhesive strength and mechanical properties of the cured product.

[0054] Component (B) is RSiO 3 / 2 (wherein R represents a substituted or unsubstituted monovalent hydrogen group), and a trifunctional siloxane unit (i.e., an organosilsesquioxane unit) represented by SiO 4 / 2 The organopolysiloxane resin of component (B) may optionally contain monofunctional siloxane units (i.e., triorganosiloxy units) and / or difunctional siloxane units (i.e., diorganosiloxane units), but preferably contains at least one branch-forming unit of the tetrafunctional siloxane unit represented by RSiO 3 / 2 Units and SiO 4 / 2 The total content of these units is preferably at least 10 mol %, and more preferably 20 to 90 mol %, of all siloxane units in the organopolysiloxane resin of component (B).

[0055] The above RSiO 3 / 2In the unit, the substituted or unsubstituted monovalent hydrocarbon group represented by R preferably has 1 to 10 carbon atoms, and specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl groups; alkenyl groups such as vinyl, allyl (2-propenyl), 1-propenyl, isopropenyl, butenyl, pentenyl, hexenyl, and cyclohexenyl groups (alkenyl groups are used herein to encompass cycloalkenyl groups); aryl groups such as phenyl, tolyl, xylyl, naphthyl, and biphenylyl groups; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups; and alkaryl groups such as methylbenzyl groups. In addition, one or more hydrogen atoms of these hydrocarbon groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom, or a cyano group. Examples of such substituted hydrocarbon groups include halogenated alkyl groups such as a chloromethyl group, a 2-bromoethyl group, a 3-chloropropyl group or a 3,3,3-trifluoropropyl group.

[0056] Examples of such component (B) include R 1 3SiO 1 / 2 Units and R 1 R 2 SiO 2 / 2 Units and SiO 4 / 2 a copolymer consisting of R 1 3SiO 1 / 2 Units and R 1 2SiO 2 / 2 Units and R 1 R 2 SiO 2 / 2 Units and SiO 4 / 2 a copolymer consisting of R 1 3SiO 1 / 2 Units and R 1 2nd Race 2 SiO 1 / 2 Units and R 1 2SiO 2 / 2 Units and SiO 4 / 2 a copolymer consisting of R1 3SiO 1 / 2 Units and R 1 2nd Race 2 SiO 1 / 2 Units and SiO 4 / 2 a copolymer consisting of R 1 2nd Race 2 SiO 1 / 2 Units and R 1 2SiO 2 / 2 Units and SiO 4 / 2 a copolymer consisting of R 1 R 2 SiO 2 / 2 Units and R 1 SiO 3 / 2 Units and / or R 2 SiO 3 / 2 and copolymers consisting of units.

[0057] In the above formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group that does not have an unsaturated aliphatic bond, and examples thereof include the monovalent hydrocarbon groups exemplified above for R, other than alkenyl groups. Particularly preferred are alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, and n-heptyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl and phenethyl; and halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl. 2 is an alkenyl group, and examples thereof include vinyl, allyl, butenyl, pentenyl, hexenyl, and heptenyl groups.

[0058] More specifically, for example, (CH3)3SiO 1 / 2 Units and (CH2=CH)SiO 3 / 2 Units and SiO 4 / 2 a copolymer consisting of (CH2=CH)(CH3)2SiO units, 1 / 2 Units and SiO 4 / 2 a copolymer consisting of (CH2=CH)(CH3)2SiO units, 1 / 2 Units and (CH2=CH)SiO 3 / 2 Units and SiO 4 / 2 a copolymer consisting of (CH3)3SiO units, 1 / 2Units and (CH2=CH)(CH3)2SiO 1 / 2 Units and SiO 4 / 2 and copolymers in which some of the methyl groups have been substituted with phenyl groups.

[0059] Specific examples of component (B) include those represented by the following average unit formula: (MeSiO 1 / 2 ) 0.35 (ViMeSiO 1 / 2 ) 0.1 (SiO 4 / 2 ) 0.55 (MeSiO 1 / 2 ) 0.4 (ViMeSiO 1 / 2 ) 0.1 (SiO 4 / 2 ) 0.5 (ViMeSiO) 0.4 (MeSiO) 0.15 (MeSiO 3 / 2 ) 0.45 (ViMeSiO 1 / 2 ) 0.2 (MeSiO) 0.25 (MeSiO 3 / 2 ) 0.55 (MeSiO 1 / 2 ) 0.2 (ViMeSiO 1 / 2 ) 0.05 (MeSiO 3 / 2 ) 0.75

[0060] The blending amount of the (B) component is 5 to 500 parts by mass, preferably 10 to 400 parts by mass, per 100 parts by mass of the (A) component. If the (B) component is less than 5 parts by mass, sufficient adhesiveness as a temporary fixing material cannot be obtained, and if it exceeds 450 parts by mass, adhesiveness is not exhibited. The (B) component may be used alone or in combination of two or more types.

[0061] (C) Organohydrogenpolysiloxane Component (C) contains at least two (usually 2 to 300), preferably three or more (for example, about 3 to 150) silicon-bonded hydrogen atoms (i.e., SiH groups) per molecule, and may be a resinous substance with a linear, branched, cyclic, or three-dimensional network structure. This organohydrogenpolysiloxane may have a silicon atom count (i.e., degree of polymerization) of typically 2 to 300, preferably about 3 to 200, per molecule. Representative examples of such organohydrogenpolysiloxanes include organohydrogenpolysiloxanes represented by the following average composition formula (1): H a R 3 b SiO (4-a-b) / 2 ...(1) (wherein, R 3 are each independently an unsubstituted or substituted monovalent hydrocarbon group containing no aliphatic unsaturated bonds, and a and b are numbers satisfying 0 < a < 2, 0.8 ≦ b ≦ 2, and 0.8 < a + b ≦ 3, preferably 0.05 ≦ a ≦ 1, 1.5 ≦ b ≦ 2, and 1.8 ≦ a + b ≦ 2.7.

[0062] The above R 3The monovalent hydrocarbon group not containing an aliphatic unsaturated bond preferably has 1 to 10 carbon atoms, and specific examples thereof include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl, and biphenylyl; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl; alkaryl groups such as methylbenzyl, and halogenated alkyl groups such as chloromethyl, 2-bromoethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl, in which one or more hydrogen atoms of these hydrocarbon groups have been substituted with a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom, or a cyano group. Among these, those having 1 to 7 carbon atoms are preferred, and alkyl groups having 1 to 3 carbon atoms such as methyl groups, phenyl groups, and 3,3,3-trifluoropropyl groups are more preferred.

[0063] Specific examples of such organohydrogenpolysiloxanes include siloxane oligomers such as 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,8-pentamethylcyclopentasiloxane, tris(dimethylhydrogensiloxy)methylsilane, and tris(dimethylhydrogensiloxy)phenylsilane; methylhydrogencyclopolysiloxane, and methylhydrogensiloxane-dimethylsiloxane cyclic polysiloxanes. copolymers, methylhydrogenpolysiloxanes terminally capped with trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymers terminally capped with trimethylsiloxy groups, dimethylpolysiloxanes terminally capped with dimethylhydrogensiloxy groups, methylhydrogenpolysiloxanes terminally capped with dimethylhydrogensiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymers terminally capped with dimethylhydrogensiloxy groups, etc.; R 3 2(H)SiO 1 / 2 Units and SiO 4 / 2units, optionally R 3 3SiO 1 / 2 Unit, R 3 2SiO 2 / 2 Unit, R 3 (H)SiO 2 / 2 Units: (H)SiO 3 / 2 Unit or R 3 SiO 3 / 2 Silicone resins that may contain units (wherein R 3 has the same meaning as above.) and compounds in which some of the methyl groups in the above exemplary compounds have been substituted with other alkyl groups such as ethyl groups and n-propyl groups and / or phenyl groups.

[0064] The organohydrogenpolysiloxane used in the composition of the present invention can be obtained by a known method, for example, 3 SiHCl2 and R 3 2SiHCl (wherein R 3 has the same meaning as above.) or by co-hydrolyzing the chlorosilane with R 3 3SiCl and R 3 2SiCl2 (wherein, R 3 has the same meaning as above.) The organohydrogenpolysiloxane used in the composition of the present invention may also be a product obtained by subjecting the polysiloxane obtained by such cohydrolysis to an equilibration reaction.

[0065] The amount of component (C) is such that the number of silicon-bonded hydrogen atoms (i.e., SiH groups) in the organohydrogenpolysiloxane of component (C) per silicon-bonded alkenyl group in the organopolysiloxanes of components (A) and (B) is 0.1 to 5.0, and preferably 0.2 to 2.0. Note that component (C) may be used alone or in combination of two or more.

[0066] (D) Platinum Group Metal Catalyst The platinum group metal catalyst of component (D) may be any catalyst known in the art, as long as it promotes the addition reaction between the alkenyl groups of components (A) and (B) and the Si-H groups of component (C). However, catalysts selected from platinum and platinum compounds are preferred. Specific examples of catalysts include platinum group metals such as platinum (including platinum black), rhodium, and palladium; platinum chlorides such as HPtCl.nH2O, HPtCl.H2O, NaHPtCl.nH2O, KHPtCl.nH2O, NaPtCl.nH2O, KPtCl.nH2O, PtCl.nH2O, PtCl, and NaHPtCl.nH2O (where n is an integer of 0 to 6, preferably 0 or 6); chloroplatinic acid; and chloroplatinic acid. Examples of suitable catalysts include platinate salts, alcohol-modified chloroplatinic acid; complexes of chloroplatinic acid with olefins; platinum black, platinum group metals such as palladium supported on a support such as alumina, silica, or carbon; rhodium-olefin complexes, chlorotris(triphenylphosphine)rhodium (Wilkinson's catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate salts with vinyl group-containing siloxanes, and the like. These may be used alone or in combination of two or more.

[0067] The amount of component (D) to be blended is an effective amount as a catalyst, and may be any amount that can promote the reaction between components (A) and (B) and component (C), and may be adjusted appropriately depending on the desired curing rate. In particular, an amount that is 0.1 to 10,000 ppm, calculated as platinum group metal atoms, relative to the mass of component (A) is preferred, and an amount that is 1 to 5,000 ppm is more preferred. When the amount of component (D) is within the above range, more efficient catalytic action can be expected.

[0068] (E) Organic Solvent The silicone composition can be a solventless composition obtained by blending the above components (A) to (D) in predetermined amounts, or it can be used as a solvent-based composition diluted with an organic solvent as needed. Diluting with an organic solvent offers practical advantages such as improved coating workability, improved application properties and film thickness control with a spin coater, and improved coating film condition, including the thickness and surface finish of the coating film.

[0069] Any organic solvent can be used as long as it is capable of dissolving silicone, and examples thereof include aromatic hydrocarbon compounds such as toluene and xylene; aliphatic hydrocarbon compounds such as hexane, heptane, and isoparaffin; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester compounds such as ethyl acetate and butyl acetate; and ether compounds such as diisopropyl ether and 1,4-dioxane. These may be used alone or in combination of two or more. When an organic solvent is used, the amount thereof is preferably 1 to 10,000 parts by weight, and more preferably 10 to 5,000 parts by weight, per 100 parts by weight of component (A). If the amount is less than 1 part by weight, the benefits of dilution may not be obtained, while if the amount is more than 10,000 parts by weight, the film thickness after application may be too thin.

[0070] (F) Antistatic Agent An antistatic agent may be added as component (F) to the composition of the present invention for the purpose of reducing surface resistivity and imparting antistatic properties to the material. Examples of antistatic agents include alkali metal or alkaline earth metal salts, and ionic liquids. Here, ionic liquids are molten salts that are liquid at room temperature (25°C), also known as room-temperature molten salts, and particularly refer to those with a melting point of 50°C or less, with melting points of -100 to 30°C being preferred, and those of -50 to 20°C being more preferred. Such ionic liquids have properties such as no vapor pressure (non-volatility), high heat resistance, non-flammability, and chemical stability.

[0071] Examples of alkali metal or alkaline earth metal salts include alkali metal salts such as lithium, sodium, and potassium; and alkaline earth metal salts such as calcium and barium. Specific examples of these include alkali metal salts such as LiClO, LiCFSO, LiN(CFSO), LiAsF, LiCl, NaSCN, KSCN, NaCl, NaI, and KI; and alkaline earth metal salts such as Ca(ClO) and Ba(ClO). Among these, lithium salts such as LiClO, LiCFSO, LiN(CFSO), LiAsF, and LiCl are preferred from the viewpoints of low resistance and solubility, with LiCFSO and LiN(CFSO) being more preferred.

[0072] The ionic liquid comprises a quaternary ammonium cation and an anion, the quaternary ammonium cation being imidazolium, pyridinium, or an anion of the formula: 6 4N + [In the formula, R 6 are each independently a hydrogen atom or an organic group having 1 to 20 carbon atoms.

[0073] The above R 6 Specific examples of the organic group represented by the formula (I) include monovalent hydrocarbon groups having 1 to 20 carbon atoms, alkoxyalkyl groups, etc., and more specific examples include alkyl groups such as methyl, pentyl, hexyl, and heptyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; aralkyl groups such as benzyl and phenethyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups; and alkoxyalkyl groups such as ethoxyethyl group (-CH2CHOCH2CH3). 6 Two of the organic groups represented by the formula (I) may be bonded to form a cyclic structure, and in this case, the two R 6 together form a divalent organic group. The main chain of this divalent organic group may be composed of only carbon, or may contain heteroatoms such as oxygen atoms and nitrogen atoms. Specific examples include divalent hydrocarbon groups [e.g., alkylene groups having 3 to 10 carbon atoms], the formula: -(CH2) c —O—(CH2) d- [wherein c is an integer of 1 to 5, d is an integer of 1 to 5, and c+d is an integer of 4 to 10].

[0074] The above R 6 4N + Specific examples of the cation represented by the formula (I) include methyltri-n-octylammonium cation, ethoxyethylmethylpyrrolidinium cation, ethoxyethylmethylmorpholinium cation, etc. The anion is not particularly limited, but examples thereof include AlCl4 - , AlCl 10 - , Al2Cl7 - , ClO - , PF6 - , BF4 - , CF3SO3 - , (CF3SO2)2N - , (CF3SO2)3C - is preferred, and PF6 - , BF4 - , CF3SO3 - , (CF3SO2)2N - is more preferred.

[0075] When component (F) is used, the blending amount thereof is preferably 0.001 to 10 parts by mass, and more preferably 0.005 to 10 parts by mass, per 100 parts by mass of component (A) from the viewpoints of antistatic properties and heat resistance. The antistatic agents may be used alone or in combination of two or more.

[0076] The antistatic performance of the cured product obtained from the addition-curable silicone pressure-sensitive adhesive composition according to the present invention containing component (F) is measured by charging the surface of the cured product with 6 kV of static electricity by corona discharge using a Static Honest Meter (manufactured by Shishido Electrostatic Corporation). The time it takes for the charged voltage to decrease by half (half-life) is preferably within 2 minutes, and more preferably within 1 minute.

[0077] (G) Reaction Retardant The composition of the present invention may contain a reaction retardant as component (G) for the purpose of suppressing the curing reaction at room temperature and extending shelf life and pot life. Any reaction retardant capable of suppressing the catalytic activity of component (D) may be used, and any conventionally known reaction retardant may be used. Specific examples include acetylene alcohol compounds such as 1-ethynyl-1-cyclohexanol and 3-butyn-1-ol; various nitrogen compounds; organic phosphorus compounds; oxime compounds; and organic chloro compounds. These may be used alone or in combination of two or more. Among these, acetylene alcohol compounds that are not corrosive to metals are preferred.

[0078] When component (G) is used, the amount thereof is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of component (A). If the amount of reaction inhibitor is less than 0.001 part by mass, sufficient shelf life and pot life may not be obtained, and if it exceeds 5 parts by mass, the curability of the composition may be reduced. Note that the reaction inhibitor may be diluted with an organic solvent such as toluene, xylene, or isopropyl alcohol to improve dispersibility in the silicone resin.

[0079] The composition according to the present invention may contain additives such as coloring materials (pigments or dyes), silane coupling agents, adhesion aids, polymerization inhibitors, antioxidants, ultraviolet absorbers as light resistance stabilizers, light stabilizers, etc., within the scope of not impairing the effects of the present invention. The composition according to the present invention may also be used by appropriately mixing it with other resin compositions.

[0080] The addition-curable silicone pressure-sensitive adhesive composition according to the present invention can be obtained by mixing the above components (A) to (D), and, if necessary, other components, in any order, followed by stirring, etc. The process for mixing and stirring the components is not particularly limited. The composition may be in the form of either a one-component or two-component type, and one-component compositions can be stored for long periods by refrigeration or freezing, while two-component compositions can be stored for long periods at room temperature.

[0081] For example, a one-component composition containing components (A) to (G) can be obtained by placing components (A), (B), (D), (E), and (F) in a Gate Mixer (manufactured by Inoue Seisakusho Co., Ltd., trade name: Planetary Mixer), mixing them at room temperature for 30 minutes, then adding component (G) and mixing them at room temperature for 30 minutes, and then adding component (C) and mixing them at room temperature for 30 minutes.

[0082] On the other hand, a two-component composition containing components (A) to (G) as a whole can be composed of any combination, as long as the combination of components (A), (C), and (D) and the combination of components (B), (C), and (D) are not the only components that coexist. For example, components (A), (B), (D), (E), and (F) can be placed in a gate mixer and mixed under heat at room temperature for 30 minutes to obtain a composition called component A, and components (A), (C), and (G) can be placed in a gate mixer and mixed at room temperature for 30 minutes to obtain a composition called component B, thereby obtaining a two-component composition consisting of components A and B.

[0083] From the viewpoint of moldability and workability during application, the viscosity of the addition-curable silicone pressure-sensitive adhesive composition according to the present invention is preferably 1,000 Pa·s or less, more preferably 500 Pa·s or less, and even more preferably 100 Pa·s or less, as measured at 23° C. using a rotational viscometer. If the viscosity exceeds 5,000 Pa·s, workability may be significantly impaired.

[0084] The curing conditions for the addition-curable silicone composition according to the present invention are not particularly limited, and can be the same as those for known curable silicone compositions. Curing can be carried out at room temperature or by heating, preferably at a temperature of 20 to 180°C, more preferably 50 to 150°C, for a reaction time of preferably 0.1 to 3 hours, more preferably 0.5 to 2 hours.

[0085] 1(g) to 1(k), the second resin pattern molding step is a step of forming a second resin pattern 120 on the second surface 12 after the protective film attachment step. The second resin pattern 120 may be formed in any manner, for example, by using a well-known imprinting method such as photoimprinting or thermal imprinting. Alternatively, the second resin pattern 120 may be formed by applying a resin such as a resist to which the imprinting method can be applied onto the substrate 1, transferring a pattern to the resin by the imprinting method, and then performing etching using the resin with the pattern formed as a mask.

[0086] Furthermore, as shown in FIG. 1(l), the double-sided molding method of the present invention may include a protective film peeling step of peeling off the protective film 2 attached to the first surface 11 after the second resin pattern molding step. The protective film 2 may be peeled off mechanically or manually. For example, the protective film 2 may be peeled off by pinching the edge of the protective film 2 with tweezers or the like. When packaging and transporting the double-sided molded product, the protective film may be left in place. In this case, the protective film may be peeled off when the double-sided molded product is to be used after transportation.

[0087] 1(f), the molded product of the present invention is composed of a substrate 1 having a first surface 11 and a second surface 12, a first resin pattern 110 formed on the first surface 11, and a protective film 2 having a silicone rubber layer attached onto the first resin pattern 110. In this molded product, a second resin pattern 120 can be formed on the second surface 12 of the substrate 1 while protecting the first resin pattern 110.

[0088] Furthermore, the molded product of the present invention may have a second resin pattern 120 formed on the second surface 12 of the substrate 1, as shown in FIG. 1(k).

[0089] The substrate 1, the protective film 2, the first resin pattern 110, and the second resin pattern 120 are the same as those described above in the double-sided molding method of the present invention, and therefore a description thereof will be omitted.

[0090] Although the above describes an embodiment using silicone rubber, the present invention does not necessarily require a silicone rubber layer using silicone rubber. As long as the effect of the present invention, namely, suppressing pattern damage, can be achieved, a rubber layer using a rubber other than silicone rubber may also be used. Examples of such rubbers other than silicone rubber include nitrile rubber, fluororubber, urethane rubber, acrylic rubber, isoprene rubber, styrene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-vinyl acetate rubber, and chloroprene rubber. The various properties and usage of rubber layers using these rubbers, such as tensile strength, adhesive strength, modulus of elasticity, and thickness, can be the same as those of the silicone rubber layer described above. Using rubber makes it easier to control adhesion to the fine pattern, suppressing adhesive residue due to excessive adhesion. Therefore, pattern damage can be suppressed.

[0091] Furthermore, in the present invention, the term "rubber" often refers to a thermosetting elastomer. It is preferable that the thermosetting elastomer has rubber elasticity and does not soften easily even when heated. A thermosetting elastomer allows for greater flexibility in the thermal environment during the molding process. On the other hand, a thermoplastic elastomer may be used if the thermal environment during the molding process can be controlled. Furthermore, gels that have rubber elasticity, known as elastomer gels, are known among gels in which dispersoids are connected in a network-like manner in a liquid dispersion medium and have lost fluidity. Such elastomer gels can be used instead of rubber. These applications can be adopted depending on the size and distribution of the pattern to be molded and the desired degree of suppression of pattern damage. Therefore, the silicone rubber layer in the present invention can be generally referred to as a rubber layer or a thermosetting elastomer layer, and can also be generally referred to as an elastomer layer, which includes a thermoplastic elastomer layer and an elastomer gel layer. As described above, the various properties such as tensile strength, adhesive strength, elastic modulus, thickness, etc., and usage of layers using these elastomers such as thermosetting elastomers, thermoplastic elastomers, and elastomer gels can in many cases be the same as the various properties and usage of the silicone rubber layer described above.

[0092] While the embodiments of the present invention have been described in detail above, the present invention can be expressed from different perspectives as follows (1-1) to (9-4). (1-1) A double-sided molding method for forming a first resin pattern on a first surface of a substrate and a second resin pattern on a second surface of the substrate, the double-sided molding method comprising: a protective film attaching step of attaching the silicone rubber layer side of a protective film having a silicone rubber layer onto the first resin pattern; and a second resin pattern molding step of forming a second resin pattern on the second surface after the protective film attaching step. (1-2) A molded product comprising: a substrate having a first surface and a second surface; a first resin pattern formed on the first surface; and a protective film having a silicone rubber layer attached onto the first resin pattern. (2-1) A double-sided molding method for forming a first pattern on a first surface of a substrate and a second pattern on a second surface of the substrate, comprising: a protective film attaching step of attaching the silicone rubber layer side of a protective film having a silicone rubber layer onto the first pattern, and a second pattern molding step of forming a second pattern on the second surface after the protective film attaching step. (2-2) A molded product comprising: a substrate having a first surface and a second surface, a first pattern formed on the first surface, and a protective film having a silicone rubber layer attached onto the first pattern. (3-1) A double-sided molding method for forming a first resin pattern on a first surface of a substrate and forming a second resin pattern on a second surface of the substrate, the double-sided molding method comprising: a protective film attaching step of attaching the rubber layer side of a protective film having a rubber layer onto the first resin pattern, and a second resin pattern molding step of forming a second resin pattern on the second surface after the protective film attaching step. (3-2) A molded product comprising: a substrate having a first surface and a second surface, a first resin pattern formed on the first surface, and a protective film having a rubber layer attached onto the first resin pattern.(4-1) A double-sided molding method for forming a first pattern on a first surface of a substrate and a second pattern on a second surface of the substrate, comprising: a protective film attaching step of attaching the rubber layer side of a protective film having a rubber layer onto the first pattern; and a second pattern molding step of forming a second pattern on the second surface after the protective film attaching step. (4-2) A molded product comprising: a substrate having a first surface and a second surface; a first pattern formed on the first surface; and a protective film having a rubber layer attached onto the first pattern. (4-3) A double-sided molding method for forming a second pattern on the second surface of a substrate having a first pattern formed on its first surface, comprising: a preparation step of preparing a substrate in which the rubber layer side of a protective film having a rubber layer is attached onto the first pattern; and a second pattern molding step of forming a second pattern on the second surface after the preparation step. (5-1) A method for manufacturing a double-sided molded product having a first pattern formed on a first surface of a substrate and a second pattern formed on a second surface of the substrate, comprising: a protective film attaching step of attaching the rubber layer side of a protective film having a rubber layer onto the first pattern, and a second pattern molding step of forming a second pattern on the second surface after the protective film attaching step. (5-2) A method for manufacturing a double-sided molded product having a first pattern formed on a first surface of a substrate and a second pattern formed on the second surface of the substrate, comprising: a preparation step of preparing a substrate having a rubber layer attached with the rubber layer side of a protective film having a rubber layer onto the first pattern, and a second pattern molding step of forming a second pattern on the second surface after the preparation step. (6-1) A double-sided molding method for forming a first pattern on a first surface of a substrate and a second pattern on a second surface of the substrate, the double-sided molding method comprising: a rubber layer forming step of providing a rubber layer on the first pattern; and a second pattern molding step of forming a second pattern on the second surface after the rubber layer is formed.(6-2) A molded product comprising: a substrate having a first surface and a second surface; a first pattern formed on the first surface; and a rubber layer provided on the first pattern. (6-3) A double-sided molding method for forming a second pattern on a second surface of a substrate having a first pattern formed on its first surface, the double-sided molding method comprising: a preparation step of preparing a substrate having a rubber layer provided on the first pattern; and a second pattern molding step of forming a second pattern on the second surface after the preparation step. (7-1) A method for manufacturing a double-sided molded product having a first pattern formed on the first surface of a substrate and a second pattern formed on the second surface of the substrate, the method comprising: a rubber layer providing step of providing a rubber layer on the first pattern; and a second pattern molding step of forming a second pattern on the second surface after the rubber layer is provided. (7-2) A method for manufacturing a double-sided molded product having a first pattern formed on a first surface of a substrate and a second pattern formed on a second surface of the substrate, the method comprising: a preparation step of preparing a substrate having a rubber layer provided on the first pattern; and a second pattern molding step of forming a second pattern on the second surface after the preparation step. (8-1) A protective film used to form a second resin pattern on a second surface of a substrate having a first resin pattern formed on its first surface, the protective film having a silicone rubber layer, and used to protect the first resin pattern by adhering the silicone rubber layer onto the first resin pattern when forming the second resin pattern. (8-2) A protective film used to form a second pattern on a second surface of a substrate having a first pattern formed on its first surface, the protective film having a rubber layer, and used to protect the first pattern by adhering the rubber layer onto the first pattern when forming the second pattern.(8-3) A rubber layer used to form a second pattern on a second surface of a substrate having a first pattern formed on its first surface, the rubber layer being used to protect the first pattern by being attached onto the first pattern when the second pattern is being formed. (8-4) A rubber used to form a second pattern on a second surface of a substrate having a first pattern formed on its first surface, the rubber being used to protect the first pattern by being provided onto the first pattern when the second pattern is being formed. (9-1) An application of a protective film for forming a second resin pattern on a second surface of a substrate having a first resin pattern formed on its first surface, the protective film having a silicone rubber layer, the silicone rubber layer being attached onto the first resin pattern when the second resin pattern is being formed, the protective film protecting the first resin pattern. (9-2) An application of a protective film for forming a second pattern on a second surface of a substrate having a first pattern formed on its first surface, the protective film having a rubber layer, wherein the rubber layer is attached onto the first pattern when the second pattern is being formed, thereby protecting the first pattern. (9-3) An application of a rubber layer for forming a second pattern on a second surface of a substrate having a first pattern formed on its first surface, the rubber layer being attached onto the first pattern when the second pattern is being formed, thereby protecting the first pattern. (9-4) An application of rubber for forming a second pattern on a second surface of a substrate having a first pattern formed on its first surface, the rubber being attached onto the first pattern when the second pattern is being formed, thereby protecting the first pattern. Each of the constituent elements in the many embodiments described above can be subdivided, and the subdivided constituent elements can be introduced into these (1-1) to (9-4) individually or in combination. Furthermore, any constituent element may be omitted as long as the process conditions permit.

[0093] REFERENCE SIGNS LIST 1 substrate 2 protective film 4 primer 11 first surface 12 second surface 31 first resin 32 second resin 110 first resin pattern 120 second resin pattern

Claims

1. A double-sided molding method for forming a first resin pattern on a first surface of a substrate and a second resin pattern on a second surface of the substrate, comprising: a protective film attachment step of attaching the silicone rubber layer side of a protective film having a silicone rubber layer onto the first resin pattern; and a second resin pattern molding step of forming a second resin pattern on the second surface after the protective film attachment step.

2. The double-sided molding method according to claim 1, wherein the tensile strength of said silicone rubber layer is greater than the adhesive strength of said silicone rubber layer.

3. The double-sided molding method according to claim 2, wherein the tensile strength of the silicone rubber layer is 0.5 MPa or more.

4. The double-sided molding method according to claim 2, wherein the adhesive strength of the silicone rubber layer is 10 kPa or more and 1500 kPa or less.

5. A double-sided molding method according to any one of claims 1 to 4, characterized in that the elastic modulus of the silicone rubber layer is smaller than the elastic modulus of the first resin constituting the first resin pattern.

6. The double-sided molding method according to claim 5, wherein the modulus of elasticity of said silicone rubber layer is less than 200 MPa.

7. The double-sided molding method according to claim 5, wherein the modulus of elasticity of said first resin is 200 MPa or more.

8. A double-sided molding method according to any one of claims 1 to 4, characterized in that the thickness of the silicone rubber layer is 1 µm or more and 1 mm or less.

9. A double-sided molding method according to any one of claims 1 to 4, characterized in that it comprises a protective film peeling step of peeling off the protective film attached to the first surface after the second resin pattern molding step.

10. The double-sided molding method described in any one of 1 to 4, characterized in that the silicone rubber layer is obtained by curing an addition-curable silicone pressure-sensitive adhesive composition that does not contain a non-crosslinkable organopolysiloxane resin, and that contains: (A) 100 parts by mass of an organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and having a viscosity of 0.01 to 1,000 Pa·s at 25°C; (B) 5 to 500 parts by mass of an organopolysiloxane resin having alkenyl groups; (C) an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms per molecule, in an amount such that the number of silicon-bonded hydrogen atoms in component (C) is 0.1 to 5.0 times the molar ratio of all silicon-bonded alkenyl groups in the composition; and (D) a platinum group metal catalyst.

11. A molded product comprising: a substrate having a first surface and a second surface; a first resin pattern formed on the first surface; and a protective film having a silicone rubber layer attached onto the first resin pattern.

12. The molded product according to claim 11, wherein the tensile strength of said silicone rubber layer is greater than the adhesive strength of said silicone rubber layer.

13. The molded product according to claim 12, characterized in that the tensile strength of said silicone rubber layer is 1.0 MPa or more.

14. The molded product according to claim 12, wherein the adhesive strength of the silicone rubber layer is 10 kPa or more and 1500 kPa or less.

15. A molded product according to claim 11 or 14, characterized in that the elastic modulus of the silicone rubber layer is smaller than the elastic modulus of the first resin constituting the first resin pattern.

16. The molded product according to claim 15, wherein the modulus of elasticity of said silicone rubber layer is less than 200 MPa.

17. The molded product according to claim 15, wherein the first resin has a modulus of elasticity of 200 MPa or more.

18. A molded product according to either claim 11 or claim 14, characterized in that the thickness of the silicone rubber layer is 1 μm or more and 1 mm or less.

19. A molded product according to any one of claims 11 to 14, characterized in that it has a second resin pattern formed on the second surface.

20. The molded product according to any one of claims 11 to 14, characterized in that the silicone rubber layer is obtained by curing an addition-curable silicone pressure-sensitive adhesive composition that does not contain a non-crosslinkable organopolysiloxane resin, and that contains: (A) 100 parts by mass of an organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule and having a viscosity of 0.01 to 1,000 Pa·s at 25°C; (B) 5 to 500 parts by mass of an organopolysiloxane resin having alkenyl groups; (C) an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms per molecule, in an amount such that the number of silicon-bonded hydrogen atoms in component (C) is 0.1 to 5.0 times the molar ratio of all silicon-bonded alkenyl groups in the composition; and (D) a platinum group metal catalyst.

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