JP2007270133A - Composition for sheet having easily formable surface, sheet having easily formable surface using it, laminate of sheet easily forming surface, and method of forming surface using it and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for a sheet having an easily formable surface capable of favorably giving a form for various forms of highly meticulous, with a high aspect ratio, etc., and forming a sheet excellent in long given-shape stability, a sheet having an easily formable surface formed using the comosition, a laminate of the sheets having an easily formable surface, and a method of forming a surface using the composition. <P>SOLUTION: This composition has an initiation temperature of phase difference increase (Ts) measured using a scanning viscoelasticity microscope of not lower than 25°C, and this sheet having an easily formable surface is prepared by processing the resin composition into a sheet form. This laminate comprises a plurarity of layers at least containing a base material as a support and a layer of the sheet having an easily formable surface, and the laminate has the layer of the sheet having an easily formable surface located at least as one surface layer of the laminate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a resin composition for a sheet material that can be easily shaped on a surface, in particular, a composition for a sheet material that can be easily shaped on a surface in various shapes such as high definition and high aspect ratio, and the like The present invention relates to a sheet material using a composition for sheet material, a surface shaping method using the sheet, and a molded product thereof.

  In recent years, the importance of a technique for forming a fine structure is increasing in various fields such as the optical field and the semiconductor field. In the optical field, high-precision fine structure forming technology is required. In the semiconductor manufacturing field, in addition to high-precision fine structure forming technology, miniaturization of processing dimensions is required to improve the degree of integration of semiconductor integrated circuits.

  Therefore, also in photolithography, which is a representative technique for microfabrication, it is necessary to increase the resolution and control the fine dimensions with high precision, and attempts to shorten the exposure wavelength are being studied. To date, a resolution of a minimum line width of 100 nm using an ArF laser, a resolution of several tens of nanometers using electron beams and X-rays, a so-called nanostructure formation technology has also been achieved, and the practical application of these technologies has been studied. Progressing.

  However, since these techniques improve the resolution by shortening the exposure wavelength, it is inevitable that the initial cost of the exposure apparatus itself and the price of the mask to be used are increased, resulting in a very disadvantageous cost. . In addition, there is a problem that the irradiation spot diameter is small and the productivity is low to form a fine structure with a large area.

  In recent years, therefore, imprint lithography has been proposed by Chou et al. As a technique for easily shaping a fine structure (see Non-Patent Document 1). This imprint lithography is a technique for transferring a pattern on a mold onto a resin, and there are two types of methods, thermal and optical. The former thermal method means that a thermoplastic resin is heated to a glass transition temperature Tg or higher and lower than a melting point Tm, and then a mold having an uneven pattern is pressed on the surface of the thermoplastic resin. The expression is a technique for transferring a pattern on a mold to each resin by irradiating and curing the light with the mold pressed against the photocurable resin. Although these technologies require initial costs for mold fabrication, many microstructures can be replicated from a single mold, resulting in a microstructure that is cheaper than photolithography. Technology that can.

  Therefore, in recent years, by making full use of this imprint lithography, optical elements such as members for flat panel displays such as liquid crystal display devices (Patent Document 1), optical waveguides used for optical communication (Patent Document 2), cell culture elements, etc. Development of plastic elements is being promoted in various fields such as bioelements (Patent Document 3).

In industrial production of these plastic elements, it is desired that resin materials can be rapidly formed into a wide variety of shapes in a wide range of dimensions from the micron order to the nano order.
S. Y. Chou et al., “Appl. Phys. Lett.”, American Physical Society, 1995, Vol. 67, No. 21, p. 3314 JP 2005-168494 A (all pages) JP 2005-140822 A (all pages) JP 2005-168495 A (all pages) JP 2005-140822 A (all pages) JP 2005-168495 A (all pages)

  However, in the thermal imprint lithography, a thermoplastic resin such as polymethyl methacrylate, which has been conventionally studied, cannot satisfy all the above requirements. For example, although it has been reported that low molecular weight PMMA is capable of forming a high-definition (nano-order), high-aspect ratio structure, the mold is released with high accuracy in the imprint process. However, even if it can be released from the mold, there is a problem that the formed pattern strength is weak, it easily deforms against external force, and the pattern shape collapses during long-term storage. . In addition, there are similar problems in optical imprint lithography.

  In view of the background of such prior art, the present invention can be easily released from a wide variety of shaped shapes such as high-definition (particularly nano-order) and high aspect ratio by imprint lithography. Composition for easy surface formable sheet capable of forming sheet having excellent long-term stability of shape, easy surface formable sheet formed using the same, easy surface formable sheet laminate, and use thereof It is intended to provide a surface shaping method and a molded product.

  The present invention employs the following means in order to solve such problems.

  That is, the resin composition for an easily surface-shaped sheet of the present invention has a phase difference increase starting temperature Ts of 25 ° C. or higher measured by a measurement method described later using a scanning viscoelastic microscope. It is characterized by this.

  In addition, the easy-surface formable sheet of the present invention is obtained by processing the resin composition for an easy-surface formable sheet into a sheet shape.

  Further, the easy-surface-formable sheet laminate of the present invention is a laminate comprising a plurality of layers including at least a layer comprising the above-described easy-surface-formable sheet and a base material layer serving as a support, and The easy-surface formable sheet layer is disposed on at least one surface layer of the laminate.

  Moreover, the surface shaping method of the present invention uses a mold to form the surface layer side constituted by the easy surface shaping sheet or the easy surface shaping sheet of the easy surface shaping sheet laminate. Pressurizing and then releasing the mold (mold release temperature: T3) is a surface shaping method for forming a molded product having the mold shape transferred to the surface, and the mold release temperature T3 is 20 ° C. ≦ T3 ≦ Ts.

  Finally, the molded product of the present invention is a molded product having a concavo-convex shape on the surface obtained by such a surface shaping method, and the aspect ratio (H ′ / S ′) of the concavo-convex convex portion is 0.1 to 0.1. It is characterized by being 15.

  According to the present invention, it is possible to obtain a resin composition for an easily surface-formable sheet that can be easily released during molding of a nano-order structure and has excellent long-term storage stability of the structure. The sheet obtained by processing into a sheet can easily form a nano-order high aspect ratio pattern on the sheet surface.

  The inventors of the present invention have earnestly devised a resin composition for a sheet that can be easily released even when various shapes such as high definition and high aspect ratio are formed, and the shape has excellent long-term stability. We studied and made a resin composition that can control the physical properties of the outermost surface in the range of several nm from the surface of the resin composition to specific conditions, and found that the above problems could be solved at once. It is. That is, according to such a resin composition, a sheet having excellent surface formability, particularly releasability at the time of nano-order shape shaping, and its shape has excellent long-term stability (hereinafter referred to as easy surface shaping). Sex sheet) can be provided.

  The resin composition for an easily surface-shaped sheet of the present invention has a phase difference increase starting temperature Ts of 25 ° C. or higher of the resin composition obtained by the following procedures (1) to (7) using a scanning viscoelastic microscope. It is characterized by being.

That is, first,
(1) A thin film (dry film thickness: 250 nm) of the resin composition is formed on a silicon wafer.
(2) A sine having an amplitude of 1 nm in the film thickness direction and a frequency of 100 Hz while contacting a probe of a scanning viscoelastic microscope with a cantilever (spring constant 0.1 N / m) on the surface of the thin film under vacuum conditions. The response vibration phase δa detected by the cantilever when the vibration is applied to the thin film sample is measured.
(3) Similar to (2) above, a sine vibration with an amplitude of 1 nm and a frequency of 100 Hz is applied to a silicon wafer surface while contacting the same probe as in (2) above the surface of the silicon wafer under the same temperature and vacuum conditions. The phase δb of the response vibration when applied to is measured.
(4) The relative phase difference Δδ = δa−δb between the thin film surface and the silicon wafer surface is obtained.
(5) The above measurements (2) and (3) are carried out every 1 ° C. within a temperature range of −50 ° C. to (Tg 1 + 20 ° C.) (Tg 1 is the glass transition temperature of the resin composition). From the obtained phase, as in (4), the relative phase difference Δδ = δa−δb between the surface of the thin film and the surface of the silicon wafer is obtained.
(6) The phase difference Δδ obtained in (1) to (4) is plotted against temperature.
(7) The plot of (5) is observed from the lowest temperature side, and the temperature at which the increase starts with the temperature rise is defined as the phase difference increase start temperature Ts.

Here, the scanning viscoelastic microscope is a kind of scanning force microscope. As shown in FIG. 1A, a constant amplitude is obtained while contacting the surface of the sample 102 with the probe 103 provided at the tip of the cantilever 102. The response vibration l ₂ detected by the cantilever 102 when the sinusoidal vibration l ₁ is applied to the sample 102, and the reflected light of the laser beam 104 applied to the back surface of the cantilever 102 as the vibration of the electric signal (potential) by the photodetector 105. By detecting and analyzing it, the mechanical properties of the outermost surface several nanometers from the sample surface can be evaluated, and a temperature control mechanism is attached to the measurement environment and measurement of temperature dispersion is also possible. That is. As an example of the scanning viscoelastic microscope accompanied with these temperature component measurement functions, there are those equipped with a lock-in amplifier on “E-sweep” manufactured by SII Nanotechnology Co., Ltd. However, the present invention is not limited thereto, and any apparatus that satisfies the above conditions can be used.

  Next, the phase difference Δδ will be described with reference to FIG. This phase difference Δδ is a value measured using the scanning viscoelastic microscope and is obtained as follows.

First, when the sine vibration l _1a is applied to the sample 101 at a constant amplitude in a direction perpendicular to the film surface (xy plane) while the probe 103 of the cantilever 102 is in contact with the surface of the thin film 101 as the sample, The phase δa of the response vibration l _2a detected by the cantilever 102 is obtained, and then the probe 103 of the cantilever 102 is brought into contact with the surface of the blank silicon wafer 111 under the same temperature condition, while being perpendicular to the film surface (xy plane). The phase δb of the response vibration l _2b detected by the cantilever 102 when a sinusoidal vibration l _1b having a constant amplitude is applied to the silicon wafer 111 in the direction, and the relative phase difference Δδ = between the thin film surface and the silicon wafer surface is obtained. It is a value obtained as δa−δb, and is a value representing the degree of hardness / softness of the sample surface.

Here, the phase difference Δδ in the present invention refers to a probe 103 having a cantilever 102 (spring constant 0.1 N / m), which is a probe of a scanning viscoelastic microscope, on the surface of a thin film 101 formed on a silicon wafer under vacuum conditions. The phase δa of the response vibration l _2a detected by the cantilever 102 when the sine vibration l _1a is applied to the sample 101 at an amplitude of 1 nm and a frequency of 100 Hz in a direction perpendicular to the film surface (xy plane) Next, a sine vibration l _1b having an amplitude of 1 nm and a frequency of 100 Hz in the direction perpendicular to the film surface (xy plane) is contacted with silicon while the probe 103 of the same cantilever 102 is brought into contact with the surface of a blank silicon wafer 111 under the same temperature condition. when given to the wafer 111, it obtains a phase δb response vibration l _2b the cantilever 102 detects, thin film surface and the sheet To a value obtained as a relative phase difference Δδ = δa-δb con wafer surface.

  Here, the phase difference observed by the above method is a value representing the degree of hardness / softness of the sample surface. When the sample surface is hard, the phase difference is small, and when it is soft, the phase difference is large. Therefore, evaluating the temperature dependence of the phase difference Δδ directly evaluates the temperature dependence of the hard / soft surface of the sample, that is, viscoelasticity. Therefore, the temperature at which the phase difference starts to increase, that is, the phase difference increase start temperature Ts can be the glass transition temperature (surface Tg) of the outermost surface (about 1 to 10 nm) of the thin film. Here, the molecules in the vicinity of the surface of the thin film 101 are in contact with a different medium (air) and are in an energetically unstable state as compared with the inside (bulk) of the resin. The surface Tg is a temperature lower than the bulk glass transition temperature (bulk Tg) obtained by a general method (such as suggested scanning calorimetry (DSC)). Therefore, the resin composition for an easily surface-shaped sheet according to the present invention is not limited to bulk thermal characteristics, but by controlling the thermal characteristics of the outermost surface, that is, the glass transition temperature (surface Tg) of the surface to a specific condition. In particular, it exhibits an excellent effect that has not been achieved so far, such as excellent releasability at the time of shape shaping on the nano order and excellent long-term storage stability of the shape.

  Hereinafter, a method for obtaining the phase difference increase start temperature Ts will be described in detail.

  As a method for obtaining the retardation increase starting temperature Ts of the resin composition for an easily surface-shaped sheet of the present invention, first, it is necessary to form a thin film 101 of the resin composition on a silicon wafer with a dry film thickness of 250 nm. . Here, the film thickness of the thin film 101 of the resin composition is preferably a dry film thickness of 250 nm, but the retardation increase start temperature Ts does not change in the dry film thickness range of 200 nm to 300 nm. 101 may be formed.

  As a method of forming the thin film 101 of the resin composition on a silicon wafer, when the resin composition contains a thermoplastic resin as a main component, the resin composition is dissolved in a solvent, and the solution is used. It can be produced by applying a known coating method such as spin coating, dip coating, bar coating, gravure coating or blade coating on a silicon wafer and then removing the solvent by drying. Here, the solvent using the resin composition is a solvent in which the resin composition dissolves, and it does not repel when coated on a silicon wafer and dried, and can be removed by drying. Is preferably selected. In addition, when the resin composition contains organic fine particles, inorganic fine particles, metals, metal salts, other additives and other components that are insoluble in the solvent, the resin composition can be obtained by filtration through a filter or centrifugation. After removing insoluble components from the product, a solution in which the resin composition is dissolved in a solvent is prepared and applied. Further, when there is a possibility that the resin composition contains additives such as a plasticizer, a surfactant, and a dye, as described above, after removing insoluble components from the resin composition, After removing these additives by a recrystallization method, a chromatography method, an extraction method or the like, a solution dissolved in the solvent of the resin composition is prepared and applied.

  As a drying method for removing the solvent, a known method such as hot drying using a hot air oven, a hot plate, infrared rays, vacuum drying, freeze drying, or a combination thereof may be used. It is necessary to sufficiently remove the solvent, and the solvent content in the coating film must be 100 ppm or less. When drying by heating, the drying temperature is preferably not less than the bulk glass transition temperature Tg1 of the resin composition and less than the decomposition temperature, more preferably not less than Tg1 and not less than the boiling point of the solvent and less than the decomposition temperature of the resin composition. . However, when drying at a temperature equal to or higher than the boiling point of the solvent, if the temperature is increased to a predetermined drying temperature after application, the solvent will rapidly evaporate, creating voids inside the thin film or causing repelling, resulting in a thin film surface. After coating, it is preferable that the coating is dried for a while at Tg1 or higher and lower than the boiling point of the solvent, and then raised to Tg1 or higher and higher than the boiling point of the solvent and lower than the decomposition temperature. . The drying time is preferably 4 hours or longer, more preferably 5 hours or longer. In addition, after drying, in order to prevent moisture absorption, drying is performed immediately before measurement, and measurement is performed immediately after the completion of drying. If measurement immediately after drying is impossible, it is preferable to store the sample in a desiccator, storage, etc. under conditions that do not absorb moisture, such as dry conditions, dry nitrogen conditions, and vacuum conditions, until immediately before measurement.

  In the case where the resin composition is mainly composed of a curable resin such as a photo-curable resin or a thermosetting resin, a method for forming the thin film 101 of the resin composition on a silicon wafer is as follows. If the resin composition is in a liquid state, the resin composition is applied onto a silicon wafer using a known coating method such as spin coating, dip coating, bar coating, gravure coating, blade coating, and the coating film is cured. Can be formed. In addition, when the resin composition is in a solid state or is in a liquid state but has a very high viscosity, a solution in which the resin composition is dissolved in a solvent is applied using the above-described method, and then dried. It can be formed by curing the coating film after removing the solvent.

As a curing method, in the case of a photocurable resin, it is only necessary to irradiate light having a wavelength at which the resin composition is sensitized. As a measurement sample, it is cured by irradiation with 500 mJ / cm ² or more. Is used.

  Moreover, in the case of a thermosetting resin, it may be cured by heating for a certain time to a temperature not lower than the thermal polymerization start temperature. Use However, the heating temperature is less than the decomposition temperature of the cured product of the resin composition.

  In the case of using a solvent, as a drying method, a known method such as hot air oven, hot plate, heat drying with infrared rays, vacuum drying, freeze drying, or a combination thereof may be used. It is necessary to prevent the solvent from being contained in the subsequent thin film, and the solvent content in the cured film needs to be 100 ppm or less. In order to set the solvent content in the coated film after curing to 100 ppm or less, drying is preferably performed after curing as necessary.

Next, using the thin film 101 produced by the above method, the temperature dispersion of the phase difference Δδ on the surface of the thin film 101 is obtained by the following procedure using a scanning viscoelastic microscope. As the procedure, first, as a measurement condition, a probe 103 of a cantilever 102 (spring constant 0.1 N / m), which is a probe of a scanning viscoelastic microscope, is placed on the surface of the sample 101 under vacuum conditions. The phase δa ₁ of the response vibration l _1a detected by the cantilever 102 when a sinusoidal vibration l _1a having an amplitude of 1 nm and a frequency of 100 Hz is applied to the sample 101 in a direction perpendicular to the film surface (xy plane) while contacting is obtained. . Note that δa ₁ is measured 10 times or more at the same measurement point, and the average value of 60% of the obtained values is the phase δa _{1 of the} sample surface. Next, in this measurement, the phase δa ₂ , δa ₃ ,... Δa _na of the response signal l _1a is measured while changing the na location (na ≧ 5), and an average value of 60% intermediate values of the obtained values Therefore, the phase δa of the sample surface is set.

Subsequently, a sine vibration l _1b having an amplitude of 1 nm and a frequency of 100 Hz in a direction perpendicular to the film surface (xy plane) while contacting the probe 103 of the same cantilever 102 with the surface of the silicon wafer 111 that is a blank under the same temperature condition. Is applied to the silicon wafer 111, the phase δb ₁ of the response vibration l _2b detected by the cantilever 102 is obtained. Note that δb ₁ is measured 10 times or more at the same measurement point, and is a phase value δb ₁ of the silicon wafer surface, which is an average value of 60% intermediate values of the obtained values. Next, in this measurement, the phase δb ₂ , δb ₃ ,... Δb _nb of the response signal l _2b is measured by changing the nb location (nb ≧ 5), and an average value of 60% intermediate values of the obtained values Therefore, the phase δb of the sample surface is set. From the obtained δa and δb, a relative phase difference Δδ = δa−δb between the thin film surface and the silicon wafer surface is obtained.

  The above conditions are measured every 1 ° C. within a temperature range of −50 ° C. to (Tg 1 + 20 ° C.) (Tg 1 is the glass transition temperature of the resin composition), and the temperature dispersion of the phase difference Δδ is measured. At this time, measurement is performed by changing the measurement point for each temperature. Next, the obtained phase difference Δδ at each temperature is plotted against the temperature. This plot is observed from the lowest temperature side, and the temperature at which the increase starts as the temperature rises is defined as a phase difference increase start temperature Ts.

Here, the phase difference increase start temperature Ts is obtained as shown in FIG. 2A when the plot is observed from the lowest temperature side with respect to the group P11 of plots serving as a baseline, the phase difference Δδ is When the temperature range Tp gradually increases as a whole and the increasing temperature range Tp is 10 ° C. or more, a phase difference increasing region P12 is set, and a straight line l ₁₁ extending from the low temperature side base line to the high temperature side from the phase difference increasing region is the temperature at the intersection of the tangent line l ₁₂ the tangent slope of the phase difference increased area drawn to maximize, to the phase difference increases starting temperature Ts.

  Here, when obtaining the phase difference increase start temperature Ts, the temperature dispersion curve is low as shown in FIG. 2A and the phase difference Δδ is substantially constant, as shown in FIG. 2B. In some cases, the dispersion curve gradually decreases on the low temperature side or gradually increases on the low temperature side as shown in FIG. 2C. In this case, the plot groups P21 and P31 are set as the baseline. When the phase difference Δδ increases from the base line and the increasing temperature range Tp is 10 ° C. or more, the phase difference Δδ increase regions P22 and P32 are set, and the same procedure as in FIG. Ask.

  The material of the cantilever 102 used for the series of measurements is not particularly specified, but a material whose spring constant does not change in the measurement temperature range is used. For example, silicon, silicon nitride, or a silicon-deposited metal such as gold or platinum is preferably used. Specific examples include OMCL-RC800PB-1 manufactured by Olympus Co., Ltd., in which metal such as gold or platinum is vapor-deposited on both sides, but is not limited thereto.

  As described above, the resin composition for an easily surface-shaped sheet according to the present invention has a retardation increase start temperature Ts determined by the above-described method of 25 ° C. or more, more preferably a retardation increase start. The temperature Ts is preferably 30 ° C. or higher, most preferably 40 ° C. or higher. That is, in the easy-surface formable sheet made of the resin composition whose retardation increase start temperature Ts obtained by the above method is less than the above range, the surface is softened during the shaping of the nano-order structure. , Adhesion to the mold surface, mechanical strength of the molded product is greatly reduced, the pattern breaks at the time of mold release, and even if it can be released, the pattern is deformed at the time of mold release and the pattern collapses Even if the mold can be released without deformation, it is not preferable because the stability over time and the impact resistance during long-term storage of the shape deteriorate. In the pattern forming method of the present invention, the effect of the present invention can be achieved for the first time by controlling the retardation increase starting temperature Ts, that is, the glass transition temperature (surface Tg) of the outermost surface within the above range. is there. In particular, at the time of nano-order shape shaping, the mold can be released without breaking or falling down, and even if the pattern is stored for a long period of time, the shape can be maintained without breaking the pattern. This is the first time.

  In addition, the resin composition for an easily surface-shaped sheet of the present invention is preferably composed of a resin composition mainly composed of any one of a thermoplastic resin, a photocurable resin, and a thermosetting resin, or a mixture thereof. . Here, the main component indicates that the above-mentioned resin preferably comprises 50% by weight or more, more preferably 60% by weight or more, and most preferably 70% by weight or more. As such a resin, in the case of a thermoplastic resin, specifically, polyester resins such as polyethylene terephthalate, polyethylene-2, 6-naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, Polyolefin resins such as polymethylpentene, polyamide resins, polyimide resins, polyether resins, polyester amide resins, polyether ester resins, acrylic resins, polyurethane resins, polycarbonate resins, polyvinyl chloride resins Etc. can be used. Among them, polyester resins, polyolefin resins, polyamide resins, acrylic resins, polycarbonate resins or the like are particularly preferred because of the variety of monomer types to be copolymerized and the ease of adjusting the material properties. A thermoplastic resin selected from these mixtures is preferably used.

  Moreover, as an example of a photocurable resin, the compound which has at least 1 radical polymerizability in a molecule | numerator, or a compound which has cationic polymerizability etc. are mentioned. Compounds having radical polymerizability are active in the presence of a compound that generates radicals or cations by active energy rays to polymerize or cross-link, or a polymerization initiator that generates radicals or cations by active energy rays. Examples thereof include compounds that are polymerized or cross-linked by irradiation with energy rays. Examples thereof include those containing at least one ethylenically unsaturated bond in the structural unit, those containing a polyfunctional vinyl monomer in addition to a monofunctional vinyl monomer, and oligomers, polymers and mixtures thereof. Examples of the compound having at least one cationic polymerizability in the molecule include compounds selected from one or more compounds selected from a compound having an oxirane ring, a compound having an oxetane ring, and a vinyl ether compound.

  Examples of thermosetting resins include acrylic resins, epoxy resins, unsaturated polyester resins, phenol resins, urea / melamine resins, polyurethane resins, silicone resins, and the like, one or two selected from these. A mixture of the above can be used.

  It is preferable that a polymerization initiator is blended in the photocurable resin and the thermosetting resin. In the case of a photo-curing resin, a photo-polymerization initiator that generates radical species or cationic species by irradiation with active energy rays is used in accordance with the photosensitive wavelength and polymerization type, and in the case of a thermosetting resin, it is adjusted to the process temperature. It is preferable to use a thermal polymerization initiator.

  Further, in the resin composition for an easily surface-shaped sheet of the present invention, in order to set the retardation increase starting temperature Ts to 25 ° C. or higher, when the resin as the main component is a thermoplastic resin, differential scanning calorimetry (Hereinafter referred to as DSC), the glass transition temperature Tg1 in the temperature rising process (temperature rising rate: 10 ° C./min), that is, the bulk Tg is preferably 70 to 160 ° C., more preferably 90 to 160 ° C., most preferably Preferably, it is in the range of 110 to 150 ° C.

  The glass transition temperature Tg1 here is a value obtained by a method based on JIS K-7121 (1999), and is a glass transition of a differential scanning calorimetry chart obtained when scanning at a heating rate of 10 ° C./min. The value obtained from the point where the straight line equidistant in the vertical axis direction from the extended straight line of each base line and the curved line of the step-like change part of the glass transition intersect. When the glass transition temperature Tg1 is lower than 70 ° C., when the resin composition is formed into a sheet and shaped, when a high-definition pattern or a high aspect ratio pattern is formed, the pattern may be deformed at the time of release. Even if the mold can be released, the thermal stability of the molded product is low, and the shape changes with time. When the glass transition temperature Tg1 is higher than 160 ° C., the forming temperature is high and energy is inefficient, and the volume fluctuation during heating / cooling of the sheet becomes large so that the sheet can be released from the mold. Even if it can be eliminated or released, it is not preferable because the transfer accuracy of the pattern is lowered, or the pattern is partially lost to cause a defect. In the case where the resin whose main component is the resin composition for an easily surface-shaped sheet of the present invention is a thermoplastic resin, by controlling the glass transition temperature Tg1 to the above specific range, good transferability and releasability can be obtained. I was able to get it.

  Further, when the resin as the main component is a curable resin, the glass transition temperature Tg3 after curing, that is, the bulk Tg is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and particularly preferably 60 ° C. or higher.

  That is, when the glass transition temperature Tg3 is lower than this range, when the resin composition is formed into a sheet, when forming a high-definition pattern or a high aspect ratio pattern, the pattern is deformed at the time of mold release, Moreover, even if it can release, it is not preferable because the thermal stability of the molded product is low and the shape changes over time. When the resin which is the main component of the resin composition for an easily surface-shaped sheet of the present invention is a thermoplastic resin, good transferability and releasability are obtained by controlling the glass transition temperature Tg3 within the specific range. It can be done.

  In the resin composition for an easily surface-shaped sheet of the present invention, when the resin as the main component is a thermoplastic resin, the polystyrene equivalent weight average molecular weight Mw by gel permeation chromatography (hereinafter referred to as GPC) is preferably 10,000 to 10,000. 100000, More preferably, it is 15000-90000, Most preferably, it is 20000-80000. When the resin composition contains organic fine particles, inorganic fine particles, metals, metal salts, other additives and other components that are insoluble in the solvent, the resin composition can be obtained by filtration with a filter or centrifugation. It is a value measured by adjusting a solvent solution of the resin composition after removing insoluble components from the product. If there is a possibility that the resin composition contains additives such as plasticizers, surfactants, dyes, etc., as described above, after removing insoluble components, reprecipitation, recrystallization, chromatography, etc. It is a value measured by adjusting the solvent solution of the resin composition again after performing the graphic method, the extraction method, and the like.

  In the resin composition for an easily surface-shaped sheet of the present invention, when the polystyrene-equivalent weight average molecular weight Mw is less than 10,000, not only the mechanical strength is weakened, but also the retardation increase start temperature Ts is decreased to less than 25 ° C. In particular, when a nano-order high-accuracy pattern or high aspect ratio pattern is molded and released from the mold, the pattern breaks or deforms. This is not preferable because the durability and the thermal stability of the shape deteriorate. In addition, when the polystyrene-equivalent weight average molecular weight Mw is more than 100,000, there is a drawback that it is difficult to form, particularly in the nano-order shape shaping, and the entire pattern is poorly formed or the pattern is partially missing. This is not preferable because it causes. In the easy-surface-formable sheet composition of the present invention, by controlling the polystyrene-equivalent weight average molecular weight Mw to the above specific range, formability is imparted while maintaining the retardation increase starting temperature Ts at 25 ° C. or higher. As a result, it is possible to release the pattern without rupture, collapse, etc. at the time of mold release, particularly at the time of nano-order shape shaping, and even if the pattern is stored for a long time, the pattern does not collapse, The shape was able to be maintained.

  Further, in the resin composition for an easily surface-shaped sheet of the present invention, in order to set the retardation increase starting temperature Ts to 25 ° C. or higher, when the resin as the main component is a thermoplastic resin, It is also preferable to remove the low molecular weight component by a technique such as GPC, recrystallization, or most precipitation. In that case, in the molecular weight distribution curve by GPC, the content R of the component having a polystyrene-equivalent molecular weight Mw of 5,000 or less with respect to the integral value of the entire molecular weight distribution is preferably 3% by weight or less, more preferably 2% by weight or less, particularly It is preferable to control to 1% by weight or less. In some cases, the phase difference increase start temperature Ts can be set to 25 ° C. or higher by narrowing the molecular weight distribution. In that case, the polydispersity Mw / Mn, which is the ratio between the polystyrene-equivalent weight average molecular weight Mw and the polystyrene-equivalent number average molecular weight Mn by GPC, is preferably 3 or less, more preferably 2.5 or less, and particularly preferably 2 or less. It is good.

In the resin composition for an easily surface-shaped sheet according to the present invention, when the resin as the main component is a thermoplastic resin, the intrinsic viscosity is preferably 0.30 to 0.65 dl / g. More preferably, it is 0.32-0.65, More preferably, it is 0.35-0.65. The intrinsic viscosity here is the same as the value obtained by dissolving the resin in 100 ml of orthochlorophenol (solution concentration C = 1.2 g / ml) and measuring the viscosity of the solution at 25 ° C. using an Ostwald viscometer. The value obtained as [η] in the following formula using the value obtained by measuring the viscosity of the solvent.
Ηsp / C = [η] + K [η] ² · C
(Where ηsp = (solution viscosity / solvent viscosity) −1, K is the Huggins constant (assuming 0.343))
If the resin composition contains organic fine particles, inorganic fine particles, metals, metal salts, and other additives that are insoluble in the solvent, the insoluble components may be removed by filtration with a filter or centrifugation. It is the value measured by adjusting the solution after the removal. If there is a possibility that the resin composition contains additives such as plasticizers, surfactants, dyes, etc., after removing insoluble components, reprecipitation method, recrystallization method, chromatography method, extraction This is a value measured by adjusting the solution again after performing the method. If the intrinsic viscosity is larger than the above range, deformation of the sheet is difficult to occur during shaping, and the mold shape is not filled with resin filling in the mold especially during nano-order shape shaping. Even if it cannot be transferred sufficiently, the forming speed tends to be slow, or residual stress remains in the molded product, which tends to lower the shape stability. For this reason, it is necessary to increase the load to increase the press pressure, or to increase the pressurization time. However, this is not efficient and is not preferable. Moreover, when the load is increased, the load on the mold is increased, and repeated use durability may be deteriorated. In addition, if the above range is not satisfied, the mechanical strength of the molded product is greatly reduced, the pattern breaks at the time of mold release, or even if the mold can be released, the pattern collapses due to deformation at the time of mold release. Even if it occurs or can be released without deformation, it is not preferable because the stability over time and the impact resistance during long-term storage of the shape deteriorate. In the easy-surface formable sheet of the present invention, by setting the intrinsic viscosity of the resin composition constituting the sheet within this range, it can be easily molded even during nano-order shape shaping.

  Moreover, the resin composition for an easily surface-shaped sheet of the present invention is more preferably a polyester resin as a main component when the resin having a main component is a thermoplastic resin. In particular, a polyester obtained by copolymerizing a dicarboxylic acid or an ester-forming derivative thereof and a copolymer of a diol is preferably used because of easy polymerization.

  Dicarboxylic acid components include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalonic acid, ethylmalonic acid, etc. Aliphatic dicarboxylic acids, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexane dicarboxylic acid, decalin dicarboxylic acid, and the like, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1 , 5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyletherdicarboxylic acid, 5-sodium sulfoisophthalic acid, phenylendane Zikal Typical examples include dicarboxylic acids such as acid, anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, aromatic dicarboxylic acid such as 9,9′-bis (4-carboxyphenyl) fluorenic acid, or ester derivatives thereof. It is not limited. A compound having two carboxyl groups in the molecule is appropriately selected and used. Moreover, these may be used independently or may be used in multiple types as needed.

  In addition, dicarboxy compounds obtained by adding oxyacids such as l-lactide, d-lactide, hydroxybenzoic acid, and derivatives thereof, and a combination of a plurality of the oxyacids to the carboxy terminus of the dicarboxylic acids described above are also preferable. Used.

  Examples of the diol component include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol. Alicyclic diols such as cyclohexanedimethanol, spiroglycol and isosorbide, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9′-bis (4-hydroxyphenyl) fluorene, Diols such as aromatic diols are given as representative examples, but are not limited thereto. A compound having two hydroxyl groups in the molecule is appropriately selected and used. Moreover, these may be used independently or may be used in multiple types as needed.

  In addition, dihydroxy compounds obtained by adding diols to the hydroxy terminus of the diols described above are also preferably used. The glycols used include ethylene glycol, 1,2-propanediol 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, neopentyl glycol, 1, Aliphatic diols such as 5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2′-bis (4′-β-hydroxyethoxyphenyl) propane, 1,2- Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, alicyclic diols such as 1,4-cyclohexanedimethanol, and aromatic diols such as bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol And so on. In these diols, different diols may be added to the two hydroxy ends, respectively, and a plurality of diols may be linked. When a plurality are connected, different diols may be mixed.

  The polyester resin constituting the resin composition for an easily surface-shaped sheet of the present invention can be obtained by appropriately selecting and copolymerizing the above-mentioned dicarboxylic acid component and diol component.

  Here, it is particularly preferable that the polyester resin constituting the resin composition for an easily surface-shaped sheet of the present invention contains at least a repeating unit having a fluorene skeleton as a copolymerization component. By including a repeating unit having a fluorene skeleton as a copolymerization component, not only is it particularly excellent in nano-order shape-shaping property, but also high transparency and the effect of reducing optical distortion are preferable.

  In order to introduce such a fluorene skeleton into the polyester resin, it can be obtained by copolymerizing a diol having a fluorene skeleton as a diol component or a derivative thereof. It can also be obtained by copolymerizing a dicarboxylic acid having a fluorene skeleton or a derivative thereof.

  Examples of the diol having a fluorene skeleton include 9,9′-bis (4-hydroxyphenyl) fluorene, 9,9′-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9′-bis. (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9'-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9'-bis (4-hydroxy-3,5-ethylphenyl) Fluorene, 9,9'-bis (4-hydroxy-3-propylphenyl) fluorene, 9,9'-bis (4-hydroxy-3,5-dipropylphenyl) fluorene, 9,9'-bis (4- Hydroxy-3-isopropylphenyl) fluorene, 9,9'-bis (4-hydroxy-3,5-diisopropylphenyl) fluorene, 9,9'-bis (4 Hydroxy-3-n-butylphenyl) fluorene, 9,9'-bis (4-hydroxy-3-di-n-butylphenyl) fluorene, 9,9'-bis (4-hydroxy-3-isobutylphenyl) fluorene 9,9′-bis (4-hydroxy-3,5-diisobutylphenyl) fluorene, 9,9′-bis (4-hydroxy-3- (1-methylpropyl) phenyl) fluorene, 9,9′-bis (4-hydroxy-3,5-bis (1-methylpropyl) phenyl) fluorene, 9,9′-bis (4-hydroxy-3-phenylphenyl) fluorene, 9,9′-bis (4-hydroxy-3) , 5-diphenylphenyl) fluorene, 9,9′-bis (4-hydroxy-3-benzylphenyl) fluorene, 9,9′-bis (4-hydroxy-) 3,5-dibenzylphenyl) fluorene and the like.

  A dihydroxy compound in which a diol is added to the hydroxy terminal of the diol having the fluorene skeleton is also preferably used. Examples of glycols used include ethylene glycol, 1,2-propanediol 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, neopentyl glycol, 1, Aliphatic diols such as 5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2′bis (4′-β-hydroxyethoxyphenyl) propane, 1,2-cyclohexane Alicyclic diols such as dimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and aromatic diols such as bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol Etc. In these diols, different diols may be added to the two hydroxy ends of the diol having a fluorene skeleton, and a plurality of diols may be linked. When a plurality are connected, different diols may be mixed.

  Examples of dicarboxylic acids having a fluorene skeleton include 9,9′-bis (4-carboxyphenyl) fluorene, 9,9′-bis (4-carboxyphenyl) fluorene, 9,9′-bis ( 4-carboxy-3-methylphenyl) fluorene, 9,9′-bis (4-carboxy-3,5-dimethylphenyl) fluorene, 9,9′-bis (4-carboxy-3-ethylphenyl) fluorene, 9 , 9′-bis (4-carboxy-3,5-ethylphenyl) fluorene, 9,9′-bis (4-carboxy-3-propylphenyl) fluorene, 9,9′-bis (4-carboxy-3, 5-dipropylphenyl) fluorene, 9,9'-bis (4-carboxy-3-isopropylphenyl) fluorene, 9,9'-bis (4-carboxy- 3,5-diisopropylphenyl) fluorene, 9,9′-bis (4-carboxy-3-n-butylphenyl) fluorene, 9,9′-bis (4-carboxy-3-di-n-butylphenyl) fluorene 9,9′-bis (4-carboxy-3-isobutylphenyl) fluorene, 9,9′-bis (4-carboxy-3,5-diisobutylphenyl) fluorene, 9,9′-bis (4-carboxy- 3- (1-methylpropyl) phenyl) fluorene, 9,9'-bis (4-carboxy-3,5-bis (1-methylpropyl) phenyl) fluorene, 9,9'-bis (4-carboxy-3) -Phenylphenyl) fluorene, 9,9'-bis (4-carboxy-3,5-diphenylphenyl) fluorene, 9,9'-bis (4-carboxy-3- Benzylphenyl) fluorene, 9,9'-bis (4-carboxy-3,5-dibenzylphenyl) fluorene, and the like.

  In addition, oxyacids such as l-lactide, d-lactide, and hydroxybenzoic acid, and derivatives thereof, a combination of a plurality of the oxyacids, and the like were added to the carboxyl group terminal of the dicarboxylic acid having the fluorene skeleton. Dicarboxy compounds are also preferably used.

  The polyester resin having a fluorene skeleton constituting the resin composition for an easily surface-shaped sheet of the present invention is copolymerized by appropriately selecting the above-mentioned dicarboxylic acid and diol, dicarboxylic acid having a fluorene skeleton, and diol having a fluorene skeleton. Can be obtained. As the polymerization method, a known technique such as transesterification method, direct polymerization method, solution polymerization method, and interfacial polymerization method can be used.

  Here, in the polyester resin having a fluorene skeleton constituting the resin composition for an easy-surface-formable sheet of the present invention, the amount of diol having a fluorene skeleton contained in 100 mol of all diol components is n1, and the moles of other diols. A diol having a fluorene skeleton contained in 100 mol of all diol components, where n3 is the molar amount of dicarboxylic acid having a fluorene skeleton contained in 100 mol of all dicarboxylic acid components and n2 is the mol amount of other dicarboxylic acids. The sum n1 + n2 of the molar amount n2 of the dicarboxylic acid having a fluorene skeleton contained in 100 mol of all dicarboxylic acid components is preferably n ≦ n1 + n2 ≦ 160, more preferably 30 ≦ n1 + n2 ≦ 150, most preferably 40 ≦ n1 + n2 ≦ 14 In which the good is. When the n1 + n2 is less than 20, the polyester resin has crystallinity and the moldability is deteriorated. In particular, it is difficult to form a nano-order shape, or the birefringence of the polyester resin is increased. Since distortion may remain, it is not preferable. On the other hand, when n1 + n2 exceeds 160, the sheet itself becomes brittle and the mechanical strength may be lowered. The polyester resin having a fluorene skeleton constituting the easy-surface formable sheet of the present invention, the molar amount n1 of a diol having a fluorene skeleton contained in 100 mol of all diol components, and the fluorene skeleton contained in 100 mol of all dicarboxylic acid components By controlling the sum n1 + n2 of the mol amount n2 of dicarboxylic acid within the range of the above-mentioned specific ratio, not only the nano-order shape shaping property is particularly excellent, but also the optical distortion of the molded product is reduced and the mechanical strength It was possible to achieve both.

  Further, in the polyester resin having a fluorene skeleton constituting the resin composition for an easily surface-shaped sheet according to the present invention, the molar amount of the diol having a fluorene skeleton contained in 100 mol of all diol components is n1, and the moles of other diols. The ratio n1 / n3 of the quantity n3 is preferably in the range of 20/80 to 100/0, more preferably 30/70 to 100/0, most preferably 40/60 to 100/0. When the ratio n1 / n3 is less than 20/80, the moldability of the polyester resin is lowered, and in particular, it becomes difficult to form a nano-order shape, the birefringence increases, and strain remains after molding. This is not preferable. In the polyester resin having a fluorene skeleton constituting the resin composition for an easily surface-shaped sheet of the present invention, by controlling the ratio n1 / n3 within the above-described specific range, particularly in the nano-order shape shapeability. Not only is it excellent, but also the optical distortion of the molded product can be reduced. Among these diols having a fluorene skeleton, diols were added to the hydroxy terminal of the diol having a fluorene skeleton as a copolymer component from the viewpoint of the reactivity during the polymerization reaction and the mechanical properties of the molded product. It preferably contains at least a dihydroxy compound. In this case, out of 100 mol of the diol having a fluorene skeleton, when the molar amount of the diol added to the hydroxy terminus is n1 ′ and the molar amount of the diol not added is n1 ″, the ratio n1 ′ / n1 ″ is preferably 50/50 to 100/0. More preferably, it is 60 / 40-100 / 0, Most preferably, it is 70 / 30-100 / 0.

  Further, in the polyester resin having a fluorene skeleton constituting the resin composition for an easily surface-formable sheet of the present invention, the amount of dicarboxylic acid having a fluorene skeleton contained in 100 mol of all dicarboxylic acid components is n2, and other dicarboxylic acids. Although the ratio n2 / n4 of the amount of mol of acid n4 is arbitrary, it is preferably 0/100 to 60/40, more preferably 0/100 to 50/50, and most preferably 0/100 to 40/60. It is good. That is, when n2 / n4 exceeds 60/40, polymerization is difficult, or even if polymerization can be performed, the sheet itself becomes brittle and mechanical strength may be lowered. In the polyester resin having a fluorene skeleton constituting the resin composition for an easily surface-formable sheet of the present invention, mechanical strength is imparted to the polyester resin by controlling n2 / n4 within the specific range described above. Is possible.

  Here, in the polyester resin having a fluorene skeleton constituting the resin composition for an easily surface-shaped sheet of the present invention, in 100 mol% of other dicarboxylic acid components, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexane dicarboxylic acid, etc. When the molar amount of the alicyclic dicarboxylic acid is n4 ′ and the molar amount of other dicarboxylic acids other than the alicyclic dicarboxylic acid is n4 ″, the ratio n4 ′ / n4 ″ is preferably 50/50 to 100 / 0, more preferably 60/40 to 100/0, and most preferably 70/30 to 100/0. When the ratio n4 ′ / n4 ″ is less than 50/50, it is not preferable because the optical distortion of the molded product increases. The polyester resin having a fluorene skeleton constituting the resin composition for an easily surface-formable sheet of the present invention. By controlling the ratio n4 ′ / n4 ″ to the above-mentioned specific value, it is not only possible to shape at high speed, but also higher transparency and optical distortion can be reduced, which is preferable. .

Moreover, in the polyester resin which has a fluorene skeleton which comprises the resin composition for easily surface-shaped formable sheets of this invention, it is preferable to control a copolymerization rate so that the following relational expressions (1)-(3) may be satisfy | filled.
30 ≦ n1 + n2 ≦ 150 (1)
n1 / n3 = 30/70 to 100/0 (however, n1 + n3 = 100) (2)
n2 / n4 = (arbitrary) (however, n2 + n4 = 100) (3)
More preferably,
40 ≦ n1 + n2 ≦ 150 (1)
n1 / n3 = 40 / 60-100 / 0 (however, n1 + n3 = 100) (2)
n2 / n4 = (arbitrary) (however, n2 + n4 = 100) (3)
Most preferably 40 ≦ n1 + n2 ≦ 150 (1)
n1 / n3 = 40 / 60-100 / 0 (however, n1 + n3 = 100) (2)
n2 / n4 = 0/100 to 50/50 (where n2 + n4 = 100) (3)
It is.

  In the present invention, by satisfying this relational expression, not only is the nano-order shape-forming property particularly excellent, but it is possible to achieve both reduction in optical distortion of the molded product and mechanical strength.

  In addition, various additives can be added to the resin composition for an easily surface-shaped sheet of the present invention within the range where the effects of the present invention are not lost, during or after the polymerization. Examples of such additives include, for example, organic fine particles, inorganic fine particles, dispersants, dyes, fluorescent brighteners, antioxidants, weathering agents, antistatic agents, mold release agents, thickeners, plasticizers, pH adjusters. Agents and salts can be used. In particular, as a releasing agent, low surface tension carboxylic acids such as long chain carboxylic acids or long chain carboxylates and derivatives thereof, and low surface tension alcohols such as long chain alcohols and derivatives thereof, and modified silicone oils. It is preferable to add a small amount of a compound or the like during polymerization. By adding these low surface tension compounds during polymerization, a low surface tension component can be introduced at the end of the polyester skeleton, thereby reducing the adhesion of the resin to the mold without bleedout of the release agent. This is preferably performed because the releasability can be improved.

  The easily surface-shaped sheet of the present invention can be obtained by processing the above-mentioned resin composition for an easily surface-shaped sheet into a sheet shape. In addition, hereinafter, when the resin composition for an easily surface-shaped sheet constituting the sheet has a thermoplastic resin as a main component, the easily surface-shaped sheet (1) and a curable resin as a main component Let it be an easily surface-shaped sheet (2).

In addition, the easily surface-shaped sheet (1) of the present invention has a dynamic storage elastic modulus E2 ′ obtained by dynamic viscoelasticity measurement (hereinafter referred to as DMA) at the glass transition temperature Tg2 + 40 ° C. of the sheet, Preferably it is 1 × 10 ^{4 to} 5 × 10 ⁶ Pa, more preferably 1 × 10 ^{4 to} 2.0 × 10 ⁶ Pa.

  The glass transition temperature Tg2 here is a glass transition step of a differential scanning calorimetry (1st RUN) chart obtained when scanning at a heating rate of 10 ° C./min by a method based on JIS K-7121 (1999). It is a value obtained from the point at which the straight line equidistant in the vertical axis direction from the straight line obtained by extending each base line intersects the curve of the step-like changing part of the glass transition in the shape changing part.

  The dynamic storage elastic modulus E2 ′ referred to here is a method based on JIS K-7244, the tensile mode, the sample dynamic vibration speed (drive frequency) is 1 Hz, the distance between chucks is 5 mm, the strain amplitude is 10 μm, This value is obtained when temperature dependence (temperature dispersion) is measured under the measurement conditions with an initial value of force amplitude of 100 mN and a heating rate of 2 ° C./min.

In the easily surface formable sheet (1) of the present invention, when the dynamic storage elastic modulus E2 ′ at the glass transition temperature Tg2 + 40 ° C. of the sheet is higher than 1 × 10 ⁴ Pa, the sheet is deformed during shaping. Since the resin does not progress from the middle of the mold, the mold shape cannot be transferred sufficiently, or even if it can be transferred, the forming speed is slow, or the residual stress is applied to the molded product. Tends to remain and shape stability tends to decrease. Therefore, it is necessary to increase the load to increase the pressing pressure or to increase the pressing time, but this is not efficient and is not preferable. Further, when forming a high-definition pattern or a large aspect ratio pattern with a large area, a pressure imbalance may occur in the surface, which may reduce the in-plane uniformity of transfer, which is not preferable. Further, the larger the load, the greater the load on the mold, and the repeated use durability is lowered, which is not preferable. Further, if the dynamic storage elastic modulus E2 ′ is lower than 5 × 10 ⁶ Pa, the fluidity of the resin at the time of pressing becomes too high and the resin flows without being filled into the mold at the time of pressing. It is not preferable.

  In the easy-surface formable sheet (1) of the present invention, by setting the dynamic storage elastic modulus E2 ′ within the specific range, even when shaping a high-definition pattern or a high aspect ratio pattern. In addition to being able to obtain good transfer accuracy, it was also possible to obtain good transfer accuracy and in-plane uniformity.

Further, the easily surface-shaped sheet (1) of the present invention preferably has a dynamic loss elastic modulus E2 ″ obtained by DMA of 1 × 10 ^{3 to} 1.8 × at the glass transition temperature Tg2 + 40 ° C. of the sheet. 10 ⁶ Pa, more preferably 1 × 10 ^{3 to} 1.5 × 10 ⁶ Pa. In other words, when the dynamic loss elastic modulus E2 ″ is higher than 1 × 10 ³ Pa, it is shaped. At this time, deformation of the sheet is less likely to occur, and filling of the resin into the mold does not proceed from the middle, and the shape of the mold cannot be transferred sufficiently. Residual stress remains in the product and the shape stability tends to decrease. For this reason, it is necessary to increase the load to increase the press pressure or to increase the pressurization time. However, this is not efficient and is not preferable. Further, when forming a high-definition pattern or a large aspect ratio pattern with a large area, a pressure imbalance may occur in the surface, which may reduce the in-plane uniformity of transfer, which is not preferable. Further, the larger the load, the greater the load on the mold, and the repeated use durability is lowered, which is not preferable. Further, when the dynamic loss elastic modulus E2 ″ is lower than 1.8 × 10 ⁶ Pa, the fluidity of the resin at the time of pressing becomes too high, and the resin flows without being filled into the mold at the time of pressing. Therefore, in the easy-surface formable sheet (1) of the present invention, by controlling the dynamic loss elastic modulus E2 ″ within the above specific range, a large area of a high-definition pattern or a high aspect ratio pattern is obtained. Even during shaping, good transfer accuracy can be obtained, and good transfer accuracy and in-plane uniformity can be obtained.

In addition, the easily surface-shaped sheet (1) of the present invention has a dynamic storage elastic modulus E1 ′ obtained by DMA at 25 ° C. of preferably 0.1 × 10 ^{9 to} 2.5 × 10 ⁹ Pa, more preferably in the range of ^{0.5 × 10 9 ~2 × 10 9} Pa. When the dynamic storage elastic modulus E1 ′ exceeds 0.1 × 10 ⁹ Pa, the rigidity of the resin increases, and the mold is released from the mold when forming a high-definition pattern or a large aspect ratio pattern with a large area. Is not preferable because it becomes difficult. Further, when the dynamic storage elastic modulus E1 ′ is less than 2.5 × 10 ⁹ Pa, the mechanical strength of the molded product is lowered, and even if deformation occurs at the time of mold release or the mold can be released from the mold, Since stability, impact resistance, etc. deteriorate, it is not preferable. In the easily surface formable sheet (1) of the present invention, by controlling the dynamic storage elastic modulus E1 ′ within the above specific range, a high-definition pattern or a high aspect ratio pattern can be formed at the time of large area shaping. It was possible to achieve both releasability and mechanical strength of the molded product.

In addition, the easy-surface formable sheet (1) of the present invention has a dynamic storage elastic modulus E1 ′ at 25 ° C. obtained by DMA measurement under the above-mentioned conditions of 0.1 × 10 ^{9 to} 2.5 × 10. It is preferably ⁹ Pa, and the dynamic storage elastic modulus E2 ′ at Tg2 + 40 ° C. is preferably 1 × 10 ^{4 to} 5.0 × 10 ⁶ Pa. More preferably, the dynamic storage elastic modulus E1 ′ at 25 ° C. is 0.5 × 10 ⁹ to 2 × 10 ⁹ Pa, and the dynamic storage elastic modulus E2 ′ at Tg2 + 40 ° C. is 1.0 × 10 ⁴ to 2 × 10 ⁶ Pa. In the present invention, by taking such a specific range, it is possible to obtain releasability, high-speed shapeability, transfer accuracy, in-plane uniformity, and mechanical strength of a molded product when forming a large area of a high aspect ratio pattern. Can do.

  In addition, the easily surface-shaped sheet (1) of the present invention has a crystallization enthalpy ΔHcc of 1 J / in a temperature rising process (temperature rising rate: 10 ° C./min) obtained by differential scanning calorimetry (hereinafter referred to as DSC). g or less is preferable.

  The crystallization enthalpy ΔHcc here is a value obtained by a method based on JIS K7122 (1999), and is a differential scanning calorimetry (1st RUN) chart obtained when scanning at a heating rate of 10 ° C./min. The value obtained from the area of the exothermic peak accompanying crystallization. Preferably, it is an amorphous resin having a crystallization enthalpy ΔHcc of 0.1 J / g or less, most preferably 0 J / g. When the crystallization enthalpy ΔHcc is greater than 0.1 J / g, crystallization progresses with time during long-term storage of the sheet before shaping, or when the temperature rises during shaping on the surface The resin constituting the material crystallizes quickly, making it difficult to form. Therefore, not only is high-speed shaping difficult when forming a high-definition pattern or a large aspect ratio pattern, but also the resin is not sufficiently filled in the mold, resulting in a decrease in transfer accuracy. This is not preferable because a pressure imbalance occurs in the surface and the in-plane uniformity of transfer is lowered. In the present invention, by controlling the crystallization enthalpy ΔHcc within the above-mentioned specific range, good high-speed formability, transferability and in-plane uniformity can be obtained even when a high aspect ratio pattern is formed. Can do.

Further, the easily surface-shaped sheet (1) of the present invention has a photoelastic coefficient k at 25 ° C. of preferably 50 × 10 ⁻¹² Pa ⁻¹ or less, more preferably 40 × 10 ⁻¹² Pa ^−1. Hereinafter, it is most preferable that it is 30 × 10 ⁻¹² Pa ⁻¹ or less.

Here, the photoelastic coefficient k is generated when a tensionless phase difference Γ1 (nm) and tension F (Pa) are applied to a sheet of thickness d (nm) in an atmosphere of 25 ° C. and 65 RH%. When the phase difference is Γ2 (nm),
K = (Γ2-Γ1) / (d × F)
It is a value defined by. The phase difference Γ was measured in a state where a tension of 1 kg / mm ² (9.81 × 10 ⁶ Pa) was applied to the film, a polarization microscope equipped with crossed Nicols and sodium D line (wavelength 589 nm) as a light source. In an atmosphere at 25 ° C.

If the photoelastic coefficient k is larger than 50 × 10 ⁻¹² Pa ⁻¹ , optical distortion may remain during processing, and optical characteristics may change in the surface of the molded product, resulting in uneven color tone. It is not preferable. In the easy-surface formable sheet (1) of the present invention, by controlling the photoelastic coefficient k to the above-mentioned specific range, the optical characteristics uniform in the surface of the molded product without remaining optical distortion during processing. Can be obtained.

  The glass transition temperature Tg2 of the easily surface-shaped formable sheet (1) of the present invention is preferably in the range of 70 to 160 ° C, more preferably 80 to 160 ° C, and still more preferably 100 to 150 ° C. When the glass transition temperature Tg2 is lower than 70 ° C., the pattern is deformed at the time of mold release of a high-definition pattern or a high aspect ratio pattern, and even if it can be released, the thermal stability of the molded product shape is low. Since the shape changes with time, it is not preferable. If the glass transition temperature Tg2 is higher than 160 ° C., the shaping temperature is high and energy is inefficient, and the volume fluctuation during heating / cooling of the sheet becomes large, and the sheet is caught in the mold and separated. Even if the mold cannot be formed or released, it is not preferable because the transfer accuracy of the pattern is lowered, or the pattern is partially lost to cause a defect. In the easy-surface formable sheet (1) of the present invention, good transferability and releasability can be obtained by controlling the glass transition temperature Tg2 of the sheet to a specific range.

  The glass transition temperature Tg2, the dynamic storage elastic modulus E ′, the dynamic loss elastic modulus E ″, the photoelastic coefficient k, etc. of the easy-surface formable sheet (1) of the present invention are the monomer types of the resin constituting the sheet. For example, by introducing a rigid skeleton such as bisphenol-A or spiroglycol as other diol components, the glass transition temperature Tg2 and the dynamic storage elastic modulus E ′ can be adjusted. When a flexible skeleton such as polyethylene glycol is introduced, the glass transition temperature Tg2 and the dynamic storage elastic modulus E ′ are lowered.

  Further, the glass transition temperature Tg2, the dynamic storage elastic modulus E ′, the dynamic loss elastic modulus E ″, etc. can also be controlled by introducing a plasticizer or a crosslinking agent. The glass transition temperature Tg2, the dynamic storage elastic modulus E ′, and the dynamic loss elastic modulus E ″ decrease as the amount of the plasticizer increases, but conversely, the elongation at break etc. improves. In the case of a crosslinking agent, if the amount of addition is increased or the degree of progress of crosslinking is increased, the glass transition temperature Tg2, the dynamic storage elastic modulus E ′, and the dynamic loss elastic modulus E ″ are increased. In consideration of these, the sheet can be provided by appropriately adjusting and adding it to satisfy the above-mentioned specific condition range.

  Moreover, you may add the component etc. which harden | cure by electromagnetic wave irradiation etc. to the easily surface formable sheet | seat (1) of this invention. In this case, in the molding process, the mechanical strength and thermal stability of the molded product are improved by irradiating the molded product with electromagnetic waves before curing from the mold or after releasing from the mold. Can do.

  Moreover, various additives can be added to the easy-surface formable sheet (1) of the present invention within the range where the effects of the present invention are not lost. Examples of such additives include, for example, organic fine particles, inorganic fine particles, dispersants, dyes, fluorescent brighteners, antioxidants, weathering agents, antistatic agents, polymerization inhibitors, mold release agents, thickeners, pH Conditioners and salts can be used.

  The easily surface-shaped sheet (1) of the present invention may be stretched in a uniaxial or biaxial direction. However, depending on the material used, orientation crystallization proceeds by stretching at a high magnification. As a result, the glass transition temperature Tg2, the dynamic storage elastic modulus E ′, and the dynamic loss elastic modulus E ″ increase, and the moldability decreases. Therefore, it is preferable to perform stretching while appropriately controlling in accordance with changes in physical property values.

  Moreover, it is preferable that the easily surface formable sheet (2) of the present invention has resistance to deformation after curing. Specifically, when a sheet having a thickness of 100 μm is formed and cured, it is preferable that the sheet does not break even if it is bent 180 ° along a mandrel having a diameter of 100 mm. More preferably, it should not break even if it is bent 180 ° along a mandrel having a diameter of 50 mm. By satisfying this condition, even if it is used alone, it has resistance to deformation in normal use, and even if the area is increased, it does not break by its own weight.

  Moreover, you may add resin components, such as a thermoplastic resin, to the easily surface formable sheet | seat (2) of this invention. In this case, resistance to deformation after curing can be further increased.

Moreover, various additives can be added to the easy-surface-formable sheet (2) of the present invention within the range where the effects of the present invention are not lost. Examples of such additives include, for example, organic fine particles, inorganic fine particles, dispersants, dyes, fluorescent brighteners, antioxidants, weathering agents, antistatic agents, polymerization inhibitors, mold release agents, thickeners, pH Conditioners and salts can be used.
The easy-surface-shaped sheet (1) or the easy-surface-shaped sheet (2) of the present invention may be a sheet composed of the above-mentioned resin alone or a laminate composed of a plurality of layers. However, in the case of such a laminate, it is necessary to provide the above-described layer, that is, an easily surface-formable sheet, on at least one surface (surface layer, surface layer) of the laminate.

  That is, the easily surface formable sheet laminate of the present invention is a laminate composed of a plurality of layers including at least an easily surface formable sheet layer made of the easy surface formable sheet and a base material layer to be a support. The laminate has a laminate structure in which the easy-surface-formable sheet (1) or the easy-surface-formable sheet (2) layer is arranged on at least one surface layer of the laminate. In addition, hereinafter, as a resin composition for an easily surface-shaped sheet, when a thermoplastic resin is the main component, an easily surface-shaped sheet laminate (1), and when a curable resin is the main component, an easy surface Let it be a shapeable sheet laminate (2).

  In the case of such a laminate, it is possible to impart surface properties such as slipperiness and friction resistance, mechanical strength, and thermal stability of the molded product shape as compared with a single sheet. In the case of a laminate composed of a plurality of layers in this way, it is preferable that the entire sheet satisfies the above-mentioned requirements, but even if the entire sheet does not satisfy the above-mentioned requirements, a layer that satisfies at least the above-mentioned requirements is a surface layer. If formed, the surface can be easily shaped. That is, even if the easy-surface formable sheet laminate of the present invention as a whole does not meet the above-mentioned requirements, the easy-surface formable sheet is formed as a surface layer, so that the surface can be easily shaped. Can do.

  The base material to be the support may be a sheet-like material whose shape changes during shaping, a sheet-like material whose shape does not change during shaping, or a combination thereof. However, from the viewpoint of dimensional stability of the molded product after shaping, it is preferable to include at least one sheet-like material whose shape does not change during shaping. In this case, the easy-surface formable sheet layer is formed on either the sheet-like side where the shape changes during shaping, or the sheet-like side where the shape does not change during shaping. It does not matter.

Here, in the case of the easily surface-shaped sheet (1), the sheet-like material whose shape does not change at the time of shaping, at the glass transition temperature of the surface layer (hereinafter, Tg21) + 40 ° C. The dynamic storage elastic modulus E3 ′ of the base material obtained by DMA is preferably 5 × 10 ⁷ Pa or more, more preferably 1.0 × 10 ⁸ Pa or more.

  Here, the glass transition temperature Tg21 of the surface layer of the easy-surface-formable sheet (1) is based on JIS K-7121 (1999) by scraping off the surface layer of the laminate 1 with a cutter. In the stepwise change portion of the glass transition of the differential scanning calorimetry (1st RUN) chart obtained when scanning at a heating rate of 10 ° C./min, a straight line extending each base line. Is a value obtained from the point where a straight line equidistant in the vertical axis direction intersects with the curve of the step-like change portion of the glass transition.

  If the dynamic storage elastic modulus E3 ′ of the base material obtained by DMA is less than the above value, when pressure is applied for molding, the surface layer is not sufficiently pressurized and the pattern accuracy is low. Therefore, it is not preferable. The easy-surface formable sheet laminate (1) of the present invention includes at least one base material whose dynamic storage elastic modulus E3 ′ is controlled in the above-mentioned specific range as such a base material, so that the surface layer has an accuracy. It was possible to obtain a well moldable sheet.

  Further, the glass transition temperature Tg21 of the easy-surface-formable sheet (1) layer constituting the surface layer of the easy-surface-formable sheet laminate (1) of the present invention is preferably 70 to 160 ° C, more preferably. It is good to be in the range of 80 to 160 ° C, particularly preferably 100 to 150 ° C. When the glass transition temperature Tg21 is lower than 70 ° C., the pattern is deformed at the time of mold release of a nano-order high-definition pattern or a high aspect ratio pattern. Since stability is low and a shape changes with time, it is not preferable. When the glass transition temperature Tg21 is higher than 160 ° C., the forming temperature is high and energy is inefficient, and the volume fluctuation during heating / cooling of the sheet becomes large, and the sheet is caught in the mold and separated. Even if the mold cannot be formed or released, it is not preferable because the transfer accuracy of the pattern is deteriorated or the pattern is partially lost to cause a defect. In the easy-surface formable sheet laminate (1) of the present invention, good transferability and releasability can be obtained by controlling the glass transition temperature Tg21 within the specific range.

  Moreover, the glass transition temperature Tg31 after hardening of the surface layer of the easily surface-shaped sheet laminate (2) of the present invention is 40 ° C. or higher, more preferably 50 ° C., and particularly preferably 60 ° C. When the glass transition temperature Tg31 is lower than the above specific range, when a fine pattern or a high aspect ratio pattern is molded, the pattern is deformed at the time of mold release, and even if the mold can be released, the thermal stability of the molded product is reduced. This is not preferable because it is low and the shape changes over time. In the easily surface formable sheet laminate (2) of the present invention, by controlling the glass transition temperature Tg31 after curing of the surface layer to the above specific range, good transferability and releasability can be obtained. It is a thing.

  In the easily surface-shaped sheet laminate (1) of the present invention, the peel strength F between the substrate and the surface layer is preferably 50 mN / cm or more, more preferably 70 mN / cm or more, and most preferably 100 mN. / Cm or more. In the easy-surface formable sheet laminate (2) of the present invention, the peel strength F between the substrate and the cured surface layer is preferably 50 mN / cm or more, more preferably 70 mN / cm or more. Most preferably, it is 100 mN / cm or more.

  The peel strength F here refers to the surface layer of the easily surface-shaped sheet laminate (1) of the present invention or the surface layer after curing of the surface-friendly sheet laminate (2) as a base material. The peel strength F when peeled in the direction of 180 °, and the peel strength F (N / cm) from the average peel force T (N) of 50 mm or longer excluding the rising portion of the SS curve of the peel force = T / W (where T (N): average peel force, W (cm): sample width).

  When the peel strength between the substrate and the surface layer is less than 50 mN / cm, the substrate is pressed against the surface of the easily surface-shaped sheet laminate of the present invention and then released. Since peeling occurs between the surface layers and release is not possible, it is not preferable. In the easy-surface formable sheet laminate (1) or the easy-surface formable sheet laminate (2) of the present invention, a high-definition pattern or a high aspect ratio can be obtained by setting the peel strength to 50 mN / cm or more. Even during pattern formation, the mold can be released without peeling between the substrate and the surface layer.

  Examples of the substrate serving as a support in the easily surface-shaped sheet laminate (1) or the easily surface-shaped sheet laminate (2) of the present invention include a polyester resin, a biaxially stretched polyester film, and a polyolefin resin. Organic film base materials such as acrylic resin, polyamide resin, polyimide resin, polyether resin, polycarbonate resin, metal base materials such as silicon, glass, stainless steel, aluminum, aluminum alloy, iron, steel, titanium, concrete, etc. Inorganic base materials, organic-inorganic composite base materials such as silicon-based resins, and combinations thereof can be applied, but it is more preferable to use a flexible base material to reduce handling and weight. Good from the point of. More preferably, the biaxially stretched polyester film not only has both handleability and mechanical strength, but is also preferable in that other functions can be easily imparted. Further, a composite with a base material having another function is also preferably used as the base material.

  The difference ΔN = | between the refractive index N1 of the surface layer of the easily surface-shaped sheet laminate (1) of the present invention or the cured surface layer of the surface-friendly sheet (2) and the refractive index N2 of the substrate. N1−N2 | is preferably as small as possible, preferably the refractive index difference ΔN is 0 to 0.10, more preferably 0 to 0.08, and even more preferably 0 to 0.06. When the base material has a different refractive index depending on the direction, that is, has a birefringence, the refractive index N2max in the direction with the highest refractive index and the average value of the refractive index N2min in the direction with the lowest refractive index are used. The refractive index of the material is N2. If the refractive index difference ΔN is out of the above range, when the molded product is used for optical applications, color unevenness appears due to color unevenness due to thin film interference derived from the refractive index difference with the base material. This is not preferable. In the easy-surface formable sheet laminate (1) or the easy-surface formable sheet laminate (2) of the present invention, the difference ΔN = | N1−N2 | between the refractive index N1 of the surface layer and the refractive index N2 of the substrate By making the above-mentioned range, a sheet having excellent color uniformity can be obtained. Specifically, when a biaxially stretched polyester film is used as the substrate, the surface layer of the easily surface-shaped sheet laminate (1) or the surface after curing of the easily surface-shaped sheet (2) The refractive index N1 of the easily surface-shaped sheet constituting the layer is preferably 1.55 to 1.7, more preferably 1.58 to 1.68, and still more preferably 1.60 to 1.68. If the refractive index N1 of the surface layer is out of this range, the refractive index difference ΔN from the base polyester film becomes large, and color uniformity due to thin film interference decreases, which is not preferable. By setting the refractive index N1 of the surface layer in the above range, a sheet having good color uniformity can be obtained.

  In addition, various additives can be added to the base material as long as the effects of the present invention are not lost. Examples of additives that can be added and blended include, for example, organic fine particles, inorganic fine particles, dispersants, dyes, fluorescent brighteners, antioxidants, weathering agents, antistatic agents, polymerization inhibitors, mold release agents, Thickeners, pH adjusters, salts and the like can be used.

  The thickness (thickness, film thickness) of the easily surface-shaped sheet (1) or (2) of the present invention is preferably 10 μm to 5 mm, more preferably 20 μm to 2 mm. In the case of the easily surface-shaped sheet laminate (1) or the easily surface-shaped sheet laminate (2), the easily surface-shaped sheet (1) or the easily surface-shaped sheet laminated on the substrate. The thickness of the conductive sheet (2) is preferably 0.1 μm to 5 mm, more preferably 0.2 μm to 1 mm, and particularly preferably 0.2 to 500 μm. It is. In this case, the thickness of the substrate is not particularly limited.

  As a method for forming the easily surface-shaped sheet (1) of the present invention, for example, in the case of a single sheet, the sheet forming material is heated and melted in an extruder and extruded from a die onto a cast drum cooled to be processed into a sheet shape. The method (melt cast method) can be used. As another method, a sheet forming material is dissolved in a solvent, and the solution is extruded from a die onto a support such as a cast drum or an endless belt to form a film, and then the solvent is dried and removed from the film layer to form a sheet. A method of processing into a solution (solution casting method) or the like can be used. Moreover, as a formation method of an easily surface formable sheet (2), a solution cast method can be used among the above-mentioned methods.

  In addition, as a method for producing the easy-surface formable sheet laminate (1) of the present invention, two different thermoplastic resins are put into two extruders, melted and cooled on a cast drum. A method of extruding and processing into a sheet (coextrusion method), a method in which a coating layer material is put into an extruder into a sheet made of a single film, melt extrusion and laminating while extruding from a die (melt lamination method), Easy-to-surface formable sheet (1) is prepared separately and thermocompression bonded with a heated group of rolls (thermal laminating method), bonded with an adhesive (adhesive method), and other sheet formation A method of dissolving the material for use in a solvent and applying the solution onto a sheet (coating method), a method combining these, and the like can be used.

  Moreover, as a manufacturing method of the easily surface formable sheet | seat laminated body (2) of this invention, a base material layer and an easy surface formable sheet (2) are each produced separately, and it bonds together through an adhesive agent etc. Method (adhesion method) and other materials for sheet formation, that is, when the resin composition for easily surface-shaped sheet is liquid, the resin composition is applied on the base material layer, or the material for sheet formation is solid The resin composition is dissolved in a solvent, and the solvent is removed after coating the solution on the base material layer (coating method). And a method combining these can be used.

  Here, as a manufacturing method of the easily surface formable sheet laminate (1) of the present invention, a substrate used in a melt laminating method, a heat laminating method, an adhesion method, a coating method, or the like, or the easily surface forming property of the present invention. As the base material used for the sheet laminate (2), a substrate in which a coating layer such as an easy-adhesion layer is formed is preferably used in terms of adhesive strength with the surface layer. In this case, as a resin constituting the coating layer, for example, polyester resin, polyamide resin, polystyrene resin, polyurethane resin, polyolefin resin, acrylic resin, phenol resin, epoxy resin, melamine resin, polyamide resin, polyimide A resin, a polyether resin, a polycarbonate resin, a thermoplastic resin such as a silicon resin, and a mixture thereof are appropriately selected according to the base material and surface layer to be used. In the body (1), when a biaxially stretched polyester film is used as the base material and the surface layer is mainly composed of a polyester resin, a polyester resin is preferably the main component from the viewpoint of adhesiveness. Used. The main component here means that, among the thermoplastic resins constituting the coating layer, the polyester resin preferably consists of 50% by weight or more, more preferably 60% by weight or more, and most preferably 70% by weight or more. It is shown.

  Moreover, it is preferable to contain a crosslinking agent in a coating layer at points, such as an adhesive improvement with a base material and prevention of blocking resistance. As such a crosslinking agent, a resin or a compound that undergoes a crosslinking reaction with a functional group present in the resin constituting the coating layer, for example, a hydroxyl group, a carboxyl group, a glycidyl group, an amide group, or the like is preferably used. It is possible to use alkylolated urea-based, melamine-based, acrylamide-based, polyamide-based resins and epoxy compounds, isocyanate compounds, coupling agents, aziridine compounds, oxazoline compounds, and mixtures thereof. The type and content of the cross-linking agent are appropriately selected depending on the base material, the surface layer, the resin constituting the coating layer, the type of the cross-linking agent, and the like. The range is from 01 to 50 parts by weight, more preferably from 0.2 to 30 parts by weight. Moreover, it is also preferable to promote a crosslinking reaction by using a catalyst in combination with such a crosslinking agent. In addition, as a crosslinking reaction system, any of a heating system, an electromagnetic wave irradiation system, a moisture absorption system, etc. may be used, but usually a method by heating is preferably used.

  The coating layer preferably contains fine particles for improving the slipperiness of the coating layer and for blocking resistance. For example, inorganic fine particles or organic fine particles can be used. Examples of the inorganic fine particles include gold, silver, copper, platinum, palladium, rhenium, vanadium, osmium, cobalt, iron, zinc, ruthenium, praseodymium, chromium, nickel, aluminum, tin, zinc, titanium, tantalum, zirconium, Metal oxides such as antimony, indium, yttrium, lanthanium, etc., metal oxides such as zinc oxide, titanium oxide, cesium oxide, antimony oxide, tin oxide, indium tin oxide, yttrium oxide, lanthanum oxide, zirconium oxide, aluminum oxide, silicon oxide Metal fluoride such as lithium fluoride, magnesium fluoride, aluminum fluoride, cryolite, metal phosphate such as calcium phosphate, carbonate such as calcium carbonate, sulfate such as barium sulfate, other talc and kaolin, etc. The It is possible to have. In addition to the crosslinked fine particles such as crosslinked styrene and crosslinked acrylic, the organic fine particles are also incompatible with the thermoplastic resin that constitutes the coating layer, but the thermoplastic resin that is finely dispersed to form a sea-island structure is also used as the fine particles. It can also be used. Examples of the shape of the fine particles include a spherical shape, a spheroid shape, a flat shape, a bead shape, a plate shape, and a needle shape, but are not particularly limited. The average particle size of such fine particles is preferably 0.05 to 15 μm from the viewpoint of dispersibility, slipperiness and blocking resistance, and more preferably 0.1 to 10 μm. The amount of the fine particles added is arbitrary, but is usually 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the resin solid content.

  Moreover, various additives can be added to the coating layer as necessary within a range where the effect is not lost. Examples of additives that can be added and blended include, for example, dispersants, dyes, fluorescent brighteners, antioxidants, weathering agents, antistatic agents, polymerization inhibitors, thickeners, antifoaming agents, and UV absorption. Agents, leveling agents, pH adjusters, salts and the like can be used.

  As a method for forming the coating layer on the substrate, means for applying and drying a coating solution in which the material constituting the coating layer is dissolved / dispersed in a solvent is employed. In this case, the solvent to be used is arbitrary, but it is preferable to use water as a main component from the viewpoint of safety. In that case, a small amount of an organic solvent that dissolves in water may be added in order to improve applicability and solubility. Examples of such organic solvents include aliphatic or alicyclic alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, and n-butyl alcohol, diols such as ethylene glycol, propylene glycol, and diethylene glycol, methyl cellosorb, Diol derivatives such as ethyl cellosolve propylene glycol monomethyl ether, ethers such as dioxane and tetrahydrofuran, esters such as methyl acetate, ethyl acetate and amyl acetate, ketones such as acetone and methyl ethyl ketone, amides such as N-methylpyrrolidone Etc. and mixtures thereof may be used, but are not limited to these.

  Examples of the method for coating the coating layer on the substrate include an in-line coating method for coating the substrate during film formation, and an off-line coating method for coating the original film after film formation. However, the in-line coating method is preferably used because it is efficient because it can be formed simultaneously with the formation of the substrate, and the adhesion of the coating layer to the substrate is high. Further, when coating, corona treatment or the like is preferably performed on the surface of the substrate from the viewpoint of improving the wettability of the coating solution onto the substrate and improving the adhesive strength.

  Moreover, when a biaxially stretched polyester film is selected as the base material of the easy-surface-formable sheet laminate (1) of the present invention, the melt laminate described above is used as a method for producing the easy-surface-formable sheet laminate (1). In addition to the methods such as the method, thermal laminating method, coating method, etc., the sheet forming material and the polyester material for the base material are respectively charged into two extruders, and melted and cooled on the cast drum. A method of performing heat treatment after extrusion and biaxial stretching (coextrusion biaxial stretching method) is also preferably performed.

  The biaxial stretching method may be either a sequential biaxial stretching method in which stretching in the longitudinal direction and the width direction is separated or a simultaneous biaxial stretching method in which stretching in the longitudinal direction and the width direction is performed simultaneously. Absent.

  The heat treatment temperature Ta in the heat treatment step is preferably Tm2> Ta> Tm1, where Tm1 is the melting point (or softening point) of the surface layer and Tm2 is the melting point of the substrate. By performing heat treatment in this temperature range, the substrate can be heat-set to impart mechanical strength, and at the same time, the surface layer can be melted and homogenized to impart easy moldability.

  Using the easily surface-shaped sheet (1) or the easily surface-shaped sheet (2) and the easily surface-shaped sheet laminate (1) or the easily surface-shaped sheet laminate (2) of the present invention. An example of a method for forming a pattern will be described with reference to FIG.

  The easily surface-shaped sheet (1) or the easily surface-shaped sheet (2) and the easily surface-shaped sheet laminate (1) or the easily surface-shaped sheet laminate (2) of the present invention are heated. A pattern can be formed on the surface by mold transfer using pressure or electromagnetic wave irradiation. In the method using heating / pressurization, as shown in FIG. 3 (a), the easy surface formable sheet (1) or the easy surface formable sheet (2) of the present invention, and the easy surface formability. A sheet | seat laminated body (1) or an easily surface formable sheet | seat laminated body (2) 1 and the metal mold | die 2 are piled up, and a mold shape is transcribe | transferred to the base material 1 surface by heating and pressurizing and releasing. At this time, it is preferable that at least the surface facing the mold is made of a thermoplastic resin or a thermosetting resin. Moreover, in the method using electromagnetic wave irradiation, as shown in FIG. 3B, the mold 2 is obtained by directly filling the mold 2 with the resin composition for an easily surface-formable sheet or processing it into a sheet shape. After pressing, electromagnetic wave irradiation is performed, the resin is cured, and the mold 2 is transferred by releasing. At this time, it is preferable that at least the surface facing the mold is made of a resin that is cured by electromagnetic waves such as ultraviolet rays, visible light, and electron beams.

  Hereinafter, the easily surface-shaped sheet (1) or the easily surface-shaped sheet (2) and the easily surface-shaped sheet laminate (1) or the easily surface-shaped sheet laminate (2) of the present invention. An example of a method for forming a pattern on the surface will be described in more detail with reference to FIG.

  FIG. 3A shows an example in the case of mold forming using heating and pressurization. Easy surface of easy surface formable sheet (1) or easy surface formable sheet (2) (or easy surface formable sheet laminate (1) or easy surface formable sheet laminate (2) of the present invention The glass transition temperature Tg2 of the sheet is obtained by forming the moldable sheet (1) or the surface layer side composed of the easy-surface-formable sheet (2)) 1 and the mold 2 having the inverted irregularities. (In the case of the easily surface-shaped sheet laminate (1), Tg21, hereinafter referred to as Tg2) is heated to a temperature range of not less than the melting point Tm (FIG. 3 (a-1)) and the easy surface of the present invention. The moldable sheet (1) (or the surface layer side constituted by the easy-surface-formable sheet (1) of the easy-surface-formable sheet laminate (1)) 1 and the mold 2 are brought close to each other, and a predetermined pressure is maintained. And press and hold for a predetermined time (FIG. 3 (a-2)). Next, the temperature is lowered while maintaining the pressed state. Finally, the press pressure is released to release the sheet from the mold 2 (FIG. 3 (a-3)).

  In the surface shaping method of the present invention, in the case of shaping using heating / pressurization, the heating temperature and the press temperature T1 are in the range of Tg2 ° C. to (Tg2 + 60 ° C.) and less than the melting point Tm of the sheet. It is preferable. If it is less than this range, the dynamic storage elastic modulus E ′ and the dynamic loss elastic modulus E ″ are not sufficiently lowered, so that deformation when the mold is pressed is less likely to occur, and the pressure required for molding is reduced. Beyond this range, the heating temperature and press temperature T1 are high and inefficient in energy, and the difference in volume fluctuation during heating / cooling of the mold and the sheet becomes too large. Thus, even if the sheet is bitten into the mold and cannot be released, or the mold can be released, the accuracy of the pattern is lowered, or the pattern is partially missing, which is not preferable. In the shaping method, when shaping is performed using heating and pressurization, by setting the heating temperature and the press temperature T1 within this range, both good moldability and release properties can be achieved.

  In the surface shaping method of the present invention, when shaping is performed using heating / pressurization, the press pressure depends on the dynamic storage elastic modulus E ′, dynamic loss elastic modulus E ″, etc. at the press temperature T1. Although it is adjusted as appropriate, it is preferably 0.5 to 50 MPa, more preferably 1 to 30 MPa, and if it is less than this range, the resin is insufficiently filled in the mold and the pattern accuracy is lowered. Exceeding this range is not preferable because the required load increases, the load on the mold increases, and the durability of repeated use decreases, which is not preferable. .

  In the surface shaping method of the present invention, when shaping is performed using heating and pressing, the press pressure holding time is a value of dynamic storage elastic modulus E ′ and dynamic loss elastic modulus E ″ at the press temperature T1. However, in the case of a flat plate press, 10 seconds to 10 minutes is preferable.If it is not within this range, the resin is not sufficiently filled in the mold, and the pattern accuracy is reduced. If the above range is exceeded, deterioration due to thermal decomposition of the resin may occur and the mechanical strength of the molded product may decrease, which is not preferable.・ When shaping using pressure, keeping the holding time within this range makes it possible to achieve both good transferability and mechanical strength of the molded product, but in the case of roll-to-roll molding, press time It may be 10 seconds or less.

  Further, in the surface shaping method of the present invention, when shaping is performed using heating / pressurization, the press pressure release temperature T2 is within the temperature range of (Tg2-10 ° C) to (Tg2 + 30 ° C), and the phase difference starts to increase. It is preferable that the temperature is higher than the temperature Ts and lower than the press temperature T1. More preferably, they are (Tg2-10 degreeC)-(Tg2 + 30 degreeC). If it is less than this range, the deformation of the resin at the time of pressing remains as residual stress, and even if the pattern is collapsed at the time of mold release or even if it can be released, the thermal stability of the molded product is lowered, which is not preferable. On the other hand, if it exceeds this range, the flowability of the resin at the time of pressure release is high, so that the pattern is deformed and the transfer accuracy is lowered. In the surface shaping method of the present invention, when shaping is performed using heating and pressurization, by setting the press pressure release temperature T2 within this range, both good transferability and releasability can be achieved. .

  Moreover, in the surface shaping | molding method of this invention, when shape | molding using heating and pressurization, it is preferable that mold release temperature T3 exists in the temperature range of 20 degreeC-T2 degreeC. More preferred is a temperature range of 20 ° C. to Tg 2 ° C., and most preferred is a temperature range of 20 ° C. to Ts ° C. Exceeding this range is preferable because the flowability of the resin at the time of mold release is high, or the surface is softened and has adhesiveness, and the pattern may be deformed at the time of mold release to reduce the accuracy. Absent. In the surface shaping method of the present invention, when shaping is performed using heating / pressurization, the mold can be released with good pattern accuracy by setting the temperature at the time of release within this range.

    FIG.3 (b) shows the example in the case of metal mold shaping using electromagnetic wave irradiation. The easy-surface-formable sheet (2) of the present invention (or the surface layer side constituted by the easy-surface-formable sheet (2) of the easy-surface-formable sheet laminate (2)) 1 and the pattern to be transferred And the mold 2 having the inverted irregularities are brought close to each other, or the base material is brought close to the mold 50 directly filled with the resin composition for easily surface-forming sheet (FIG. 3 (b-1)). Then, after pressing at a predetermined pressure as it is, it is cured by irradiating electromagnetic waves from either the mold 2 side or the substrate side (FIG. 3 (b-2)). Next, the press pressure is released and the mold 2 is released (FIG. 3 (a-3)).

  In the surface shaping method of the present invention, when shaping using electromagnetic wave irradiation, the press pressure depends on the viscosity and the like of the resin composition for easily surface-shaped sheet, preferably 0.05 to 10 MPa, More preferably, it is 0.1-5 MPa. If it is not less than this range, the resin in the mold 2 is not sufficiently filled, and the pattern accuracy is lowered. On the other hand, exceeding this range is not preferable because the required load increases, the load on the mold 2 increases, and the repeated use durability decreases. By setting the pressing pressure within this range, good transferability can be obtained.

In the surface shaping method of the present invention, when shaping using electromagnetic wave irradiation, the amount of electromagnetic wave irradiation depends on the light absorption rate of the material at the wavelength to which the integrated energy is irradiated, but is 10 to 5000 mJ / cm ² . is there. If it is less than this range, the resin will be insufficiently cured and the pattern accuracy will be lowered, or the strength will be insufficient at the time of mold release, and it will break due to the mold release stress, so the in-plane uniformity will be reduced. On the other hand, if it exceeds this range, it will be hardened too much, and curling may occur due to hardening shrinkage, which is not preferable. By setting the irradiation amount of electromagnetic waves within this range, both good transferability and mechanical strength of the molded product can be achieved.

  In the surface shaping method of the present invention, when shaping using electromagnetic wave irradiation, the temperature during the series of steps is not particularly limited, but the press temperature is from room temperature to 200 ° C, more preferably from room temperature to 150 ° C, Most preferably, it is room temperature-100 degreeC. If it is higher than this temperature, the fluidity of the resin becomes so high that it flows before pressing, or the resin is cured before pressing, and the molding becomes insufficient. Further, the mold release temperature T3 is preferably not higher than the glass transition temperature Tg3 or Tg31 of the cured product, and more preferably in the temperature range of 20 ° C. to Ts ° C. (however, Ts <Tg3, Ts <Tg31). Exceeding this range is preferable because the flowability of the resin at the time of mold release is high, or the surface is softened and has adhesiveness, and the pattern may be deformed at the time of mold release to reduce the accuracy. Absent. In the surface shaping method of the present invention, when shaping is performed using electromagnetic wave irradiation, the mold can be released with good pattern accuracy by setting the temperature at the time of release within this range.

  In the surface shaping method of the present invention, when shaping using electromagnetic wave irradiation, the degree of cure can be further improved by applying heat treatment to the pattern obtained by shaping the mold. As the method, at the time of pressing the mold 2 described above, at least one of the mold 2 or the easy surface formable sheet (2) or the easy surface formable sheet laminate (2) is heated, by electromagnetic wave irradiation. After curing, before mold release, a method of heating at least one of the mold 2 or the easy-surface-formable sheet (2) or the easy-surface-formable sheet laminate (2), a method of performing a heat treatment after the pattern forming step, Preferably used. Among them, the method of heating at least one of the mold temperature T1 at the time of mold pressing or the temperature T2 of the laminated body 1 is preferably performed because the number of steps can be reduced. Further, in order to further increase the degree of curing, these may be combined.

  Further, as the surface shaping method of the present invention, in addition to a method of pressing a lithographic plate as shown in FIG. 3 (lithographic pressing method), a roll-shaped mold having irregularities formed on the surface is used. It may be a roll-to-roll continuous forming which is formed into a sheet to obtain a roll-shaped formed body. Roll-to-roll continuous forming is superior to the lithographic press method in terms of productivity.

  4A to 4F illustrate cross-sectional views of a mold used in the surface shaping method of the present invention. As the shape of the mold convex portion 11 observed in the cross section of FIG. 4, the shape is rectangular (FIG. 4A), trapezoid (FIG. 4B), triangle (FIG. 4C), and these are deformed. (Figs. 4 (d), (e), (f)) and mixtures thereof are preferably used, but shapes other than these can also be used. That is, in the cross-sectional view, in addition to FIG. 4A and the like in which the side surface of the mold convex portion 11 is substantially perpendicular to the sheet surface, the configurations as shown in FIGS. 4B to 4F are also included. . Although FIG. 4 shows an example in which flat portions are formed between adjacent mold convex portions 11, the space between adjacent mold convex portions 11 may not be flat. The hem may be connected. In addition, as for the shape of the mold recess 12, a shape such as a rectangle, trapezoid, triangle, bell shape, or a deformed form thereof can be preferably used as in the case of the mold protrusion 11.

  5A to 5H are cross-sectional views schematically showing the arrangement of the mold convex portion 11 and the mold concave portion 12 in a cross section when the mold is cut in parallel with the surface thereof. . As shown in FIGS. 5A to 5H, the mold recess 12 may have a shape selected from a linear shape, a substantially triangular shape, a substantially rectangular shape, a substantially hexagonal shape, a circle, an ellipse, and the like. FIGS. 5A to 5C show a case where the mold recess 12 has a stripe shape, FIG. 5D shows a case where the mold recess 12 has a circular cross section, and FIG. 5E shows a triangle shape. In this case, FIGS. 5F to 5G illustrate a case where the shape is a quadrangle, and FIG. 5H illustrates a case where the shape is a hexagon. The mold recesses 12 may be aligned as shown in the figure, may be arranged randomly, or different shapes may be mixed. Moreover, as shown in FIGS. 6A to 6D, the shape of the mold convex portion 11 may have a shape selected from a substantially triangular shape, a substantially rectangular shape, a substantially hexagonal shape, a circle, an ellipse, and the like.

  Further, the width S of the mold convex portion 11 used in the surface shaping method in the present invention is preferably 0.001 to 20 μm, more preferably 0.005 to 10 μm, and most preferably 0.01 to 5 μm. The height H is preferably 0.001 to 20 μm, more preferably 0.005 to 10 μm, and most preferably 0.01 to 5 μm. Moreover, the aspect ratio H / S of the mold convex part 11 is preferably 0.1 to 25, and more preferably 1 to 20.

  Here, the width S of the mold protrusion 11 is a unit length of the mold protrusion 11 as illustrated in FIG. In the case of the stripe pattern of FIG. 5, the measurement is performed in the direction in which the unit length is short. In the case of FIGS. 5D to 5H, the width S is the place where the unit length is the shortest. Further, when the mold convex portion 11 is circular as shown in FIG. 6 (a), the diameter thereof is indicated. When the mold convex portion 11 is elliptical, its short diameter is indicated. As shown in FIGS. In the case of a polygon, the diameter of the inscribed circle may be the mold convex portion 11 width S. Moreover, the height H of the mold convex part 11 in the mold thickness direction indicates the thickness of the mold convex part 11, as shown in FIG.

  Further, in this arrangement layer, the area ratio of the mold convex portion 11 and the mold concave portion 12 is arbitrary in the mold surface direction cross section in the arrangement layer.

  Here, the width of the mold protrusion 11 and the width of the mold recess 12 are represented by the lengths S and t, respectively, in the case of FIG. In addition, when the length unit changes with positions like FIG.4 (b) etc., it represents with the average value. The repeating unit (pitch) of the unevenness is expressed by the sum of the width S of the mold convex part and the width t of the concave part of the mold, and the pitch of the mold convex part 11 is preferably 0.002 to 40 μm, more preferably. It is 0.01-20 micrometers, Most preferably, it is 0.02-10 micrometers.

The material of the mold is not particularly limited, but from the viewpoint of mold processability, silicon and glass, and metals such as stainless steel (SUS) and nickel (Ni) from the viewpoint of mold release and durability. A material is preferred.

  Although the above-mentioned materials may be used for the mold as they are, it is preferable to treat the surface of the mold with a surface treatment agent in order to impart easy slipperiness. The contact angle of the surface layer of the mold by the surface treatment is preferably 80 ° or more, more preferably 100 ° or more.

  Surface treatment methods include fixing the surface treatment agent on the mold surface using chemical bonds (chemical adsorption method), and physically adsorbing the surface treatment agent on the mold surface (physical adsorption method). Can be used. Among these, the surface treatment is preferably performed by a chemical adsorption method from the viewpoint of repeated durability of the surface treatment effect and prevention of contamination of the molded product.

  As a preferable example of the surface treatment agent used in the chemical adsorption method, a fluorine-based silane coupling agent can be used. Surface treatment methods using this include cleaning methods such as ultrasonic cleaning in organic solvents (acetone and ethanol), boiling cleaning in acids such as sulfuric acid, and peroxides such as hydrogen peroxide. After the mold surface is cleaned, it is treated with a fluorine-based silane coupling agent. As an example of the processing method, a method of immersing a mold in a solution in which a fluorinated silane coupling agent is dissolved in a fluorinated solvent (wet method) or a method of depositing on a mold surface by vacuum deposition (dry method) Etc. can be used. In the case of a wet method, it is also preferable to heat the solution during immersion.

  The molded product obtained by the surface shaping method of the present invention is formed by using a mold on the easy-surface-shaped sheet (1) or the easy-surface-shaped sheet (2) of the present invention. As shown in FIGS. 7A to 7B, the transverse cross-sectional view is obtained by forming the shaping portion 3 on the sheet-like base portion 4. FIG. 7A shows a molded product formed on the easily surface-shaped sheet (1) or the easily surface-shaped sheet (2) of the present invention, and FIG. 7B shows the easily surface-shaped sheet of the present invention. It is a cross-sectional view which represents typically the molded article at the time of shape | molding to an adhesive sheet laminated body (1) or an easily surface formable sheet laminated body (2). As the shape of the molded product obtained by the surface shaping method of the present invention, preferably, the mold used and the unevenness are reversed, and specific cross-sectional views are illustrated in FIGS. 8 (a) to 8 (f). To do. As the shape of the convex portion 22 of the molded product observed in the cross section of FIG. 8, a rectangle (FIG. 8A), a trapezoid (FIG. 8B), a triangle (FIG. 8C), these are Deformed ones (FIGS. 8 (d), (e), (f)) and a mixture thereof are preferably used, but other shapes can also be used. That is, in the cross-sectional view, in addition to FIG. 8A in which the side surface of the convex portion 22 of the molded product is substantially perpendicular to the sheet surface, forms such as FIGS. 8B to 8E are also included. It is. Further, FIG. 8 shows an example in which the flat portion is formed between the convex portions 22 of the adjacent molded products, but the space between the convex portions 22 of the adjacent molded products may not be flat. The skirts of the convex portions 22 may be connected. In addition, as for the shape of the concave portion 21 of the molded product, similarly to the convex portion 22 of the molded product, a shape such as a rectangle, a trapezoid, a triangle, a bell shape, or a deformed shape thereof can be preferably used.

  9 (a) to 9 (h) respectively show a convex portion 22 of the molded product and a concave portion 21 of the molded product in a cross section when cut in parallel with the surface of the molded product obtained by the surface shaping method of the present invention. It is sectional drawing which shows typically arrangement | positioning. As shown in FIGS. 9A to 9H, the shape of the concave portion 21 of the molded product may have a shape selected from a linear shape, a substantially triangular shape, a substantially rectangular shape, a substantially hexagonal shape, a circle, an ellipse, and the like. 9A to 9C show a case where the concave portion 21 of the molded product has a stripe shape, FIG. 9D shows a case where the cross section of the concave portion 21 of the molded product has a circular shape, and FIG. 9 (f) to (g) exemplify the case of a quadrangular shape, and FIG. 9 (h) illustrates the case of a hexagonal shape. The concave portions 21 of the molded product may be aligned as shown in the figure, may be arranged at random, or may have different shapes mixed together. Further, as shown in FIGS. 10A to 10D, the shape of the convex portion 22 of the molded product may have a shape selected from a substantially triangular shape, a substantially rectangular shape, a substantially hexagonal shape, a circle, an ellipse, and the like. .

  Further, in the molded product obtained by the surface shaping method of the present invention, the aspect ratio H ′ / S ′ of the convex portion 22 is 0.1 to 15, preferably 1 to 10. Further, the convex portion 22 preferably has a width S ′ of 0.001 to 20 μm, more preferably 0.005 to 10 μm, and most preferably 0.01 to 5 μm. The height H ′ of the convex portion 22 is preferably 0.001 to 20 μm, more preferably 0.005 to 10 μm, and most preferably 0.01 to 5 μm.

  Here, the width S ′ of the convex portion 22 of the molded product is a unit length of the convex portion 22 of the molded product, as illustrated in FIG. In the case of the stripe patterns shown in FIGS. 9A to 9C, the measurement is performed in the direction in which the unit length is short. In the case of FIGS. 9D to 9H, the shortest unit length is defined as the width S ′. Further, when the convex portion 22 of the molded product is circular as shown in FIG. 10 (a), the diameter thereof is indicated. When the convex portion 22 is an ellipse, the short diameter thereof is indicated. As shown in FIGS. In the case of the polygon, the diameter of the inscribed circle may be set to the convex portion 22 width S ′ of the molded product. Further, the height H ′ of the convex portion 22 of the molded product in the thickness direction of the molded product indicates the thickness of the convex portion 22 of the molded product, as shown in FIG.

  Further, in this array layer, the area ratio of the convex part 22 of the molded product and the area of the concave part 21 of the molded product is arbitrary in the cross section in the surface direction of the molded product in the array layer.

  Here, the width of the convex portion 22 of the molded product and the width of the concave portion 21 of the molded product are represented by lengths S ′ and t ′, respectively, in the case of FIG. In addition, when the length unit changes with positions like FIG.8 (b) etc., it represents with the average value. Further, the repetition unit (pitch) of the unevenness is represented by the sum of the width S ′ of the convex portion 22 of the molded product and the width t ′ of the concave portion 21 of the molded product, and the pitch of the convex portion 22 of the molded product is preferably 0.002. It is -40 micrometers, More preferably, it is 0.01-20 micrometers, Most preferably, it is 0.02-10 micrometers.

  Moreover, as thickness l 'of the base 4 of the molded article obtained by the surface shaping method of this invention, although arbitrary, 20 micrometers-2 mm are preferable from surfaces, such as mechanical strength, More preferably, they are 30 micrometers-1 mm. More preferably, it is 50 micrometers-500 micrometers. However, as shown in FIG. 7B, the thickness l 'of the base is not particularly limited when it is formed on the easily surface-shaped sheet laminate of the present invention, and may be 20 μm or less.

  Further, the transferability (transfer rate) is judged by the ratio A ′ / A of the cross-sectional area A ′ of the convex part of the molded product A ′ of the cross-sectional area A of the mold concave part. Good transferability means that the ratio A '/ A is preferably 0.90 or more, more preferably 0.92 or more.

  The molded product produced using the easy-surface formable sheet of the present invention can be used for various applications. Examples of applications include biochips, semiconductor integrated materials, design members, optical circuits, An optical connector member, a display member, and the like can be used.

[Characteristic evaluation method]
A. Glass transition temperature Tg1, Tg2, Tg21, crystallization enthalpy ΔHcc
Glass transition temperatures Tg1, Tg2, and Tg21 are based on JIS K7121 (1999), and crystallization enthalpy ΔHcc is based on JIS K7122 (1999). Was obtained using a disk session “SSC / 5200” for data analysis. 5 mg of the resin composition or sheet was weighed into the sample pan and scanned at a heating rate of 10 ° C./min. The glass transition temperatures Tg1 and Tg2 are the step-like change portion of the glass transition in the differential scanning calorimetry chart, and the step-like change portion of the glass transition and the straight line equidistant in the vertical axis direction from the extended straight line of each baseline. It was calculated from the point where the curve intersects. The crystallization enthalpy ΔHcc was determined from the area of the crystallization exothermic peak. In the case of an easily surface formable sheet laminate, the surface layer of the laminate 1 is scraped off with a cutter, and the obtained product is measured by the above-mentioned method to obtain Tg21 of the glass transition temperature of the surface layer, crystallization enthalpy. ΔHcc was determined.

B. Phase difference increase start temperature Ts
The phase difference increase start temperature Ts uses E-sweep manufactured by SII Nanotechnology, Inc., and OMCL-RC800PB-1 manufactured by Olympus Corporation having a spring constant of 0.1 N / m as a cantilever. The method described in the specification was performed. The outline is the following procedures (1) to (7).
(1) A thin film (thickness 250 nm) of the resin composition was formed on a silicon wafer.
(2) A sine having an amplitude of 1 nm in the film thickness direction and a frequency of 100 Hz while contacting a probe of a scanning viscoelastic microscope with a cantilever (spring constant 0.1 N / m) on the surface of the thin film under vacuum conditions. The response vibration phase δa detected by the cantilever when the vibration was applied to the thin film sample was measured.
(3) Similar to (2) above, a sine vibration with an amplitude of 1 nm and a frequency of 100 Hz is applied to the silicon wafer while the same probe as in (2) is in contact with the surface of the silicon wafer under the same temperature and vacuum conditions. The phase δb of the response vibration was measured.
(4) The relative phase difference Δδ = δa−δb between the thin film surface and the silicon wafer surface was determined.
(5) The above measurements (2) and (3) are carried out every 1 ° C. within a temperature range of −50 ° C. to (Tg 1 + 20 ° C.) (Tg 1 is the glass transition temperature of the resin composition). From the obtained phase, the relative phase difference Δδ = δa−δb between the thin film surface and the silicon wafer surface was determined in the same manner as in (4).
(6) The phase difference Δδ obtained in (1) to (4) was plotted against temperature.
(7) The plot of (5) above was observed from the lowest temperature side, and the temperature at which the increase starts with the temperature rise was defined as Ts (phase difference increase start temperature).

C. Intrinsic viscosity The resin was dissolved in 100 ml of orthochlorophenol (solution concentration C = 1.2 g · ml), and the viscosity of the solution at 25 ° C. was measured using an Ostwald viscometer. Similarly, the viscosity of the solvent was measured. Using the obtained solution viscosity and solvent viscosity, intrinsic viscosity [η] was determined by the following formula.
ηsp / C = [η] + K [η] ² · C
(Where ηsp = (solution viscosity / solvent viscosity) −1, K is the Huggins constant (assuming 0.343)).

D. Dynamic storage modulus E ', Dynamic storage modulus E "
The dynamic storage elastic modulus E ′ and the dynamic loss elastic modulus E ″ were determined using a dynamic viscoelasticity measuring device “DMS6100” manufactured by Seiko Instruments Inc. based on JIS-K7244 (1999). The temperature dependence of the viscoelastic properties of each sheet was measured under the measurement conditions of a driving frequency of 1 Hz, a distance between chucks of 5 mm, a strain amplitude of 10 μm, an initial value of force amplitude of 100 mN, and a temperature increase rate of 2 ° C./min. From the results, the dynamic storage elastic modulus E ′ dynamic loss elastic modulus E ″ at room temperature and Tg2 + 40 ° C. was determined. In addition, in the case of the easily surface formable sheet laminate, a single film was prepared using the material of the surface layer, and the measurement was performed according to the method described above.

E. Peel strength Laminate was cut into strips 2cm wide x 12cm long, the substrate side was attached to a 2mm thick surface smooth acrylic board with double-sided tape, and polyester adhesive tape (No. made by Nitto Denko Corporation) on the surface layer side .31B and a width of 19 mm) were attached, and the upper end of the acrylic plate was suspended on a load cell of a Tensilon tensile tester (UTMIII manufactured by Toyo Sokki Co., Ltd.). Next, a strip-shaped lead paper is applied to the upper end of the adhesive tape, one end thereof is gripped by the lower chuck, and pulled downward (180 °) at a crosshead speed of 300 mm / min, and the peeling force between the base layer and the surface layer is peeled off. Was measured. The peel strength F (N / cm) was calculated from the average peel force T (N) having a peel length of 50 mm or more excluding the rising portion of the SS curve by the following formula.
・ Peel strength F (N / cm) = T / W
Here, T (N): average peeling force, W (cm): sample width.

F. Polystyrene-converted weight average molecular weight Mw, polystyrene-converted number average molecular weight Mn, dispersity Mw / Mn, component content R of Mw = 5000 or less
A differential refractive index detector RI (RI-71 type, sensitivity 64) manufactured by Showa Denko KK as a detector, and TSKgel GMHHR-M (φ7.8 mm × 30 cm, φ7.8 mm × 30 cm, theoretical plate number 14,000 plates) manufactured by Tosoh Corporation as a column. Mw, Mn, and R were determined using a gel permeation chromatograph GPC (8) manufactured by Tosoh Corporation. Chloroform was used for the moving layer. The flow rate was 1.0 mL / min, the column temperature was 23 ° C. ± 2 ° C., and the injection volume was 0.200 mL. As the standard sample, monodisperse polystyrene (TSK standard polystyrene manufactured by Tosoh Corporation) was used.

G. Shape observation For cross-sectional observation, cut out a cross section of a mold and a molded product, deposit platinum-palladium, and then take a photograph with a field emission scanning electron microscope “JSM-6700F” manufactured by JEOL Ltd. The height of the convexity of the mold and the H width S, the aspect ratio H / S, the sectional area A of the concave portion, the height H ′ and the width S ′ of the convex portion of the molded product, and the aspect ratio H ′ / S ′. , The sectional area A ′ of the convex portion was obtained. In the examples and comparative examples, when the pattern was confirmed to be broken, the above items were obtained in the unbroken portion.

The releasability was determined as follows. After cutting out the molded product and depositing platinum-palladium on the surface, perform surface observation,
The pattern is formed or is broken at a very small part: ○
A fracture mark is confirmed in a part of the pattern:
Broken traces are confirmed on most of the pattern, or release from the mold is not possible: ×
It was.

The presence or absence of pattern collapse was determined as follows. After cutting out the molded product and depositing platinum-palladium on the surface, perform surface observation,
Adjacent convex parts are not in contact, or only a very small part is in contact: ○
Part of the pattern is in contact:
Convex part is collapsed in most part of pattern: ×
It was.

The transferability was determined as follows. The ratio A ′ / A between the cross-sectional area A ′ of the concave portion of the molded product and the area A of the convex portion of the mold is obtained.
0.85 or more and less than 0.90: △
Less than 0.85: ×
It was.

The storage stability of the molded product shape was determined as follows. After cutting out the molded product and depositing platinum-palladium on the surface, perform surface observation,
1) When the pattern collapse before the test is ○, the adjacent convex portions are not in contact with each other or are in contact with a very small portion: ○
Part of the pattern is in contact:
The convex part has fallen in most parts of the pattern, or the convex part has disappeared: ×
2) If the pattern collapse before the test is △, the number of contact points has not increased: ○
The number of contact points has increased: △
The convex part has fallen in most parts of the pattern, or the convex part has disappeared: ×
It was.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not necessarily limited to these.

In addition, the metal mold | die used in the Example and the comparative example is the following three types (refer FIG. 11).
"Mold 1" (Figure 11 (a))
Material: Nickel, Size: 30 mm square Pattern: Stripe Pitch: 1 μm, Convex width: 2 μm, Convex height: 3 μm
Sectional shape: rectangular shape
“Mold 2” (FIG. 11B)
Material: Nickel, Size: 30 mm square Pattern: Stripe Pitch: 1500 nm, Convex width: 1000 nm, Convex height: 1500 nm
Sectional shape: rectangular shape
"Mold 3" ((Figure 11 (c))
Material: Nickel, Size: 30 mm square Pattern: Stripe Pitch: 150 nm, Convex width: 100 nm, Convex height: 150 nm
Cross-sectional shape: rectangular shape.

Example 1
Cyclohexanedicarboxylic acid as a dicarboxylic acid component, 9,9′-bis (4-hydroxyethoxyphenyl) fluorene as a diol component 80 mol%, ethylene glycol 20 mol% copolymerized polyester (inherent viscosity C = 0.40 dl / g) 3 parts by weight Was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm.

  About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 1. The phase difference increase start temperature Ts was 54 ° C.

  The polyester was vacuum-dried at 100 ° C. for 4 hours, then melted at 280 ° C. in an extruder, extruded from a die onto a cast drum at 20 ° C., and cooled to obtain a sheet having a thickness of 600 μm.

  The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 1.

  Moreover, the obtained sheet | seat and metal mold | die were heated at 165 degreeC, the uneven | corrugated surface of the sheet | seat and the metal mold | die was contacted, and it pressed at 20 MPa, and was hold | maintained as it was for 2 minutes. Thereafter, the press was released after cooling to 130 ° C., cooled to 30 ° C. and released from the mold to obtain a resin molded product.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold (mold 1: A ′ / A = 0.997, gold Mold 2: A ′ / A = 0.959, Mold 3: A ′ / A = 0.842). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

  Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 2.

(Example 2)
Polyester obtained by copolymerization of 70 mol% of cyclohexanedicarboxylic acid as a dicarboxylic acid component, 30 mol% of terephthalic acid, 50 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene as a diol component, and 50 mol% of ethylene glycol (inherent viscosity C = 0. 55 dl / g) 3 parts by weight was dissolved in 97 parts by weight of a cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 1. The phase difference increase start temperature Ts was 39 ° C.

  The polyester was vacuum-dried at 90 ° C. for 4 hours, then melted at 280 ° C. in an extruder, extruded from a die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

  The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1 except that the press temperature was 150 ° C. and the press release temperature was 115 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold. (Mold 1: A ′ / A = 0.969, Mold 2: A ′ / A = 0.945, Mold 3: A ′ / A = 0.930). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

  Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 2.

(Example 3)
3 parts by weight of polyester (inherent viscosity C = 0.52 dl / g) copolymerized with terephthalic acid as the dicarboxylic acid component, 40 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 60 mol% of ethylene glycol as the diol component It was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 1. The phase difference increase start temperature Ts was 61 ° C.

  The polyester was vacuum-dried at 110 ° C. for 4 hours, then melted at 280 ° C. in an extruder, extruded from the die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

  The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1 except that the press temperature was 165 ° C. and the press release temperature was 130 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold. (Mold 1: A ′ / A = 0.960, Mold 2: A ′ / A = 0.941, Mold 3: A ′ / A = 0.922). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

  Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 2.

Example 4
10 weights of polyester (inherent viscosity C = 0.59 dl / g) copolymerized with cyclohexanedicarboxylic acid as the dicarboxylic acid component, 50 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 50 mol% of ethylene glycol as the diol component % Dissolved in toluene. While stirring 100 parts by weight of the resulting solution, 50 parts by weight of isopropyl alcohol was added to cause reprecipitation. A solid obtained by filtering from the obtained solution was washed with isopropyl alcohol and then vacuum-dried at 80 ° C. for 4 hours. The obtained solid had an intrinsic viscosity of C = 0.60 dl / g.

  The obtained solid was dissolved in chloroform so as to be 0.2 g / ml, and then filtered through a membrane filter having a pore size of 0.45 μm. The obtained solution was subjected to polystyrene conversion weight average molecular weight Mw, polystyrene conversion weight average by GPC. When the component content R of molecular weight Mn, polydispersity Mw / Mn, Mw = 5000 or less was determined, Mw was 56500, Mn was 29900, Mw / Mn was 1.89, and W was 0.78%.

  Next, 3 parts by weight of the obtained solid was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Moreover, the glass transition temperature Tg1 of the said solid substance was measured. The results are shown in Table 1. The phase difference increase start temperature Ts was 32 ° C.

  The solid was vacuum dried at 80 ° C. for 4 hours and then sandwiched between two polyimide films “Kapton (registered trademark)” 500H (manufactured by Toray DuPont) and melted on a hot plate at 280 ° C. The sheet was pressed, quenched, and peeled to obtain a sheet having a thickness of 600 μm.

  The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1 except that the press temperature was 135 ° C. and the press release temperature was 100 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold. (Mold 1: A ′ / A = 0.962, Mold 2: A ′ / A = 0.948, Mold 3: A ′ / A = 0.926). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

  Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 2.

(Example 5)
3 parts by weight of polyester (inherent viscosity C = 0.64 dl / g) copolymerized with terephthalic acid as the dicarboxylic acid component, 40 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 60 mol% of ethylene glycol as the diol component It was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, the horizontal force increase temperature Ts of the surface was measured with the horizontal force microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 1. The horizontal force increasing temperature Ts was 63 ° C.

  The polyester was vacuum-dried at 110 ° C. for 4 hours, then melted at 280 ° C. in an extruder, extruded from the die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

  The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1 except that the press temperature was 165 ° C. and the press release temperature was 130 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold, although the moldability was slightly lowered in the mold 3. . (Mold 1: A ′ / A = 0.957, Mold 2: A ′ / A = 0.932, Mold 3: A ′ / A = 0.894). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

    Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 2.

(Example 6)
3 parts by weight of polyester (inherent viscosity C = 0.52 dl / g) copolymerized with terephthalic acid as the dicarboxylic acid component, 40 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 60 mol% of ethylene glycol as the diol component It was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 61 ° C.

  Further, the above polyester dried in vacuum at 110 ° C. for 4 hours as the surface layer, and polyethylene terephthalate (PET) vacuum dried at 170 ° C. for 2 hours as the base layer were melted at 280 ° C. in separate extruders. A two-layer laminated sheet was prepared by co-extrusion on a cast drum from a molten two-layer coextrusion die having PET on one side by a predetermined method and cooling. The two-layer laminate sheet thus obtained was heated to 84 ° C. and stretched 3.3 times in the longitudinal direction, and then stretched in the width direction at 90 ° C. through a preheating zone of 85 ° C. with a tenter. Thereafter, heat treatment was performed at 90 ° C. for 20 seconds and at 220 ° C. for 30 seconds to obtain a laminated sheet having a total film thickness of 100 μm. The thickness of the surface layer was 5 μm.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3.

  Moreover, the surface layer was extruded from the die onto the cast drum as a single film and cooled to obtain a single layer sheet. The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3.

  Moreover, the obtained sheet | seat and metal mold | die were heated at 165 degreeC, the surface layer of the sheet | seat and the uneven | corrugated surface of the metal mold | die were pressed, and it pressed at 20 Mpa, and hold | maintained as it was for 2 minutes. Thereafter, the press was released after cooling to 130 ° C., cooled to 30 ° C. and released from the mold to obtain a resin molded product.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold (mold 1: A ′ / A = 0.923, gold Mold 2: A ′ / A = 0.910, Mold 3: A ′ / A = 0.908). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

  Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 4.

(Example 7)
Cyclohexanedicarboxylic acid as a dicarboxylic acid component, 9,9′-bis (4-hydroxyethoxyphenyl) fluorene as a diol component 80 mol%, ethylene glycol 20 mol% copolymerized polyester (inherent viscosity C = 0.40 dl / g) 3 parts by weight Was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution to form a coating film having a thickness of 250 nm. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds), and dried in a hot air oven at 150 ° C. for 6 hours. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 54 ° C.

  The polyester was dissolved in a solution of cyclohexanone / methyl ethyl ketone = / toluene 1.5 / 1.5 / 1 at 35 ° C. to a concentration of 20% by weight. The obtained solution was applied onto a 100 μm thick polyester film “Lumirror” U46 (manufactured by Toray Industries, Inc.) using Metabar (# 30) and dried at 140 ° C. for 30 minutes to obtain a surface layer having a dry film thickness of 5 μm. The laminated body which has this was produced.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 2.

  For the surface layer, the solution was applied onto a 100 μm thick polyester film (“Lumirror” (registered trademark) T60, manufactured by Toray Industries, Inc.) using an applicator, dried at 100 ° C. for 30 minutes, and then peeled off. A single layer sheet was obtained by vacuum drying at 80 ° C. for 6 hours. The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3.

  Moreover, the obtained sheet | seat and metal mold | die were heated at 165 degreeC, the surface layer of the sheet | seat and the uneven | corrugated surface of the metal mold | die were pressed, and it pressed at 20 Mpa, and hold | maintained as it was for 2 minutes. Thereafter, the press was released after cooling to 130 ° C., cooled to 30 ° C. and released from the mold to obtain a resin molded product.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold. (Mold 1: A ′ / A = 0.969, Mold 2: A ′ / A = 0.952, Mold 3: A ′ / A = 0.939). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

  Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 4.

(Example 8)
Polyester obtained by copolymerization of 70 mol% of cyclohexanedicarboxylic acid as a dicarboxylic acid component, 30 mol% of terephthalic acid, 50 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene as a diol component, and 50 mol% of ethylene glycol (inherent viscosity C = 0. 55 dl / g) 3 parts by weight was dissolved in 97 parts by weight of a cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 39 ° C.

  Moreover, the laminated body and the single film sheet were produced similarly to Example 7 except using the said polyester as a surface layer.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3. The obtained single membrane sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3. .

  A resin molded product was obtained in the same manner as in Example 7, except that the press temperature was 150 ° C. and the press release temperature was 115 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold (mold 1: A ′ / A = 0.970, gold Mold 2: A ′ / A = 0.952, Mold 3: A ′ / A = 0.935). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

  Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 4.

Example 9
3 parts by weight of polyester (inherent viscosity C = 0.52 dl / g) copolymerized with terephthalic acid as the dicarboxylic acid component, 40 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 60 mol% of ethylene glycol as the diol component It was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 61 ° C.

  Moreover, the laminated body and the single film sheet were produced similarly to Example 7 except using the said polyester as a surface layer.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3. The obtained single membrane sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3. .

  A resin molded product was obtained in the same manner as in Example 7 except that the press temperature was 165 ° C. and the press release temperature was 130 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold (mold 1: A ′ / A = 0.939, gold Mold 2: A ′ / A = 0.828, Mold 3: A ′ / A = 0.925). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

  Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 4.

(Example 10)
10 weights of polyester (inherent viscosity C = 0.60 dl / g) copolymerized with cyclohexanedicarboxylic acid as dicarboxylic acid component, 50 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 50 mol% of ethylene glycol as diol component % Dissolved in toluene. While stirring 100 parts by weight of the resulting solution, 50 parts by weight of isopropyl alcohol was added to cause reprecipitation. A solid obtained by filtering from the obtained solution was washed with isopropyl alcohol and then vacuum-dried at 80 ° C. for 4 hours.

  The obtained solid was dissolved in chloroform so as to be 0.2 g / ml, and then filtered through a membrane filter having a pore size of 0.45 μm. The obtained solution was subjected to polystyrene conversion weight average molecular weight Mw, polystyrene conversion weight average by GPC. When the component content R of molecular weight Mn, polydispersity Mw / Mn, Mw = 5000 or less was determined, Mw was 56500, Mn was 29900, Mw / Mn was 1.89, and W was 0.78%.

  Next, 3 parts by weight of the obtained solid was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Moreover, the glass transition temperature Tg1 of the said solid substance was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 32 ° C.

  Moreover, the laminated body was produced similarly to Example 7 except using the said solid substance as a surface layer.

  The solid was vacuum dried at 80 ° C. for 4 hours, and then sandwiched between two polyimide films “Kapton (registered trademark)” 500H (manufactured by Toray DuPont) and melted on a hot plate at 280 ° C. Then, after pressing, quenching, and peeling, a single film sheet having a thickness of 600 μm was obtained.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3. The obtained single membrane sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3. .

  A resin molded product was obtained in the same manner as in Example 7 except that the press temperature was 135 ° C. and the press release temperature was 100 ° C.

    When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold. (Mold 1: A ′ / A = 0.960, Mold 2: A ′ / A = 0.941, Mold 3: A ′ / A = 0.925). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

  Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 4.

(Example 11)
3 parts by weight of polyester (inherent viscosity C = 0.64 dl / g) copolymerized with terephthalic acid as the dicarboxylic acid component, 40 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 60 mol% of ethylene glycol as the diol component It was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, the horizontal force increase temperature Ts of the surface was measured with the horizontal force microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 3. The horizontal force increasing temperature Ts was 63 ° C.

  Moreover, the laminated body and the single film sheet were produced similarly to Example 7 except using the said polyester as a surface layer.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3.

  The obtained single membrane sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3. .

  A resin molded product was obtained in the same manner as in Example 7 except that the press temperature was 165 ° C. and the press release temperature was 130 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold, although the moldability was slightly lowered in the mold 3. (Mold 1: A ′ / A = 0.935, Mold 2: A ′ / A = 0.925, Mold 3: A ′ / A = 0.890). Moreover, when the surface of the molded product was observed, it was confirmed that no pattern collapse occurred in any mold.

  Next, when the molded product was allowed to stand at 23 ° C. and 60% humidity for one month and then the surface of the molded product was observed, no pattern collapse was observed, and it was found that the shape was maintained even during long-term storage. The results are shown in Table 4.

(Comparative Example 1)
Polyester obtained by copolymerizing 100 mol% of cyclohexanedicarboxylic acid as a dicarboxylic acid component, 25 mol% of 9,9'-bis (4-hydroxyethoxyphenyl) fluorene as a diol component, and 75 mol% of ethylene glycol (inherent viscosity C = 0.54 dl / g) 3 A part by weight was dissolved in 97 parts by weight of a cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 1. The phase difference increase start temperature Ts was 15 ° C.

  Further, the polyester that had been vacuum-dried at 60 ° C. for 4 hours was melted at 280 ° C. in an extruder, extruded from a die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

  The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 1.

  Further, a resin molded product was obtained in the same manner as in Example 1 except that the press temperature was 110 ° C. and the press release temperature was 75 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was sufficiently molded in any mold (mold 1: A ′ / A = 0.962, mold 2: A ′ / A = 0.938, mold 3: A ′ / A = 0.925). When the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 2.

(Comparative Example 2)
A polyester (inherent viscosity C = 0.59 dl / g) copolymerized with cyclohexanedicarboxylic acid as a dicarboxylic acid component, 50 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 50 mol% of ethylene glycol as a diol component. After dissolving in chloroform so as to be 2 g / ml, the solution was filtered through a membrane filter having a pore size of 0.45 μm, and the obtained solution was subjected to GPC by polystyrene-converted weight average molecular weight Mw, polystyrene-converted weight average molecular weight Mn, polydispersity Mw / When the component content R of Mn and Mw = 5000 or less was determined, Mw was 44100, Mn was 10300, Mw / Mn was 4.28, and R was 3.91.

  Next, 3 parts by weight of the polyester was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Moreover, the glass transition temperature Tg1 of the said solid substance was measured. The results are shown in Table 1. The phase difference increase start temperature Ts was 22 ° C.

  The polyester is vacuum-dried at 80 ° C. for 4 hours, and then sandwiched between two polyimide films “Kapton (registered trademark)” 500H (manufactured by Toray DuPont) and melted on a hot plate at 280 ° C. Then, after pressing, quenching and peeling, a sheet having a thickness of 600 μm was obtained.

  The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1 except that the press temperature was 135 ° C. and the press release temperature was 100 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was sufficiently molded in any mold (mold 1: A ′ / A = 0.965, mold 2: A ′ / A = 0.949, mold 3: A ′ / A = 0.828). When the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 2.

(Comparative Example 3)
Spiroglycol 30 mol% copolymerized PET (“S-PET30”, manufactured by Mitsubishi Gas Chemical Co., Inc., intrinsic viscosity C = 0.68 dl / g) 3 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution 97 weight Was dissolved in a portion. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 1. The phase difference increase start temperature Ts was 22 ° C.

  Further, the polyester that had been vacuum-dried at 80 ° C. for 4 hours was melted at 280 ° C. in an extruder, extruded from a die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

  The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E 'at Tg2 + 40 ° C, and dynamic loss elastic modulus E2 "at Tg2 + 40 ° C. The results are shown in Table 1.

A resin molded product was obtained in the same manner as in Example 1 except that the press temperature was 140 ° C. and the press release temperature was 105 ° C.
When the cross section of the obtained molded product was observed with a scanning electron microscope, the molds 1 and 2 were sufficiently molded, but the mold 3 was rounded and the mold was not fully molded. (Mold 1: A ′ / A = 0.960, Mold 2: A ′ / A = 0.929, Mold 3: A ′ / A = 0.742). Further, when the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 1.

(Comparative Example 4)
1 part by weight of isophthalic acid 17.5 mol% copolymerized PET3 (intrinsic viscosity C = 0.66 dl / g) was dissolved in 97 parts by weight of N-methylpyrrolidone. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 1. The phase difference increase start temperature Ts was 14 ° C.

  The polyester was vacuum-dried at 150 ° C. for 2 hours, then melted at 250 ° C. in an extruder, extruded from the die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

  The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 1.

  Further, a resin molded product was obtained in the same manner as in Example 1 except that the press temperature was 110 ° C. and the press release temperature was 75 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the molds 1 and 2 were sufficiently molded, but the mold 3 was rounded and the mold was not fully molded. (Mold 1: A ′ / A = 929, Mold 2: A ′ / A = 0.863, Mold 3: A ′ / A = 0.710). Further, when the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 2.

(Comparative Example 5)
10 parts by weight of dimer acid 15 mol% and 1,4-butanediol 62 mol% copolymerized PET (inherent viscosity C = 0.74 dl / g) was dissolved in chloroform 90 parts by weight. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 1. The phase difference increase start temperature Ts was −30 ° C.

  The polyester was vacuum dried at 120 ° C. for 2 hours, then melted at 250 ° C. in an extruder, extruded from a die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

  The obtained sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 1.

A resin molded product was obtained in the same manner as in Example 1 except that the press temperature was 45 ° C., the press release temperature was 20 ° C., and the mold release temperature was 20 ° C.
When the cross section of the obtained molded product was observed with a scanning electron microscope, the vertex was rounded in any mold, and the molding was not sufficiently performed (mold 1: A ′ / A = 0. 347, mold 2: A ′ / A = 0.272, mold 3: A ′ / A = 0.102). Further, when the surface of the molded product was observed, the mold 3 was hardly molded, and therefore pattern collapse could not be confirmed.

  Next, when the molded product was allowed to stand at 25 ° C. for one month and the surface of the molded product was observed, it was found that the patterns almost disappeared in the molds 2 and 3. The results are shown in Table 2.

(Comparative Example 6)
25 parts by weight of polymethyl methacrylate (manufactured by Sigma-Aldrich Co., Ltd., weight average molecular weight 15000, intrinsic viscosity 0.28 dl / g) was dissolved in 75 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied on a silicon wafer by a spin coating method (1st-1500 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polymethyl methacrylate was measured. The results are shown in Table 1. The phase difference increase start temperature Ts was −7 ° C.

  Further, 30 parts by weight of the polymer was dissolved in 70 parts by weight of cyclohexanone / methyl ethyl ketone = 1/1 solution. This solution was cast from the die onto an endless belt, and then the solvent was removed by drying with hot air at 120 ° C. and then peeled off. Next, it was vacuum dried at 75 ° C. for 4 hours to obtain a sheet having a thickness of 600 μm.

  The obtained sheet and sheet were measured for glass transition temperature Tg2, dynamic storage elastic modulus E 'at room temperature and Tg2 + 40 ° C, and dynamic loss elastic modulus E2 "at Tg2 + 40 ° C. The results are shown in Table 1.

  Further, except that the press temperature was 140 ° C. and the press release temperature was 105 ° C., an attempt was made to obtain a resin molded product by the same method as in Example 1. In either case, a resin molded product could not be obtained. It was confirmed that the molds 1 and 2 were sufficiently formed (mold 1: A ′ / A = 0.952, mold 2: A ′ / A = 0.923). The results are shown in Table 2.

(Comparative Example 7)
Polyester obtained by copolymerizing 100 mol% of cyclohexanedicarboxylic acid as a dicarboxylic acid component, 25 mol% of 9,9'-bis (4-hydroxyethoxyphenyl) fluorene as a diol component, and 75 mol% of ethylene glycol (inherent viscosity C = 0.54 dl / g) 3 A part by weight was dissolved in 97 parts by weight of a cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 15 ° C.

  Further, a laminate and a single film sheet were produced in the same manner as in Example 6 except that the above polyester that had been vacuum-dried at 60 ° C. for 4 hours was used as the surface layer.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3. The obtained single membrane sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3. .

  A resin molded product was obtained in the same manner as in Example 6 except that the press temperature was 110 ° C. and the press release temperature was 70 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was sufficiently molded in any mold (mold 1: A ′ / A = 0.965, mold 2: A ′ / A = 0.950, mold 3: A ′ / A = 0.934). When the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 4.

(Comparative Example 8)
Spiroglycol 30 mol% copolymerized PET (“S-PET30”, manufactured by Mitsubishi Gas Chemical Co., Inc., intrinsic viscosity C = 0.68 dl / g) 3 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution 97 weight Was dissolved in a portion. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 22 ° C.

  Further, a laminate and a single film sheet were produced in the same manner as in Example 6 except that the above polyester that had been vacuum-dried at 80 ° C. for 4 hours was used as the surface layer.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3. The obtained single membrane sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 2. .

  A resin molded product was obtained in the same manner as in Example 6 except that the press temperature was 140 ° C. and the press release temperature was 105 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the molds 1 and 2 were sufficiently molded, but the mold 3 was rounded and the mold was not fully molded. (Mold 1: A ′ / A = 0.925, Mold 2: A ′ / A = 0.902, Mold 3: A ′ / A = 0.826). Further, when the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 4.

(Comparative Example 9)
3 parts by weight of isophthalic acid 17.5 mol% copolymerized PET (inherent viscosity C = 0.66 dl / g) was dissolved in 97 parts by weight of N-methylpyrrolidone. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 14 ° C.

  Further, a laminate and a single film sheet were produced in the same manner as in Example 6 except that the above polyester that had been vacuum-dried at 150 ° C. for 2 hours was used as the surface layer.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3. Further, the obtained single film sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3. .

  A resin molded product was obtained in the same manner as in Example 6 except that the press temperature was 110 ° C. and the press release temperature was 75 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the vertex was rounded in any mold, and the molding was not sufficiently performed (mold 1: A ′ / A = 0. 872, mold 2: A ′ / A = 0.854, mold 3: A ′ / A = 0.621). Further, when the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 2.

(Comparative Example 10)
Polyester obtained by copolymerizing 100 mol% of cyclohexanedicarboxylic acid as a dicarboxylic acid component, 25 mol% of 9,9'-bis (4-hydroxyethoxyphenyl) fluorene as a diol component, and 75 mol% of ethylene glycol (inherent viscosity C = 0.54 dl / g) 3 A part by weight was dissolved in 97 parts by weight of a cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. The results are shown in Table 3. The phase difference increase start temperature Ts was 15 ° C.

  Further, a laminate and a single film sheet were produced in the same manner as in Example 7 except that the above polyester that had been vacuum-dried at 60 ° C. for 4 hours was used as the surface layer.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3. Further, the obtained single film sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3. .

  A resin molded product was obtained in the same manner as in Example 7 except that the press temperature was 110 ° C. and the press release temperature was 75 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was sufficiently molded in any mold (mold 1: A ′ / A = 0.966, mold 2: A ′ / A = 0.957, mold 3: A ′ / A = 0.939). When the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 4.

(Comparative Example 11)
A polyester (inherent viscosity C = 0.59 dl / g) copolymerized with cyclohexanedicarboxylic acid as a dicarboxylic acid component, 50 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 50 mol% of ethylene glycol as a diol component. After dissolving in chloroform so as to be 2 g / ml, the solution was filtered through a membrane filter having a pore size of 0.45 μm, and the obtained solution was subjected to GPC by polystyrene-converted weight average molecular weight Mw, polystyrene-converted weight average molecular weight Mn, polydispersity Mw / When the component content R of Mn and Mw = 5000 or less was determined, Mw was 44100, Mn was 10300, Mw / Mn was 4.28, and R was 3.91.

  Next, 3 parts by weight of the polyester was dissolved in 97 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface retardation increase starting temperature Ts was measured with a scanning viscoelastic microscope. Moreover, the glass transition temperature Tg1 of the said solid substance was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 22 ° C.

  Moreover, the laminated body and the single film sheet were produced similarly to Example 7 except using the said solid substance as a surface layer.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 2. The obtained single membrane sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3. .

  A resin molded product was obtained in the same manner as in Example 7 except that the press temperature was 135 ° C. and the press release temperature was 100 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, it was sufficiently molded in any mold (mold 1: A ′ / A = 0.963, mold 2: A ′ / A = 0.948, mold 3: A ′ / A = 0.828). When the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 4.

(Comparative Example 12)
Spiroglycol 30 mol% copolymerized PET (“S-PET30”, manufactured by Mitsubishi Gas Chemical Co., Inc., intrinsic viscosity C = 0.68 dl / g) 3 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution 97 weight Was dissolved in a portion. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 22 ° C.

  Further, a laminate and a single film sheet were prepared in the same manner as in Example 7 except that the above polyester that had been vacuum-dried at 80 ° C. for 4 hours was used as the surface layer.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3. The obtained single membrane sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3. .

  A resin molded product was obtained in the same manner as in Example 7 except that the press temperature was 140 ° C. and the press release temperature was 105 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the molds 1 and 2 were sufficiently molded, but the mold 3 was rounded and the mold was not fully molded. (Mold 1: A ′ / A = 0.925, Mold 2: A ′ / A = 0.901, Mold 3: A ′ / A = 0.826). Further, when the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 4.

(Comparative Example 13)
3 parts by weight of isophthalic acid 17.5 mol% copolymerized PET (inherent viscosity C = 0.66 dl / g) was dissolved in 97 parts by weight of N-methylpyrrolidone. The obtained solution was applied onto a silicon wafer by spin coating (1st-700 rpm for 10 seconds, 2nd-1000 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polyester was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was 14 ° C.

  Further, a laminate and a single film sheet were produced in the same manner as in Example 7 except that the above polyester dried in vacuum at 150 ° C. for 2 hours was used as the surface layer and N-methylpyrrolidone was used as the solvent.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer were determined. The results are shown in Table 3. The obtained single membrane sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 3. .

  A resin molded product was obtained in the same manner as in Example 7 except that the press temperature was 110 ° C. and the press release temperature was 75 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the vertex was rounded in any mold, and the molding was not sufficiently performed (mold 1: A ′ / A = 0. 887, mold 2: A ′ / A = 0.865, mold 3: A ′ / A = 0.638). Further, when the surface of the molded product was observed, pattern collapse occurred in the mold 3. The results are shown in Table 4.

(Comparative Example 14)
25 parts by weight of polymethyl methacrylate (manufactured by Sigma-Aldrich Co., Ltd., weight average molecular weight 15000, intrinsic viscosity 0.28 dl / g) was dissolved in 75 parts by weight of cyclohexanone / methyl ethyl ketone / toluene = 1/1/1 solution. The obtained solution was applied on a silicon wafer by a spin coating method (1st-1500 rpm for 30 seconds) and dried in a hot air oven at 150 ° C. for 6 hours to form a coating film having a thickness of 250 nm. About the obtained coating film, surface phase difference increase start temperature Ts was measured with the scanning viscoelastic microscope. Further, the glass transition temperature Tg1 of the polymethyl methacrylate was measured. The results are shown in Table 3. The phase difference increase start temperature Ts was −7 ° C.

  In addition, a laminate and a single film sheet were produced in the same manner as in Example 7 except that polymethyl methacrylate (manufactured by Sigma-Aldrich Co., Ltd., weight average molecular weight 15000) was used as the surface layer.

  The glass transition temperature Tg21 of the obtained laminated sheet and the peel strength between the surface layer and the base material layer of the sheet were determined. The results are shown in Table 3. The obtained single membrane sheet was measured for glass transition temperature Tg2, room temperature and dynamic storage elastic modulus E ′ at Tg2 + 40 ° C., and dynamic loss elastic modulus E2 ″ at Tg2 + 40 ° C. The results are shown in Table 2. .

  Further, except that the press temperature was set to 140 ° C. and the press release temperature was set to 105 ° C., an attempt was made to obtain a resin molded product by the same method as in Example 7, but peeling occurred between the surface layer and the substrate, and the mold Could not be released from. The results are shown in Table 4.

  The surface shaping sheet of the present invention or the molded product obtained by the surface shaping method can be applied to various fields such as optical elements and biochips.

FIG. 1A shows the principle of a scanning viscoelastic microscope, and FIGS. 2B and 2C show a method of obtaining a phase difference obtained using a scanning viscoelastic microscope. 2A to 2C show a method for obtaining the phase difference increase start temperature Ts from the phase difference temperature dispersion. 3A to 3B schematically illustrate the steps of the surface shaping method using the easily surface-shaped sheet of the present invention. FIGS. 4A to 4F are all cross-sectional views showing a mold used in the surface shaping method of the present invention, and schematically illustrate the shape of the convex portion 11 in the cross-section. FIGS. 5A to 5H are cross-sectional views in a cross section parallel to the surface of the mold used in the surface shaping method of the present invention, and schematically illustrate the shape of the convex portion 11. . 6A to 6D are cross-sectional views in a cross section parallel to the surface of the mold used in the surface shaping method of the present invention, and schematically illustrate the shape of the convex portion 11. FIG. 7A shows a molded product formed on the easily surface-shaped sheet of the present invention, and FIG. 7B shows a molded product formed on the easily surface-shaped sheet laminate of the present invention. It is a transverse cross section showing typically. FIGS. 8A to 8F are cross-sectional views each showing a molded product obtained by the surface shaping method of the present invention, and schematically illustrate the shape of the convex portion 22 in the cross-section. is there. FIGS. 9A to 9H are cross-sectional views in a cross section parallel to the surface of the molded product obtained by the surface shaping method, and schematically illustrate the shape of the convex portion 22. 10A to 10D are cross-sectional views in a cross section parallel to the surface of the molded product obtained by the surface shaping method, and schematically illustrate the shape of the convex portion 22. FIGS. 11A to 11C are perspective views schematically showing a part of the mold used in the examples and comparative examples.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Easy surface formability sheet 2 Mold 3 Shaped part 4 Base 5 Base material 11 Mold convex part 12 Mold concave part 21 Molded part concave part 22 Molded product convex part S Mold convex part width H Gold Height of mold convex part t Width of mold concave part S 'Width of convex part of molded article H' Height of convex part of molded article l 'Thickness of base part of molded article t' Width of concave part of molded article 101 Thin film 111 Silicon wafer 102 Cantilever 103 Probe 104 Laser beam 105 Photodetector l ₁ , l _1a Vibration direction of sample 101 l _1b Vibration direction of silicon wafer 111 l ₂ , l _2a l _2b Response vibration direction detected by cantilever P11, P21, P31 Baseline region
P11, P21, P31 Phase difference increasing region l ₁₁ , l ₂₁ , l ₃₁ Straight line extending from the low temperature side base line to the high temperature side l ₁₂ , l ₂₂ , l ₃₂ The tangential slope of the phase difference increasing region is maximized Tangent

Claims (20)

  A resin composition for an easily surface-shaped sheet having a phase difference increase starting temperature Ts of 25 ° C. or higher measured by a measuring method defined in the specification using a scanning viscoelastic microscope.   As the main component, the resin composition for an easily surface-shaped sheet is composed of at least one thermoplastic resin selected from the group consisting of polyester resins, polyolefin resins, polyamide resins, polycarbonate resins, and acrylic resins. The resin composition for an easily surface formable sheet according to claim 1. The resin composition for an easily surface-shaped sheet according to claim 1 or 2, wherein the resin composition for an easily surface-shaped sheet has an intrinsic viscosity of 0.3 to 0.65 dl / g.   An easily surface formable sheet obtained by processing the resin composition for an easily surface formable sheet according to any one of claims 1 to 3 into a sheet shape.   The easily surface-shaped sheet is obtained by differential scanning calorimetry (hereinafter referred to as DSC), and has a crystallization enthalpy ΔHcc of 1 J / g or less in a temperature rising process (temperature rising rate: 2 ° C./min). The easy-surface formable sheet according to claim 4.   A laminate comprising a plurality of layers comprising at least a layer comprising the easy-surface-formable sheet according to claim 4 or 5 and a substrate layer serving as a support, and at least one side of the laminate. An easy surface formable sheet laminate in which the easy surface formable sheet layer is disposed on a surface layer. The movement of the substrate obtained by dynamic viscoelasticity measurement (hereinafter referred to as DMA) at the glass transition temperature (hereinafter referred to as Tg21) + 40 ° C. of the layer comprising the easy-surface formable sheet constituting the surface layer of the laminate. The easy-to-surface formable sheet laminate according to claim 6, wherein the static storage viscoelastic modulus (E2 ′) is 5 × 10 ⁷ Pa or more.   The easy-surface-formable sheet laminate according to claim 6 or 7, wherein a peel strength between the base material layer and the layer composed of the easy-surface-shaped sheet constituting the surface layer is 50 mN / cm or more.   The easily surface-formable sheet laminate according to any one of claims 6 to 8, wherein the base material layer is a flexible sheet.   The easily surface-shaped sheet laminate according to any one of claims 6 to 9, wherein the base material layer is a biaxially stretched polyester film.   The easy surface formable sheet according to claim 4 or 5 is pressed using a mold, and then the mold is released (mold release temperature: T3), whereby the surface of the easy surface formable sheet is coated with gold. A surface shaping method for forming a molded product to which a mold shape is transferred, wherein the mold release temperature T3 satisfies 20 ° C. ≦ T3 ≦ Ts. The easy-surface-formable sheet according to claim 4 or 5 is pressurized with a heated die (heating temperature: T1) using a heated mold (heating temperature: T1), and then cooled in the same state. A surface shaping method for forming a molded product having a mold shape transferred by releasing the mold after releasing the press pressure (press pressure release temperature: T2) (mold release temperature: T3). The surface shaping method in which T1, T2 and T3 satisfy the following formulas (1) to (5).
Tg2 ≦ T1 ≦ Tg2 + 60 ° C. (1)
T1 <Tm (2)
Tg2-10 ° C. ≦ T2 ≦ Tg2 + 30 ° C. (3)
Ts <T2 <T1 (4)
20 ° C. ≦ T3 ≦ Ts (5)
(However, Tg2 and Tm respectively indicate the glass transition temperature and melting point of the surface layer of the easily surface-shaped sheet.)   The surface layer side constituted by the easy-surface-formable sheet of the easy-surface-formable sheet laminate according to any one of claims 6 to 10 is pressurized using a mold, and then the mold is released. (Mold release temperature: T3) By this, a surface shaping method for forming a molded product in which the mold shape is transferred to the surface of the easily surface-formable sheet, the mold release temperature T3 satisfies 20 ° C. ≦ T3 ≦ Ts. Filling surface shaping method. A hot press using a mold (heating temperature: T1) in which the surface layer side constituted by the easy surface formable sheet of the easy surface formable sheet laminate according to any one of claims 6 to 10 is heated. After pressurizing at (press temperature: T1) and then cooling as it is, releasing the press pressure (press pressure release temperature: T2) and then releasing the mold (release temperature: T3), A surface shaping method for forming a molded product to which a mold shape is transferred, wherein the T1, T2 and T3 satisfy the following formulas (1) to (5).
Tg21 ≦ T1 ≦ Tg21 + 60 ° C. (1)
T1 <Tm (2)
Tg21-10 ° C ≦ T2 ≦ Tg21 + 30 ° C (3)
Ts <T2 <T1 (4)
20 ° C. ≦ T3 ≦ Ts (5)
(However, Tg21 and Tm indicate the glass transition temperature and melting point of the surface layer of the easily surface-forming sheet constituting the surface-forming sheet laminate)   The mold has an uneven shape on the surface, and the ratio of the height H to the width S (H / S; hereinafter, aspect ratio) of the convex section of the mold is 0.1 to 25. Item 15. The surface shaping method according to any one of Items 11 to 14.   The width | variety S of the cross section of the convex part of the said metal mold | die is 0.001-20 micrometers, and height H exists in the range of 0.001-20 micrometers. Surface shaping method.   The surface shaping method according to any one of claims 11 to 16, wherein the convex portion of the mold is formed with a pitch of 0.002 to 40 µm.   A molded product having a concavo-convex shape on the surface obtained by the surface shaping method according to any one of claims 11 to 17, wherein an aspect ratio (H '/ S') of the concavo-convex convex portion is 0.1 to A molded article characterized by being 15.   19. The molded product according to claim 18, wherein the molded product has a concavo-convex convex width S 'of 0.001 to 20 [mu] m and a height H' of 0.001 to 20 [mu] m.   The molded product according to claim 18 or 19, wherein the pitch of the convex portions is 0.002 to 40 µm.

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