JP2005297545A - Easily surface-shapable sheet, laminate of easily surface-shapable sheet, surface shaping method using the same and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface-shapable sheet having a good property and a releasing property evne if a pattern having a high aspect ratio is shaped in a large surface area. <P>SOLUTION: The easily surface-shapable sheet has a crystallization enthalpy ▵Hcc of 0-20 J/g by a temperature increasing process (temperature increasing speed: 2°C/min) obtained by differential scanning calorimetry (DSC), a dynamic storage modulus E1' of 0.1×10<SP>9</SP>to 2.5×10<SP>9</SP>Pa obtained by dynamic viscoelasticity measurement (DMA) at 25°C and a dynamic storage modulus E2' of 1×10<SP>4</SP>to 2×10<SP>7</SP>Pa at a glass transition point (Tg) of +30°C. This surface shaping method comprises steps of heating the easily surface-shapable sheet (heating temperature:T1), pressing the sheet (pressing temperature:T1) using a die, relieving pressure (pressure relieving temperature:T2) by cooling and then removing the sheet from the die (die removal temperature:T3), whereby a molded article having a form of the die transferred on it is obtained. In this method, T1, T2 and T3 are set to satisfy a predetermined relationship. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a sheet material that can be easily shaped on a surface, in particular, a sheet material capable of shaping a high aspect ratio structure in a large area, a surface shaping method using the sheet material, and a molded product thereof. is there.

  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, a high-precision fine structure forming technique is required. In the semiconductor field, in addition to a high-precision fine structure forming technique, miniaturization of processing dimensions is required to improve the integration degree of a semiconductor integrated circuit.

  Therefore, even in photolithography, which is a representative technique for microfabrication, it is necessary to increase the resolution and control the fine dimensions with high precision. Attempts have been made to shorten the exposure wavelength, and so on. A minimum line width of 100 nm resolution has been achieved using an ArF laser. Furthermore, the resolution of several tens of nanometers using electron beams and X-rays, so-called nanostructure formation technology is approaching practical use.

  However, the improvement in resolution by shortening the exposure wavelength leads to an initial cost of the exposure machine itself and an increase in the price of the mask to be used. As a result, it is very disadvantageous in terms of cost. Further, since the irradiation spot diameter is small, the productivity is low for forming a fine structure with a large area.

  Therefore, recently, imprint lithography has been proposed by Chou et al. As a technique for easily shaping a fine structure (see Non-Patent Document 1). Imprint lithography is a technique for transferring a pattern on a mold to a resin, and there are two types of methods, thermal and optical. The thermal type is a method in which a thermoplastic resin is heated to a glass transition temperature Tg or higher and lower than the melting point Tm, and a mold having a concavo-convex pattern is pressed on the thermoplastic resin. This is a technique for transferring a pattern on a mold to a resin by irradiating light in a state of pressing and curing. Although these technologies require initial costs for mold fabrication, many microstructures can be replicated from a single mold, resulting in a technology that allows the microstructure to be shaped cheaply compared to photolithography. It is.

  So far, various studies have been conducted to shape a high aspect ratio pattern with high accuracy using this technique. For example, examination of the surface treatment agent on the mold surface (see Patent Documents 1, 2, and 3), investigation of incorporating the mold surface treatment process into the molding process (see Patent Document 4), treatment with a solvent-soluble surface treatment agent In addition, a study of releasing the mold while dissolving the surface treatment agent in a solvent (Patent Document 5) can be mentioned.

Also, large area shaping has been studied for simultaneous processing of various patterns and for manufacturing large area devices. For example, in order to correct the nonuniformity of the press pressure, a study has been made to improve the in-plane uniformity at the time of forming a large area by giving a height difference to the depth of the concave portion of the mold (Patent Document 6). ).
S. Y. Chou et al., “Appl. Phys. Lett.”, American Physical Society, 1995, Vol. 67, No. 21, p. 3314 JP 2002-283354 A (page 4-7) JP 2002-270541 A (page 2-8) JP2003-0777807 (page 3-7) JP 2003-109915 A (page 3-4) Japanese Patent Laying-Open No. 2003-332211 (page 3-4) JP 2002-289560 A (page 3-5)

  However, these methods mainly improve mold releasability by controlling the mold surface treatment method and control the shape of the mold. Further, there is no description of formation of a pattern with a high aspect ratio or, furthermore, formation of a high aspect ratio pattern with a large area. When shaping a pattern with a high aspect ratio in a large area, the difference in volume variation between the mold and the resin during heating / cooling becomes too large, and the resin bites into the mold and cannot be released. There is. In addition, even if the mold can be released, there are problems that the accuracy of the pattern is reduced, or that the pattern is partially lost and becomes a defect.

  Accordingly, an object of the present invention is to overcome such problems of the prior art and to provide a sheet having good transferability and releasability even when a high aspect ratio pattern is formed on the surface with a large area (hereinafter referred to as easy surface shaping). Sheet), a surface shaping method using the sheet, and a molded product thereof.

The present invention employs the following means in order to solve such problems. That is, the easy-surface formable sheet of the present invention has a crystallization enthalpy ΔHcc of 0 to 20 J / g in a temperature rising process (temperature rising rate: 2 ° C./min) obtained by differential scanning calorimetry (hereinafter referred to as DSC). And a dynamic storage elastic modulus E1 ′ at 25 ° C. obtained by dynamic viscoelasticity measurement (hereinafter referred to as DMA) is 0.1 × 10 ^{9 to} 2.5 × 10 ⁹ Pa, and glass The dynamic storage elastic modulus E2 ′ at a transition temperature (hereinafter, Tg) + 30 ° C. is 1 × 10 ⁴ to 2 × 10 ⁷ Pa.

The easy-surface-formable sheet of the present invention has the following features (1) to (6).
(1) Dynamic storage elastic modulus E1 ′ at 25 ° C. in DMA, preferably 0.5 × 10 ^{9 to} 2.0 × 10 ⁹ Pa.
(2) The dynamic loss elastic modulus E2 ″ at the glass transition temperature (hereinafter referred to as Tg) + 30 ° C. in DMA is 1 × 10 ^{3 to} 1.8 × 10 ⁶ Pa.
(3) The elongation at break is 40% or more.
(4) It is mainly formed from a thermoplastic resin selected from a polyester resin, a polyolefin resin, a polyamide resin, an acrylic resin, or a mixture thereof.
(5) A laminate comprising a plurality of resin layers.
(6) The layer which consists of an easily surface formable sheet which satisfy | fills the above-mentioned requirements must be formed in the surface layer at least.

  The easy-surface-formable sheet laminate of the present invention is a laminate comprising an easy-surface-formable sheet that satisfies any of the requirements described above and a base material that serves as a support, and at least the easy-surface-formable sheet laminate. The easy-surface formable sheet is formed on the surface layer of the formable sheet laminate.

Further, the surface shaping method of the present invention is a method of heating the above-mentioned easy surface formable sheet or the easy surface formable sheet laminate (heating temperature: T1) and pressing it using a mold (press temperature: T1). Then, after cooling and releasing the press pressure (press pressure release temperature: T2), the mold is released (release temperature: T3) to form a molded product having the mold shape transferred thereto. The method is characterized in that T1, T2 and T3 satisfy the following formulas (1) to (5).
Tg ≦ T1 ≦ Tg + 50 ° C. (1)
T1 <Tm (2)
Tg-20 ≦ T2 ≦ Tg + 20 ° C. (3)
T2 <T1 (4)
20 ° C. ≦ T3 ≦ T2 (5)
(Here, Tm is the melting point of the surface-formable sheet surface layer).

The surface shaping method of the present invention comprises the following features (1) to (3).
(1) The mold has a concavo-convex shape on the surface, and the ratio H / S (hereinafter, aspect ratio) of the height H and width S of the convex section of the mold is 0.1 to 25, preferably 1-20.
(2) The width S of the cross section of the mold convex part is 0.01 to 100 μm, and the height H is 0.01 to 500 μm.
(3) The convex part of the mold is formed with a pitch of 0.02 to 500 μm.

The molded product of the present invention is a molded product obtained by the surface shaping method described above, and has the following features (1) to (4).
(1) The aspect ratio H ′ / S ′ of the convex portion is 0.1 to 15, preferably 1 to 10.
(2) The width S ′ of the convex portion is 0.01 to 200 μm and the height H ′ is 0.01 to 500 μm.
(3) The pitch of the convex portions is formed at 0.02 to 500 μm.
(4) The ratio A ′ / A of the cross-sectional area A ′ of the convex part of the molded product and the cross-sectional area A of the concave part of the mold is 0.90 or more.

  According to the present invention, an easily surface formable sheet excellent in transferability and releasability can be obtained, and by using this, a high aspect ratio pattern can be formed in a large area.

  The present inventors diligently studied a sheet material having good transferability to the surface, and solved the above problems by selecting a material having specific physical properties, and were excellent in transferability to the surface and releasability. The present inventors have reached the present invention by investigating that a sheet (hereinafter, a sheet having easy surface formability) can be formed.

That is, the easy-surface formable sheet of the present invention has a crystallization enthalpy ΔHcc of 0 to 20 J / g in a temperature rising process (temperature rising rate: 2 ° C./min) obtained by differential scanning calorimetry (hereinafter DSC). And the dynamic storage elastic modulus E1 ′ at 25 ° C. obtained by dynamic viscoelasticity measurement (hereinafter referred to as DMA) is 0.1 × 10 ^{9 to} 2.5 × 10 ⁹ Pa, and the glass transition The dynamic storage elastic modulus E2 ′ at a temperature (hereinafter referred to as Tg) + 30 ° C. is 1 × 10 ⁴ to 2 × 10 ⁷ Pa.

  The crystallization enthalpy ΔHcc referred to here is a value obtained according to JIS K7122 (1999). In the differential scanning calorimetry chart obtained when scanning at a temperature rising rate of 2 ° C./min, the heat generated by crystallization. It is the value obtained from the peak area. If the crystallization enthalpy ΔHcc is larger than 20 J / g, the resin constituting the sheet quickly crystallizes at the time of temperature rise when shaping on the surface, and deformation of the sheet hardly occurs when shaping. For this reason, when the high aspect ratio pattern is formed on a large area, the resin is not sufficiently filled in the mold, resulting in a decrease in transfer accuracy, or an in-plane pressure imbalance resulting in in-plane uniformity of transfer. It is not preferable for reasons such as. By making the crystallization enthalpy ΔHcc within this range, good transferability and in-plane uniformity can be obtained even when a high aspect ratio pattern is formed. Furthermore, the crystallization enthalpy ΔHcc is preferably 15 J / g or less, more preferably 5 g / J or less, and most preferably 0 J / g.

In addition, the easy-surface formable sheet of the present invention has a dynamic storage elastic modulus E1 ′ at 25 ° C. of 0.1 × 10 ^{9 to} 2.5 obtained by dynamic viscoelasticity measurement (hereinafter referred to as DMA). It is characterized by × 10 ⁹ Pa. More preferably ^{0.5 × 10 9 ~2 × 10 9} Pa. The dynamic storage elastic modulus E ′ here is a method according to JIS K-7244, the tensile mode, the sample dynamic amplitude speed (drive frequency) is 1 Hz, the distance between chucks is 5 mm, the strain amplitude is 10 μm, and the initial force amplitude. It is a value obtained when temperature dependency (temperature dispersion) is measured under the measurement conditions of a value of 100 mN and a heating rate of 2 ° C./min. If the dynamic storage elastic modulus E1 ′ at 25 ° C. exceeds this range, the rigidity of the resin becomes high, and it becomes difficult to release from the mold when forming a large area with a high aspect ratio pattern, which is not preferable. If it is less than this range, the mechanical strength of the molded product is lowered, and even when the mold is released or deformed, the stability over time of the shape, impact resistance, etc. are deteriorated. By setting the dynamic storage elastic modulus E1 ′ at 25 ° C. within this range, it is possible to achieve both the releasability when forming a large area with a high aspect ratio pattern and the mechanical strength of the molded product.

Moreover, the easy-surface formable sheet | seat of this invention is characterized by the dynamic storage elastic modulus E2 'in glass transition temperature Tg + 30 degreeC being 1 * 10 < ⁴ > -2 * 10 < ⁷ > Pa. More preferably, it is 1 * 10 < ⁴ > -1 * 10 < ⁷ > Pa. The glass transition temperature Tg here is a method according to JIS K-7244. The sample dynamic amplitude speed (driving frequency) is 1 Hz, the tensile mode, the distance between chucks is 5 mm, and the heating rate is 2 ° C./min. This is the temperature at which tan δ is maximized when temperature dependency (temperature dispersion) is measured. When the dynamic storage elastic modulus E2 ′ at Tg + 30 ° C. is higher than this value, deformation of the sheet is difficult to occur during shaping. For this reason, it is necessary to increase the load and press pressure very high, but when molding a large area with a high aspect ratio pattern, the resin is insufficiently filled in the mold and the transfer accuracy is reduced. This is not preferable for reasons such as a pressure imbalance occurring within the surface and a decrease in in-plane uniformity of transfer. Further, the larger the load, the greater the load on the mold, and the repeated use durability is lowered, which is not preferable. On the other hand, if it is lower than this value, the fluidity of the resin at the time of pressing becomes too high and the resin flows into the mold without being filled at the time of pressing. By setting the dynamic storage elastic modulus E2 ′ at Tg + 30 ° C. within this range, good transfer accuracy and in-plane uniformity can be obtained even at the time of large area shaping of a high aspect ratio pattern.

Also, easy surface shaping sheet of the present invention is a dynamic storage modulus E1 'is ^{0.1 × 10 9 ~2.5 × 10 9} Pa at 25 ° C. obtained by DMA measurement in the above conditions And the dynamic storage elastic modulus E2 ′ at Tg + 30 ° C. is 1 × 10 ⁴ to 2 × 10 ⁷ 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 Tg + 30 ° C. is 1 × 10 ⁴ to 1 × 10. ⁷ Pa. In the present invention, within this range, it is possible to obtain releasability, transfer accuracy, in-plane uniformity, and mechanical strength of a molded product when forming a large area with a high aspect ratio pattern.

In the easy-surface-shaped sheet of the present invention, the dynamic loss elastic modulus E2 ″ at Tg + 30 ° C. obtained by DMA is preferably 1 × 10 ^{3 to} 1.8 × 10 ⁶ Pa. More preferably. It is 1 × 10 ^{3 to} 1.5 × 10 ⁶ Pa. When the dynamic loss elastic modulus E2 ″ at Tg + 30 ° C. is higher than this value, deformation of the sheet is difficult to occur during shaping. For this reason, it is necessary to increase the load and press pressure very high, but when molding a large area with a high aspect ratio pattern, the resin is insufficiently filled in the mold and the transfer accuracy is reduced. This is not preferable for reasons such as a pressure imbalance occurring within the surface and a decrease in in-plane uniformity of transfer. Further, the larger the load, the greater the load on the mold, and the repeated use durability is lowered, which is not preferable. On the other hand, if it is lower than this value, the fluidity of the resin at the time of pressing becomes too high and the resin flows into the mold without being filled at the time of pressing. By setting the dynamic loss elastic modulus E2 ″ at Tg + 30 ° C. within this range, good transfer accuracy and in-plane uniformity can be obtained even when forming a large aspect ratio pattern with a large area.

  The easy-surface formable sheet of the present invention preferably has a breaking elongation of 40% or more, and preferably a breaking elongation of 80% or more. The elongation at break here is a value obtained by a method according to ASTM D638, and a 1/8 inch-thick dumbbell-shaped test piece is prepared, the temperature is 23 ° C., the humidity is 65% RH, and the speed is 5 mm. It is the elongation at break when pulled at / min. If the elongation at break is less than this range, the stress generated by volume fluctuations during heating / cooling of the sheet during large area molding of a high aspect ratio pattern cannot be relieved, and the sheet bites into the mold and is released. become unable. Even if the mold can be released, the pattern transfer accuracy is lowered, or the pattern is partially lost, which is a defect. Therefore, by setting the breaking elongation within this range, it is possible to improve the releasability while maintaining a good transfer system.

The glass transition temperature Tg of the easy-surface formable sheet of the present invention is preferably 40 to 180 ° C, more preferably 50 to 160 ° C, and most preferably 50 to 120 ° C. If the glass transition temperature Tg is below this range, the heat resistance of the molded product is lowered and the shape changes with time, which is not preferable. If the temperature exceeds this range, the forming temperature is high and energy is inefficient, and the volume change during heating / cooling of the sheet becomes large, and the sheet can bite into the mold and cannot be released. Even if it can be done, it is not preferable because the transfer accuracy of the pattern is lowered, or the pattern is partially lacked to cause a defect. In the easy-surface formable sheet of the present invention, good transferability and releasability can be obtained by setting the glass transition temperature Tg of the sheet within this range. The easy-surface formable sheet of the present invention is thermoplastic. Resins are the main components, specifically, polyester resins such as polyethylene terephthalate, polyethylene-2, 6-naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene, polystyrene, polypropylene, polyisobutylene, polybutene, poly Polyolefin resins such as methylpentene, polyamide resins, polyimide resins, polyether resins, polyester amide resins, polyether ester resins, acrylic resins, polyurethane resins, polycarbonate resins, polyvinyl chloride resins, etc. And so on. Among them, especially from polyester resins, polyolefin resins, polyamide resins, acrylic resins, or mixtures thereof because of the variety of monomer types to be copolymerized and the ease of adjusting the material properties. It is preferably formed mainly from a selected thermoplastic resin. Here, as the easy-surface formable sheet of the present invention, the above-mentioned thermoplastic resin is preferably composed of 50% by weight or more.

  The glass transition temperature Tg, dynamic storage elastic modulus E ′, dynamic loss elastic modulus E ″, elongation at break and the like of the easily surface-shaped sheet of the present invention are appropriately copolymerized with the resin monomer species constituting the sheet. For example, by introducing a rigid skeleton such as bisphenol-A, the glass transition temperature Tg and dynamic storage elastic modulus E ′ are increased, and a flexible skeleton such as polyethylene glycol is introduced. Then, the glass transition temperature Tg and the dynamic storage elastic modulus E ′ are lowered.

  Moreover, the glass transition temperature Tg, dynamic storage elastic modulus E ′, dynamic loss elastic modulus E ″, elongation at break, etc. can be controlled by introducing a plasticizer or a crosslinking agent. The glass transition temperature Tg, the dynamic storage elastic modulus E ′, the glass transition temperature Tg, the dynamic storage elastic modulus E ′, and the dynamic loss elastic modulus increase as the amount of the plasticizer increases. E ″ decreases and the elongation at break increases. In the case of a crosslinking agent, if the amount of addition is increased or the degree of crosslinking is increased, the glass transition temperature Tg, the dynamic storage elastic modulus E ′, the dynamic loss elastic modulus E ″ are improved, and the elongation at break is increased. By adding these appropriately, the sheet may be formed so as to satisfy the above-mentioned condition range.

  Moreover, you may add the component etc. which harden | cure by electromagnetic wave irradiation etc. to the easily surface formable sheet | seat of this invention. In this case, the mechanical strength and thermal stability of the molded product can be improved by irradiating and curing the electromagnetic wave on the molded product transferred from the mold.

  Moreover, various additives can be added to the easy-surface formable sheet of the present invention 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, Examples include thickeners, pH adjusters and salts.

  The easy-surface formable sheet of the present invention may be a sheet composed of the above-mentioned resin alone or a laminate composed of a plurality of resin layers. In this case, compared with a single sheet, surface properties such as slipperiness and friction resistance, mechanical strength, and heat resistance can be imparted. In the case of a laminate composed of a plurality of resin layers as described above, it is preferable that the entire sheet satisfies the above-mentioned requirements, but the entire sheet does not satisfy the above-mentioned requirements as a whole, but at least the above-mentioned requirements are satisfied. If the filling layer is formed on the surface layer, the surface can be shaped easily.

  Moreover, the easily surface-shaped formable sheet of the present invention may be stretched uniaxially or biaxially. However, depending on the material used, orientation crystallization proceeds by stretching at a high magnification. As a result, the glass transition temperature Tg, the dynamic storage elastic modulus E ′, and the dynamic loss elastic modulus E ″ increase, and the moldability decreases. Therefore, stretching is performed while appropriately controlling in accordance with changes in physical property values.

  The easy-surface-formable sheet laminate of the present invention is an easy-surface-formable sheet laminate comprising the above-mentioned easy-surface-formable sheet and a base material that serves as a support, and the easy-surface-formable sheet laminate The easy-surface formable sheet is formed on the surface layer of the laminate. The base material used as the support in this case refers to a sheet-like material whose shape does not change during shaping. In this case, the easy-surface-formable sheet laminate as a whole does not satisfy the above-mentioned requirements, but at least the above-mentioned easy-surface-formable sheet is formed on the surface layer, so that the surface can be easily shaped. . Examples of substrates used include organic film substrates such as polyester resins, biaxially stretched polyester films, polyolefin resins, acrylic resins, metal substrates such as silicon, stainless steel, aluminum, aluminum alloys, iron, steel, titanium, and the like An inorganic base material such as concrete is applicable.

  The preferred thickness (thickness, film thickness) of the easy-surface formable sheet of the present invention is preferably in the range of 0.01 to 5 mm. In the case of an easily surface-shaped sheet laminate, a sheet having a thickness in this range may be provided on the substrate. In this case, the thickness of the substrate is not particularly limited.

  For example, in the case of a single sheet, a method for forming an easy surface formable sheet of the present invention is a method in which a sheet forming material is heated and melted in an extruder and extruded from a die on a cast drum cooled to be processed into a sheet ( Melt casting method). 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. And the like (solution casting method) and the like.

  In addition, as a method for producing a laminate, two different thermoplastic resins are put into two extruders and melted and coextruded on a cast drum cooled from a die (coextrusion method). ), A method of laminating the raw material of the coating layer into a sheet made of a single film into an extruder, melting and extruding and extruding from the die (melt laminating method), a sheet made of a single film and an easily surface-shaped sheet Separately producing a single film and thermocompression bonding with a heated group of rolls (thermal laminating method), and other methods such as dissolving a sheet-forming material in a solvent and applying the solution onto the sheet (coating method), etc. Is mentioned. Also in the case of an easily surface-shaped sheet laminate, the above-described melt lamination method, heat lamination method, coating method, or the like can be used. Such a base material may have been subjected to a treatment such as a base preparation material or an undercoat material. Moreover, the structure as a composite_body | complex with the base material with another function is also preferable.

  The example of the method of forming a pattern using the easily surface-shaped sheet | seat of this invention and an easily surface-shaped sheet laminated body is demonstrated using FIG.

  The easy-surface formable sheet 1 of the present invention and the mold 2 having irregularities that are inverted from the pattern to be transferred are heated within a temperature range of the glass transition temperature Tg or more and less than the melting point Tm (FIG. 1 (a )), The easy-surface-formable sheet 1 of the present invention and the mold 2 are brought close to each other, pressed as it is at a predetermined pressure, and held for a predetermined time (FIG. 1 (b)). 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. 1 (c)).

  Further, as the surface shaping method of the present invention, in addition to the method of pressing a lithographic plate as shown in FIG. 1 (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. In the case of roll-to-roll continuous molding, the productivity is superior to the lithographic press method.

  In the surface shaping method of the present invention, the heating temperature and the press temperature T1 are preferably in the range of Tg ° C. to Tg + 50 ° C. 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 is difficult to occur when the mold is pressed, and the pressure required for molding is low. Beyond this range, the heating temperature and press temperature T1 are high and inefficient in energy, and the difference in volume variation during heating / cooling of the mold and the sheet becomes too large. Thus, it is not preferable because the sheet can not be released due to being bitten into the mold, or even if the sheet can be released, the accuracy of the pattern is reduced, or the pattern is partially missing and becomes a defect. In the surface shaping method of the invention, by setting the heating temperature and the press temperature T1 within this range, both good moldability and mold release can be achieved.

  In the surface shaping method of the present invention, the pressing pressure depends on the values of the dynamic storage elastic modulus E ′ and the dynamic loss elastic modulus E ″ at the pressing temperature T1, but is preferably 0.5 to 50 MPa. If it is less than this range, the resin is insufficiently filled in the mold and the pattern accuracy decreases, and if this range is exceeded, the required load increases, Since the load is repeated repeatedly and the durability for use decreases, it is not preferable.By setting the press pressure within this range, good transferability can be obtained.

  In the surface shaping method of the present invention, the press pressure holding time depends on the value of the dynamic storage elastic modulus E ′ and dynamic loss elastic modulus E ″ at the press temperature T1 and the molding pressure, but it is 10 seconds to 10 minutes. If it is not within this range, the resin is not sufficiently filled in the mold, resulting in a decrease in pattern accuracy and in-plane uniformity, and if this range is exceeded, deterioration due to thermal decomposition of the resin, etc. In the surface shaping method of the present invention, good transferability and mechanical strength of the molded product can be obtained by keeping the holding time within this range. Can be compatible.

  In the surface shaping method of the present invention, the press pressure release temperature T2 is preferably lower than the press temperature T1 within a temperature range of Tg-20 ° C to Tg + 20 ° C. More preferably, it is Tg-10 degreeC-Tg + 20 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, by setting the press pressure release temperature T2 within this range, both good transferability and releasability can be achieved.

  Moreover, in the surface shaping method of this invention, it is preferable that mold release temperature T3 exists in the temperature range of 25-T2 degreeC. More preferably, it is the temperature range of 20-Tg. Exceeding this range is not preferable because the flowability of the resin at the time of mold release is high, and the pattern is deformed and the accuracy is lowered. In the surface shaping method of the present invention, mold release can be performed with high pattern accuracy by setting the temperature at the time of mold release within this range.

  The cross-sectional views of the mold used in the surface shaping method of the present invention are illustrated in FIGS. The shape of the convex portion 11 observed in the cross section of FIG. 2 is a rectangle (FIG. 2 (a)), a trapezoid (FIG. 2 (b)), a triangle (FIG. 2 (c)), or a deformed form thereof. (FIGS. 2D, 2E, and 2F) and a mixture thereof are preferably used, but shapes other than these can also be used. That is, in addition to FIG. 2 (a) in which the side surface of the convex portion 11 is substantially perpendicular to the sheet surface in the cross-sectional view, forms such as FIGS. 2 (b) to 2 (f) are also included. Although FIG. 2 shows an example in which flat portions are formed between adjacent mold convex portions, the adjacent mold convex portions may not be flat, and the skirts of adjacent mold convex portions are connected. You may do it. As for the shape of the mold recess, a shape such as a rectangle, a trapezoid, a triangle, a bell shape, or a shape obtained by deforming them can be preferably used as in the case of the mold protrusion.

  3A to 3C are perspective views schematically showing a part of a mold in the surface shaping method of the present invention. As an arrangement structure of the convex portions 11 in the functional layer, for example, as shown in FIG. 3A, the convex portions 11 are arranged in a dot shape, and as shown in FIG. A structure extending in the form of stripes in the surface direction, a structure in which the convex portions 11 spread in a lattice shape in the surface direction as shown in FIG. 3C, and the like are used, but are not limited thereto.

  4A to 4H are cross-sectional views schematically showing the arrangement of the convex portions 11 and the concave portions 12 in a cross section when the mold is cut in parallel to the surface. As shown in FIGS. 4A to 4H, the shape of the 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. 4A to 4C show the case where the concave portion 12 has a stripe shape, FIG. 4D shows the case where the concave portion 12 has a circular cross section, FIG. 4E shows the case where the concave portion 12 has a triangular shape, FIG. (F)-(g) illustrates the case where it is a square shape, and FIG.4 (h) illustrates the case where it is a hexagonal shape, respectively. The recesses 12 may be aligned as shown in the figure, may be arranged randomly, or may have different shapes mixed together. Further, as shown in FIGS. 5A to 5D, the shape of the 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.

  Moreover, the width | variety S of the convex part 11 of the metal mold | die used for the surface shaping | molding method in this invention is 0.01-100 micrometers, and the height H is 0.01-500 micrometers. Moreover, the aspect ratio H / S of a convex part is 0.1-25, Preferably it is 1-20.

  Here, the width S of the convex portion 11 is a unit length of the convex portion as illustrated in FIG. In the case of the striped pattern of FIG. 3, the measurement is performed in the direction of shorter unit length. In the case of FIGS. 4D to 4H, the width S is defined as the shortest unit length. Further, when the convex portion 11 is circular as shown in FIG. 5 (a), the diameter thereof is indicated. When the convex portion 11 is elliptical, the short diameter thereof is indicated. As shown in FIGS. In this case, the diameter of the inscribed circle may be the width 11 of the convex portion. Moreover, the height H of the convex part in the thickness direction of a metal mold | die refers to the thickness of the convex part 22, as shown in FIG.

  Moreover, this array layer WHEREIN: The area ratio of the convex part 11 and the recessed part 12 is arbitrary in the mold surface direction cross section in this array layer.

  Here, the width of the convex portion 11 and the width of the concave portion 12 are represented by lengths S and t, respectively, in the case of FIG. In addition, when the length unit changes with positions like FIG.2 (b) etc., it represents with the average value. Further, the repeating unit (pitch) of the unevenness is expressed by the sum of the width S of the convex portion and the width t of the concave portion, and the pitch of the convex portion of the mold is 0.02 to 500 μm.

  The material of the mold is not particularly limited, but a metal material rich in releasability and durability such as stainless steel (SUS) and nickel (Ni) is preferable.

  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). Is mentioned. 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.

  Preferable examples of the surface treatment agent used in the chemical adsorption method include a fluorine-based silane coupling agent. 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. One example of the treatment method is to immerse the mold in a solution in which a fluorinated silane coupling agent is dissolved in a fluorinated solvent. 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 easily surface-forming sheet of the present invention, and the cross-sectional views thereof are shown in FIGS. ), The shaped part 3 is formed on the sheet-like base part 4. FIG. 6A shows a molded product formed on the easily surface-shaped sheet of the present invention, and FIG. 6B shows a molded product formed on the easily surface-shaped sheet laminate of the present invention. It is a transverse cross section showing typically. 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. 7 (a) to (f). To do. As the shape of the convex portion 22 observed in the cross section of FIG. 7, a rectangular shape (FIG. 7A), a trapezoid shape (FIG. 7B), a triangular shape (FIG. 7C), or a modified one thereof. (FIGS. 7D, 7E and 7F) and a mixture thereof are preferably used, but shapes other than these can also be used. That is, in addition to FIG. 7A and the like in which the side surface of the convex portion 22 is substantially perpendicular to the sheet surface in the cross-sectional view, forms such as FIGS. 7B to 7E are also included. Further, FIG. 7 shows an example in which flat portions are formed between adjacent molded product convex portions, but the gap between adjacent molded product convex portions may not be flat, and further, the skirt of the adjacent molded product convex portions. May be connected. In addition, as for the shape of the concave portion 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 similarly to the above-described convex portion of the mold.

  8 (a) to 8 (c) are perspective views schematically showing a part of a molded product obtained by the surface shaping method of the present invention. As an arrangement structure of the convex portions 22 in the shaping portion 3, for example, as shown in FIG. 8A, a structure in which the convex portions 22 are arranged in a dot shape, as shown in FIG. A structure in which the protrusions 22 extend in the form of stripes in the surface direction, or a structure in which the protrusions 22 extend in a lattice shape in the surface direction as shown in FIG. 8C is used, but is not limited thereto.

  9A to 9H schematically illustrate the arrangement of the convex portions 22 and the concave portions 21 in a cross section when the molded product obtained by the surface shaping method of the present invention is cut in parallel with the surface thereof. It is sectional drawing shown. As shown in FIGS. 9A to 9H, the shape of the recess 21 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 recess 21 has a stripe shape, FIG. 9D shows a case where the recess 21 has a circular cross section, FIG. 9E shows a case where the recess 21 has a triangular shape, FIG. When (f)-(g) is a square shape, FIG.9 (h) illustrates the case where it is a hexagonal shape, respectively. The recesses 21 may be aligned as shown in the figure, may be arranged randomly, or may have different shapes mixed together. Further, as shown in FIGS. 10A to 10D, the shape of the convex portion 22 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.

  Moreover, the shape of the convex part 22 of the molded product obtained by the surface shaping method of the present invention is preferably such that the convex part 22 has a width S ′ of 0.01 to 200 μm and a height H ′ of 0.01 to 500 μm. It is. The aspect ratio H ′ / S ′ of the convex portion 22 is 0.1 to 15, preferably 1 to 10.

  Here, the width S ′ of the convex portion 22 is the unit length of the convex portion as illustrated in FIG. 7A and FIG. 8. In the case of the stripe pattern shown in FIG. 8, 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 is circular as shown in FIG. 10 (a), the diameter thereof is indicated. When the convex portion 22 is elliptical, the short diameter thereof is indicated. As shown in FIGS. In this case, the diameter of the inscribed circle may be the convex portion 22 width S ′. Further, the height H ′ of the convex portion in the thickness direction of the molded product indicates the thickness of the convex portion 22 as shown in FIG. 8.

  Moreover, this array layer WHEREIN: In the molded article surface direction cross section in this array layer, the area ratio of the convex part 22 and the area of the recessed part 21 is arbitrary.

  Here, in the case of FIG. 7A, the width of the convex portion 22 and the width of the concave portion 21 are represented by the lengths S ′ and t ′, respectively. In addition, when the length unit changes with positions like FIG.7 (b) etc., it represents with the average value. The repetition unit (pitch) of the unevenness is expressed by the sum of the width S ′ of the convex portion and the width t ′ of the concave portion, and the pitch of the convex portion of the molded product is 0.02 to 500 μm.

  Further, the transferability is determined by the ratio of the cross-sectional area A ′ of the convex portion of the molded product and the cross-sectional area A of the concave portion of the mold. “Transferability is good” means that the ratio A ′ / A is preferably 0.90 or more, more preferably 0.95 or more.

  Moreover, as thickness l 'of the base 4 of the molded article obtained by the surface shaping method of this invention, although arbitrary, 20-2 mm is preferable from surfaces, such as mechanical strength, More preferably, it is 30-1 mm. More preferably, it is 50-500 micrometers. However, as shown in FIG. 6B, 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.

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

[Characteristic evaluation method]
A. Crystallization enthalpy ΔHcc
The crystallization enthalpy ΔHcc was determined according to JIS K7122 (1999) using a differential scanning calorimeter “Robot DSC-RDC220” manufactured by Seiko Denshi Kogyo Co., Ltd., and a disk session “SSC / 5200” for data analysis. 5 mg of each sheet was weighed in a sample pan and scanned at a rate of temperature increase of 2 ° C./min. The crystallization enthalpy ΔHcc was determined from the area of the crystallization exothermic peak.

B. Dynamic storage elastic modulus E ′, dynamic storage elastic modulus E ″, glass transition temperature Tg
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. according to JIS-K7244 (1999). Tensile mode, driving frequency The temperature dependence of the viscoelastic properties of each sheet was measured under the measurement conditions of 1 Hz, the distance between chucks of 5 mm, and the temperature increase rate of 2 ° C./min. Storage elastic modulus E ′ Dynamic loss elastic modulus E ″ was determined. Further, the temperature at which tan δ is maximized was defined as the glass transition temperature Tg.

C. Elongation at break The elongation at break was determined using an automatic measuring device “Tensilon AMF / RTA-100” manufactured by Orientec Co., Ltd., as defined in ASTM D638. A 1/8 inch dumbbell-shaped test piece was prepared, and the elongation at break was determined when the test piece was pulled at a temperature of 23 ° C., a humidity of 65% RH, and a speed of 5 mm / min.

D. Release properties The release properties were determined as follows. When the sheet and the mold are heated (heating temperature: T1), pressed (pressing temperature: T1), then cooled to release the pressing pressure (pressing pressure releasing temperature: T2), and then release is attempted. In addition,
If the resin can be released from the mold: ○
When resin cannot be released from the mold: ×
It was.

E. Cross-sectional structure After cutting out the cross section of the mold and the molded product and depositing platinum-palladium, the photograph was taken at 300 times using a scanning electron microscope S-2100A manufactured by Hitachi, Ltd., and the cross section was observed. Convex height, H width S, aspect ratio H / S, cross-sectional area A of concave part, convex part height H ′, width S ′, aspect ratio H ′ / S ′, convex part breakage The area A ′ was determined.

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.
Less than 0.90: ×
It was.

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

(Example 1)
Cyclohexanedimethanol 60% copolymerized PET (“Easter PET-G” DN-071: manufactured by Eastman Co., Ltd.) was dried at 70 ° C. for 4 hours and then melted at 280 ° C. in an extruder. The sheet was extruded onto a cast drum at 0 ° C. and cooled to obtain a sheet having a thickness of 600 μm.

  The obtained sheet was measured for glass transition temperature Tg, room temperature and dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break. The results are shown in Table 1. .

  Further, the obtained sheet and mold (square lattice pattern (pitch 100 μm, width 20 μm, depth 160 μm), convex portion: line width S = 20 μm, height H = 160 μm, aspect ratio H / S = 8, FIG. 11 (a))) was heated to 110 ° C., the sheet and the uneven surface of the mold were brought into contact with each other, pressed at 20 MPa, and held for 2 minutes. Thereafter, the press was released after cooling to 90 ° C., cooled to 50 ° 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, the shape of the mold was sufficiently transferred (A ′ / A = 0.962), a square with a pitch of 100 μm, a width of 80 μm, and a depth of 160 μm. It was confirmed that a lattice pattern (convex portion: width S ′ = 80 μm, height H ′ = 160 μm, aspect ratio H ′ / S ′ = 2 (see FIG. 11B)) was formed.

(Example 2)
Cyclohexanedimethanol 33% copolymerized PET ("Easter PET-G" DN-003: manufactured by Eastman Co., Ltd.) was dried at 70 ° C for 4 hours, then melted at 280 ° C in an extruder and cast from the die. It was extruded on a drum and cooled to obtain a sheet having a thickness of 600 μm.

  With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break were measured by the methods described above. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the shape of the mold was sufficiently transferred (A ′ / A = 0.957), a square having a pitch of 100 μm, a width of 80 μm, and a depth of 160 μm. It was confirmed that a lattice pattern (convex portion: width S = 80 μm, height H = 160 μm, aspect ratio H / S = 2 (see FIG. 11B)) was formed.

(Example 3)
Cyclic polyolefin (“Apel”: APL8008T: Mitsui Chemicals, Inc.) was melted at 220 ° C. in an extruder, extruded from the die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

  With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break were measured by the methods described above. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the shape of the mold was sufficiently transferred (A ′ / A = 0.997), a square having a pitch of 100 μm, a width of 80 μm, and a depth of 160 μm. It was confirmed that a lattice pattern (convex portion: width S ′ = 80 μm, height H ′ = 160 μm, aspect ratio H ′ / S ′ = 2 (see FIG. 11B)) was formed.

Example 4
Cyclic polyolefin (“Apel”: APL6509T: Mitsui Chemicals, Inc.) was melted at 220 ° C. in an extruder, extruded from a die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

  With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break were measured by the methods described above. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the shape of the mold was sufficiently transferred (A ′ / A = 0.958), a square with a pitch of 100 μm, a width of 80 μm, and a depth of 160 μm. It was confirmed that a lattice pattern (convex portion: width S ′ = 80 μm, height H ′ = 160 μm, aspect ratio H ′ / S ′ = 2 (see FIG. 11B)) was formed.

(Example 5)
50 parts by weight of polyethylene terephthalate (PET) vacuum-dried at 170 ° C. for 2 hours, and 33 mol% copolymerized PET (“Easter PET-G” DN-003) dried at 70 ° C. for 4 hours: Eastman Corporation 50 parts by weight were melted and kneaded in an extruder at 280 ° C., extruded from a die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break were measured by the methods described above. The results are shown in Table 1.
A resin molded product was obtained in the same manner as in Example 1.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the shape of the mold was sufficiently transferred (A ′ / A = 0.960), a square with a pitch of 100 μm, a width of 80 μm, and a depth of 160 μm. It was confirmed that a lattice pattern (convex portion: width S ′ = 80 μm, height H ′ = 160 μm, aspect ratio H ′ / S ′ = 2 (see FIG. 11B)) was formed.

(Example 6)
As a surface layer, cyclohexanedimethanol 60 mol% copolymerized PET ("Easter PET-G" DN-071: manufactured by Eastman Co., Ltd.) dried at 70 ° C for 4 hours, and vacuum dried at 170 ° C for 2 hours as a base material layer Each polyethylene terephthalate (PET) was melted at 280 ° C. in a separate extruder, and co-extruded on a cast drum from a melted two-layer coextrusion die having PET on one side by a predetermined method, and then cooled. A two-layer laminate sheet having a thickness of 600 μm and a thickness of 500 μm and a base material layer of 100 μm was obtained.

  With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break were measured by the methods described above. The results are shown in Table 1.

  Moreover, the resin molded product was obtained by the same method as Example 1 except pressing a metal mold | die on the surface layer side.

  When a cross section of the obtained molded product was observed with a scanning electron microscope, the shape of the mold was sufficiently transferred (A ′ / A = 0.969), a square having a pitch of 100 μm, a width of 80 μm, and a depth of 160 μm. It was confirmed that a lattice pattern (convex portion: width S ′ = 80 μm, height H ′ = 160 μm, aspect ratio H ′ / S ′ = 2 (see FIG. 11B)) was formed.

(Example 7)
As an inner layer, cyclohexanedimethanol 60 mol% copolymerized PET (“Easter PET-G” DN-071: manufactured by Eastman Co., Ltd.) dried at 70 ° C. for 4 hours, and a surface layer (both sides) at 170 ° C. for 2 hours under vacuum The dried polyethylene terephthalate (PET) is melted at 280 ° C. in separate extruders, and co-extruded on a cast drum from a molten three-layer coextrusion die having PET on both sides by a predetermined method, and cooled. A three-layer laminated sheet having an inner layer of 500 μm and a surface layer of 50 μm and a thickness of 600 μm was obtained.

  With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break were measured by the methods described above. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1.

  When the cross section of the obtained molded article was observed with a scanning electron microscope, the shape of the mold was sufficiently transferred (A ′ / A = 0.952), a square with a pitch of 100 μm, a width of 80 μm, and a depth of 160 μm. It was confirmed that a lattice pattern (convex portion: width S ′ = 80 μm, height H ′ = 160 μm, aspect ratio H ′ / S ′ = 2 (see FIG. 11B)) was formed.

(Example 8)
The mold has a rectangular lattice pattern (short axis: pitch 50 μm, width 10 μm, long axis: pitch 90 μm, width 10 μm, depth 80 μm, convex portion: line width S = 10 μm, height H = 80 μm, aspect ratio H / S = A resin molded product was obtained in the same manner as in Example 1 except that 8 (see FIG. 12 (a)) was used.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the shape of the mold was sufficiently transferred (A ′ / A = 0.965), short axis: pitch 50 μm, width 40 μm, long axis : A rectangular lattice pattern having a pitch of 90 μm, a width of 80 μm, and a depth of 80 μm (convex portion: minor axis width S ′ = 40 μm, major axis width S ′ = 80 μm, height H ′ = 80 μm, minor axis aspect ratio H ′ / S ′ = 2 and the long axis aspect ratio H ′ / S ′ = 1 (see FIG. 12B)) were confirmed.

Example 9
The mold used was a stripe pattern (pitch 50 μm, width 20 μm, depth 160 μm, convex portion: line width S = 20 μm, height H = 160 μm, aspect ratio H / S = 8 (see FIG. 13A)). Except for the above, a resin molded product was obtained in the same manner as in Example 1.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the shape of the mold was sufficiently transferred (A ′ / A = 0.955), and the stripe had a pitch of 50 μm, a width of 30 μm, and a depth of 160 μm. Pattern (convex: width S ′ = 30 μm, height H ′ = 160 μm, short axis aspect ratio H ′ / S ′ = 2, long axis aspect ratio H ′ / S ′ = 5.3 (see FIG. 13B) )) Was confirmed.

(Comparative Example 1)
Polyethylene terephthalate (PET) vacuum-dried at 170 ° C. for 2 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.

  With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break were measured by the methods described above. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the apex was rounded and the molding was not sufficiently performed (A / A ′ = 0.839).

(Comparative Example 2)
80 parts by weight of polyethylene terephthalate (PET) dried at 170 ° C. for 2 hours and 33 mol% of cyclohexanedimethanol copolymerized PET (“Easter PET-G” DN-003) dried at 70 ° C. for 4 hours: Eastman Corporation 20 parts by weight were melted and kneaded in an extruder at 280 ° C., extruded from a die onto a cast drum, and cooled to obtain a sheet having a thickness of 600 μm.

  With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break were measured by the methods described above. The results are shown in Table 1.

  Moreover, the resin molded product was obtained by the same method as Example 1 except pressing a metal mold | die on the surface layer side.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the apex was rounded, and the molding was not sufficiently performed (A ′ / A = 0.818).

(Comparative Example 3)
As an inner layer, 60 mol% cyclohexanedimethanol copolymerized PET ("Easter PET-G" DN-071: manufactured by Eastman Co., Ltd.) vacuum-dried at 70 ° C for 4 hours, and at 170 ° C for 2 hours as surface layers (both sides) Vacuum-dried polyethylene terephthalate (PET) is melted at 280 ° C. in separate extruders, and co-extruded on a cast drum from a molten three-layer coextrusion die having PET on both sides by a predetermined method, and cooled. Thus, a three-layer laminated sheet having an inner layer of 200 μm and a surface layer of 200 μm and a thickness of 600 μm was obtained.

  With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at g + 30 ° C., and elongation at break were measured by the methods described above. The results are shown in Table 1.

  A resin molded product was obtained in the same manner as in Example 1.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the apex was rounded, and the molding was not sufficiently performed (A ′ / A = 0.854).

(Comparative Example 4)
Dimer acid 15 mol%, 1,4-butanediol 62 mol% copolymerized PET was dried at 120 ° C. for 2 hours, then melted at 250 ° C. in an extruder, extruded from the die onto a cast drum, and cooled. A sheet having a thickness of 600 μm was obtained.

  With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break were measured by the methods described above. 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. and the press release temperature was 20 ° C.

  When the cross section of the obtained molded product was observed with a scanning electron microscope, the apex was rounded, and the molding was not sufficiently performed (A ′ / A = 0.386).

(Comparative Example 5)
30 parts by weight of polymethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 70 parts by weight of cyclohexanone. 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 dried under reduced pressure at 80 ° C. for 4 hours to obtain a sheet having a thickness of 600 μm.

  With respect to the obtained sheet, the glass transition temperature Tg, room temperature, dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and elongation at break were measured by the methods described above. The results are shown in Table 1.

  Further, an attempt was made to obtain a resin molded product by the same method as in Example 1 except that the press temperature was 150 ° C. and the press release temperature was 130 ° C., but it could not be released from the mold.

  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.

1A to 1G schematically illustrate the steps of a surface shaping method using the surface shaping sheet of the present invention. FIGS. 2A to 2F 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. 3A to 3C are perspective views schematically showing a part of a mold used in the surface shaping method of the present invention. 4A to 4H 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. . 5A to 5D 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. 6A shows a molded product formed on the easily surface-shaped sheet of the present invention, and FIG. 6B 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. 7A to 7F 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. 8A to 8C are perspective views schematically showing a part of a molded product obtained by the surface shaping method. 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. FIG. 11A is a perspective view schematically showing a part of the mold used in the example, and FIG. 11B is a perspective view schematically showing a part of the molded product shaped in the example. is there. FIG. 12A is a perspective view schematically showing a part of the mold used in the example, and FIG. 12B is a perspective view schematically showing a part of the molded product shaped in the example. is there. FIG. 13A is a perspective view schematically showing a part of the mold used in the example, and FIG. 13B is a perspective view schematically showing a part of the molded product shaped in the example. is there.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Surface shaping sheet 2 Mold 3 Molding 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 Mold Height of convex part t Width of mold concave part S 'Width of convex part of molded product H' Height of convex part of molded product l 'Thickness of base of molded product t' Width of concave part of molded product

Claims (19)

The crystallization enthalpy ΔHcc in the heating process (heating rate: 2 ° C./min) obtained by differential scanning calorimetry (hereinafter referred to as DSC) is 0 to 20 J / g, and dynamic viscoelasticity measurement (hereinafter referred to as DMA). The dynamic storage elastic modulus E1 ′ at 25 ° C. obtained from the above is 0.1 × 10 ^{9 to} 2.5 × 10 ⁹ Pa, and the dynamic at glass transition temperature (hereinafter referred to as Tg) + 30 ° C. An easily surface-shaped formable sheet having a storage elastic modulus E2 ′ of 1 × 10 ⁴ to 2 × 10 ⁷ Pa. The easily surface-shaped formable sheet according to claim 1, wherein the dynamic storage elastic modulus E1 ′ at 25 ° C. obtained by DMA is 0.5 × 10 ⁹ to 2 × 10 ⁹ Pa. The dynamic loss elastic modulus E2 ″ obtained by DMA at a glass transition temperature (hereinafter referred to as Tg) + 30 ° C. is 1 × 10 ^{3 to} 1.8 × 10 ⁶ Pa. The easy-surface formable sheet as described.   Breaking elongation is 40% or more, The easily surface-formable sheet in any one of Claims 1-3 characterized by the above-mentioned.   The resin composition forming the easily surface-shaped sheet is at least one thermoplastic resin composition selected from the group consisting mainly of a polyester resin, a polyolefin resin, a polyamide resin, and an acrylic resin. The easily surface-shaped formable sheet according to any one of claims 1 to 4.   The easy-surface formable sheet according to any one of claims 1 to 5, which is a laminate comprising a plurality of resin layers.   An easy-surface formable sheet comprising two or more resin layers laminated so that the easy-surface formable sheet according to any one of claims 1 to 5 is formed at least on a surface layer.   It is an easily surface formable sheet laminate comprising at least the easily surface formable sheet according to any one of claims 1 to 7 and a base material to be a support, and is a surface layer of the easily surface formable sheet laminate. The easy surface formable sheet laminate is characterized in that the easy surface formable sheet is formed on the surface. The easy-surface formable sheet according to any one of claims 1 to 7 is heated (heating temperature: T1) and pressed using a mold (pressing temperature: T1), and then cooled to release the pressing pressure ( Pressing pressure release temperature: T2) After the mold is released (release temperature: T3), a surface shaping method for forming a molded product to which the mold shape is transferred, wherein T1, T2 and T3 are The surface shaping method characterized by satisfy | filling following formula (1)-(5).
Tg ≦ T1 ≦ Tg + 50 ° C. (1)
T1 <Tm (2)
Tg-20 ≦ T2 ≦ Tg + 20 ° C. (3)
T2 <T1 (4)
20 ° C. ≦ T3 ≦ T2 (5)
(However, Tm is the melting point of the surface-formable sheet surface layer) The surface layer composed of at least the easy-surface-formable sheet of the easy-surface-formable sheet laminate according to claim 8 is heated (heating temperature: T1) and pressed using a mold (press temperature: T1). Then, after cooling and releasing the press pressure (press pressure release temperature: T2), the mold is released (mold release temperature: T3) to form a molded product to which the mold shape is transferred. And T1, T2 and T3 satisfy the following formulas (1) to (5).
Tg ≦ T1 ≦ Tg + 50 ° C. (1)
T1 <Tm (2)
Tg-20 ≦ T2 ≦ Tg + 20 ° C. (3)
T2 <T1 (4)
20 ° C. ≦ T3 ≦ T2 (5)
(However, Tm is the melting point of the surface-formable sheet surface layer)   The mold has a concavo-convex shape on the surface, and the ratio H / S (hereinafter, aspect ratio) of the height H and width S of the convex section of the mold is 0.1 to 25. Item 11. The surface shaping method according to Item 9 or 10.   The surface shaping method according to any one of claims 9 to 11, wherein the width S of the cross section of the convex portion of the mold is 0.01 to 100 µm and the height H is 0.01 to 500 µm.   The surface shaping method according to claim 9, wherein the convex portions of the mold are formed with a pitch of 0.02 to 500 μm.   The surface shaping method according to any one of claims 9 to 13, wherein an aspect ratio H / S of a convex portion of the mold having an uneven shape is 1 to 20.   It is a molded article which has an uneven | corrugated shape on the surface obtained by the surface shaping method in any one of Claims 9-14, Comprising: The aspect-ratio H '/ S' of a convex part is 0.1-15. A molded product having a concavo-convex shape on a characteristic surface.   The molded product according to claim 15, wherein the width S 'of the convex portion is 0.01 to 200 µm and the height H' is 0.01 to 500 µm.   The molded product according to claim 15 or 16, wherein the pitch of the convex portions is 0.02 to 500 µm.   The molded product having a concavo-convex shape on the surface according to any one of claims 15 to 17, wherein the aspect ratio H '/ S' of the convex portion is 1 to 10.   The unevenness on the surface according to any one of claims 15 to 18, wherein the ratio A '/ A of the cross-sectional area A' of the convex part of the molded product and the cross-sectional area A of the mold concave part is 0.90 or more. Molded product with shape.

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