JP5386774B2 - Surface-formable sheet laminate, surface-forming method and molded product using the same - Google Patents

Description

The present invention relates to a sheet material that can be easily shaped on the surface, in particular, a sheet material that can be easily shaped on the surface with various shapes such as ultra-high definition and high aspect ratio, and surface shaping using the sheet material. The present invention relates to a method 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, 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.

Thus, 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.

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 (2 Patent Document 2), and cell culture elements Development of plastic elements is being promoted in various fields such as bioelements (Patent Document 3).
In realizing these plastic elements, resin materials can be used in a wide variety of shapes, from a wide range of dimensions ranging from several hundreds of micrometers to several tens of nanometers, and from a wide range of low to high aspect ratios. It is desirable that it can be shaped. Moreover, when using the embodied element, it is also required that the shaped shape can exist stably and the mechanical strength of the shaped sheet itself is high. Furthermore, in addition to the above-mentioned requirements, the optical element is required to have a high transmittance in the visible light region and a small residual strain due to molding.
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, resins such as polymethyl methacrylate (PMMA) and polycarbonate (PC) that have been studied conventionally cannot satisfy all the above requirements. For example, in PMMA, there is an example in which a high-definition and high-aspect ratio structure can be formed by lowering the molecular weight, but the mechanical strength is poor, and the sheet is fragile and not suitable for practical use. Further, although PC has excellent heat resistance, there are problems such as poor moldability, difficulty in forming a high-definition pattern, and optical distortion remaining after molding.

In view of the background of such prior art, the present invention is capable of easily shaping various shapes such as ultra-high definition and high aspect ratio on the surface, and is an easily surface-formable sheet laminate having excellent handling. The surface shaping method and molded product used are to be provided.

The present invention employs the following means in order to solve such problems. That is, the easily surface-shaped sheet of the present invention is a sheet mainly composed of a polyester resin containing at least a repeating unit having a fluorene skeleton as a copolymerization component, and satisfies the following requirements (A) to ( E ). It is an easy-surface-formable sheet laminate obtained by laminating an easy-surface-formable sheet on at least one side of the surface of a base material serving as a support.
(A) The crystallization enthalpy ΔHcc in the heating process (heating rate: 2 ° C./min) obtained by differential scanning calorimetry (hereinafter, DSC) is 1 J / g or less.
(B) 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.
(C) The dynamic storage elastic modulus E2 ′ obtained by DMA at a glass transition temperature (hereinafter referred to as Tg) + 30 ° C. is 1 × 10 ^{4 to} 5 × 10 ⁶ Pa.
(D) In the polyester resin, the dicarboxylic acid component is composed of terephthalic acid and / or cyclohexanedicarboxylic acid.
(E) The said polyester resin consists of diol and ethylene glycol in which a diol component has a fluorene skeleton, and diol which has this fluorene skeleton is 40-80 mol% in 100 mol% of all the diol components.

Further, the surface shaping method of the present invention is a method of heating (heating temperature: T1) the above-described easy surface shaping sheet or the easy surface shaping sheet laminate and 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), thereby forming a surface product 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)
(Here, Tg is the glass transition temperature of the surface layer of the easily surface-shaped sheet or laminate of the easily surface-shaped sheet laminate, and Tm is the melting point of the surface-shaped sheet surface layer).

In addition, the molded product of the present invention is a molded product having a concavo-convex shape on the surface obtained by the surface shaping method described above, and the aspect ratio H ′ / S ′ of the concavo-convex convex portion is 0.1-15. It is characterized by being.

According to the present invention, an easily surface formable sheet capable of easily forming a wide variety of shapes such as ultra high definition and high aspect ratio on the surface is obtained. It becomes possible to shape the aspect ratio pattern in a large area.

The present invention has been intensively studied on the above-mentioned problems, that is, easy-to-surface formable sheets that can be easily shaped on the surface with various shapes such as ultra-high definition and high aspect ratio, and have a specific composition. In particular, when a specific polyester resin with a selected material having physical properties was placed on the surface layer, the above problems were solved all at once, and a sheet excellent in transferability to the surface and releasability (hereinafter referred to as easy surface) The present inventors have found that a formable sheet) can be formed and have reached the present invention.

That is, the easily surface-shaped formable sheet used in the present invention is a sheet mainly composed of a polyester resin containing at least a repeating unit having a fluorene skeleton as a copolymerization component, and the following requirements (A) to (D) It has characteristics where

That is,
(A) The crystallization enthalpy ΔHcc in the heating process (heating rate: 2 ° C./min) obtained by differential scanning calorimetry (hereinafter, DSC) is 1 J / g or less.
(B) 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.
(C) The dynamic storage elastic modulus E2 ′ obtained by DMA at a glass transition temperature (hereinafter referred to as Tg) + 30 ° C. is 1 × 10 ^{4 to} 5 × 10 ⁶ Pa.

The easy-surface formable sheet used in the present invention is important to be a sheet mainly composed of a specific copolymer component, that is, a polyester resin containing a repeating unit having a fluorene skeleton as a copolymer component. Polyester resins can be suitably used because of the variety of monomer types to be copolymerized and the ease of adjusting the material properties. In particular, a dicarboxylic acid or a copolymer of an ester-forming derivative thereof and a diol is preferably used because it is easily polymerized.

Examples of the dicarboxylic acid component constituting the polyester resin include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, dimer acid, eicosandioic acid, pimelic acid, azelaic acid, methylmalon. Aliphatic dicarboxylic acids such as acid, ethyl malonic acid, adamantane dicarboxylic acid, norbornene dicarboxylic acid, isosorbide, cyclohexanedicarboxylic acid, decalin dicarboxylic acid, 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'-diphenylether dicarboxylic acid, 5-sodium Sulfoisov Le acids, phenyl ene boys carboxylic acid, anthracene dicarboxylic acid, phenanthrene carboxylic, 9,9'-bis (4-carboxyphenyl) dicarboxylic acids such as fluorene acids and aromatic dicarboxylic acids or al cited as representative examples like an ester derivative thereof, Re that, but it is not limited to these. 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 constituting the polyester resin include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, and 1,3-butanediol. Aliphatic diols such as cyclohexanedimethanol, spiroglycol and isosorbide, bisphenol A, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 9,9′-bis (4 - hydroxyphenyl) fluorene, and the like diols and aromatic diols such as Ru is found mentioned as a typical example, but not limited to. 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. Diols 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.

The polyester resin constituting the easy-surface formable sheet used in the present invention can be obtained by appropriately selecting the above-mentioned dicarboxylic acid component and diol component and copolymerizing them. It is most important in the present invention to include a repeating unit having a fluorene skeleton, and by including such a repeating unit having a fluorene skeleton as a copolymerization component, high transparency and optical distortion can be reduced. is there.

In order to introduce 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 diols having such a fluorene skeleton include 9,9′-bis (4-hydroxyphenyl) fluorene, 9,9′-bis (4-hydroxy-3-methylphenyl) fluorene, 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-hydro) Ci-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-dibenzyl) Eniru) 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. Diols 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, dicarboxyl dicarboxylic acids having the above fluorene skeleton may be added with oxyacids such as l-lactide, d-lactide, hydroxybenzoic acid, and derivatives thereof, or a combination of a plurality of such oxyacids. Carboxy compounds are also preferably used.

The polyester resin comprising a copolymer component having a fluorene skeleton constituting the easy-to-surface formable sheet used in the present invention includes the above-mentioned dicarboxylic acid and diol, dicarboxylic acid having a fluorene skeleton, and diol having a fluorene skeleton. Can be suitably selected and copolymerized. 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 comprising a copolymer component having a fluorene skeleton constituting the easy-surface formable sheet used in the present invention , the molar amount of the diol having a fluorene skeleton contained in 100 mol of all diol components Is n1, the molar amount of the other diol is n3, the molar amount of the dicarboxylic acid having a fluorene skeleton contained in 100 mol of the total dicarboxylic acid component is n2, and the molar amount of the other dicarboxylic acid is n4, The sum n1 + n2 of the molar amount n1 of the diol having a fluorene skeleton and the molar amount n2 of the dicarboxylic acid having a fluorene skeleton contained in 100 mol of the total dicarboxylic acid component is preferably 20 ≦ n1 + n2 ≦ 160. More preferably, 30 ≦ n1 + n2 ≦ 150, and most preferably 40 ≦ n1 + n2 ≦ 140. If it is less than this range, the polyester resin has crystallinity, and when the sheet before shaping is stored for a long period of time, crystallization proceeds with time, or the sheet is heated at the time of shaping on the surface Even if the resin constituting the resin crystallizes quickly and the moldability is reduced, or even if it can be molded, the birefringence of the polyester resin increases, and distortion may remain after molding. Exceeding the range is not preferable because the sheet itself becomes brittle and the mechanical strength may decrease.

The polyester resin comprising a copolymer component having a fluorene skeleton constituting the easy-surface formable sheet used in the present invention is a molar amount n1 of diols having a fluorene skeleton contained in 100 mol of all diol components. When the sum n1 + n2 of the molar amount n2 of the dicarboxylic acid having a fluorene skeleton contained in 100 mol of the dicarboxylic acid component is set to the above ratio, not only good moldability is obtained, but also optical distortion of the molded product is reduced, and the machine It is possible to achieve a balance of mechanical strength.

Moreover, in the polyester resin comprised including the copolymerization component which has a fluorene skeleton which comprises the easily surface formable sheet | seat used for this invention , the molar amount of the diol which has a fluorene skeleton contained in 100 mol of all diol components. The ratio n1 / n3 between n1 and the molar amount n3 of other diols is preferably n1 / n3 = 20/80 to 100/0. More preferably, it is 30 / 70-100 / 0, Most preferably, it is 40 / 60-100 / 0. Below this range, the birefringence of the polyester resin becomes large, and distortion may remain after molding, which is not preferable. In the polyester resin comprising a copolymer component having a fluorene skeleton constituting the easy-surface formable sheet used in the present invention , the molar amount of the diol having a fluorene skeleton contained in 100 mol of all diol components is n1. Moreover, the optical distortion of the molded product can be reduced by setting the molar amount of diol to the ratio n1 / n3 of n3 within the above range. 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.

Moreover, in the polyester resin comprised including the copolymerization component which has a fluorene skeleton which comprises the easily surface formable sheet | seat used for this invention , the mole of dicarboxylic acid which has a fluorene skeleton contained in 100 mol of all dicarboxylic acid components. The ratio n2 / n4 of the fraction n2 and the molar fraction of other dicarboxylic acids n4 is arbitrary, but is preferably 0 / 100-60 / 40, more preferably 0 / 100-50 / 50, most preferably 0/100 to 40/60. Above this range, polymerization is difficult, or even if polymerization is possible, the sheet itself becomes brittle and mechanical strength may be reduced, which is not preferable. In the polyester resin having a fluorene skeleton constituting the easy-to-surface formable sheet used in the present invention , the molar amount of dicarboxylic acid having a fluorene skeleton contained in 100 mol of all dicarboxylic acid components is n2, and the molar amount of other dicarboxylic acid. By making the ratio n2 / n4 of n4 within the above range, it becomes possible to impart mechanical strength to the polyester resin.

Here, in the polyester resin configured to include a copolymer component having a fluorene skeleton constituting the easy-to-surface formable sheet used in the present invention , in 100 mol% of other dicarboxylic acid components, adamantane dicarboxylic acid, norbornene dicarboxylic acid, When the molar amount of alicyclic dicarboxylic acid such as isosorbide and cyclohexanedicarboxylic acid is n4 ′ and the molar fraction of other dicarboxylic acids other than alicyclic dicarboxylic acid is n4 ″, the ratio n4 ′ / n4 ″ is 50. It indicates that / 50 to 100/0 is preferable. More preferably, it is 60 / 40-100 / 0, Most preferably, it is 70 / 30-100 / 0. Below this range, the optical distortion of the molded product increases, which is not preferable.

In the polyester resin comprising a copolymer component having a fluorene skeleton constituting the easy-to-surface formable sheet used in the present invention , the molar fraction of alicyclic dicarboxylic acid in 100 mol% of other dicarboxylic acid components By making the molar ratio of n4 ′ and other dicarboxylic acids other than alicyclic dicarboxylic acids the above-mentioned value of the ratio of n4 ″, not only can shaping be performed at high speed, but also higher transparency and optical distortion can be achieved. This is preferable because it can be reduced.

Moreover, in the polyester resin comprised including the copolymerization component which has a fluorene skeleton which comprises the easily surface-shaped form sheet | seat used for this invention , a copolymerization rate so that the following relational expressions (1)-(3) may be satisfy | filled. Is preferably controlled.
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 to 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 to 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 good moldability can be obtained, but also the optical distortion of the molded product can be further reduced and the mechanical strength can be achieved at the same time.

In addition, the polyester resin comprising a copolymer component having a fluorene skeleton constituting the easy-to-surface formable sheet used in the present invention is within the range where the effects of the present invention are not lost. Various additives can be added later. 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, mold release agents, thickeners, Examples include plasticizers, pH adjusters, and salts. 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 the above-mentioned 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 bleeding out of the release agent. This is preferably performed because it can be improved.
The easy-to-surface formable sheet used in the present invention can be obtained by processing into a sheet form using, as a main component, a polyester resin containing a repeating unit having at least a fluorene skeleton obtained as described above as a copolymerization component. Here, the main component means that the polyester resin containing the above repeating unit having at least a fluorene skeleton as a copolymerization component preferably consists of 50% by weight or more, more preferably 60% or more, most preferably 70%. That's it.

In the easy-surface formable sheet used in the present invention , the polyester resin preferably has an intrinsic viscosity of 0.3 to 0.65 dl / g. More preferably, it is 0.32-0.62, More preferably, it is 0.35-0.60. 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 intrinsic viscosity is larger than the above range, deformation of the sheet is less likely to occur when shaping, and the filling of the resin into the mold does not proceed from the middle and the shape of the mold cannot be transferred sufficiently, Even if it is possible, the forming speed tends to be slow, or residual stress remains in the molded 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. 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 used in the present invention , by setting the intrinsic viscosity of the resin composition constituting the sheet within this range, a sheet that can be formed at high speed can be obtained.
In addition, the easy-surface-formable sheet used in the present invention has a crystallization enthalpy ΔHcc of 1 J / g in a temperature rising process (temperature rising rate: 2 ° C./min) obtained by differential scanning calorimetry (hereinafter referred to as DSC). It is important that:

The crystallization enthalpy ΔHcc here is a value obtained according to JIS K7122 (1999), that is, in the differential scanning calorimetry chart obtained when scanning at a temperature rising rate of 2 ° C./min. It is a value obtained from the area of the exothermic peak accompanying. The crystallization enthalpy ΔHcc according to the present invention is a value at the first temperature increase without erasing the history. An amorphous resin having a crystallization enthalpy ΔHcc of 0.1 J / g or less, more preferably 0 J / g is preferable. If the crystallization enthalpy ΔHcc is larger than the above range, the crystallization proceeds with time during long-term storage of the sheet, or the resin constituting the sheet rapidly crystallizes at the time of temperature rise when shaping the surface. This makes it difficult to shape. For this reason, when a high-definition pattern or high-aspect ratio pattern is formed on a large area, the resin is insufficiently filled in the mold, resulting in a decrease in transfer accuracy or a pressure imbalance in the surface, resulting in a transfer surface. It is not preferable for reasons such as a decrease in internal uniformity. In the present invention, by setting the crystallization enthalpy ΔHcc in the above range, good transferability and in-plane uniformity can be obtained even when a high aspect ratio pattern is formed.

In addition, the easily surface-shaped formable sheet used in the present invention has a dynamic storage elastic modulus E1 ′ at 25 ° C. obtained by dynamic viscoelasticity measurement (hereinafter referred to as DMA) of 0.1 × 10 ⁹ to 2 × 2. .5 × 10 ⁹ Pa. Preferably ^{0.5 × 10 9 ~2 × 10 9} Pa, more preferably from ^{1.0 × 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 increases, and it is difficult to release from the mold when forming a high-definition pattern or a large aspect ratio pattern with a large area. Therefore, it 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, both the releasability at the time of large-area shaping of a high-definition pattern and a high aspect ratio pattern and the mechanical strength of the molded product are compatible. be able to.

In addition, it is important that the easily surface-shaped sheet used in the present invention has a dynamic storage elastic modulus E2 ′ at a glass transition temperature Tg + 30 ° C. of 1 × 10 ^{4 to} 5 × 10 ⁶ Pa. Preferably ^{1 × 10 4 ~2.0 × 10 6} Pa, more preferably ^{0.5 × 10 6 ~2 × 10 6} , most preferably ^{1 × 10 6 ~3 × 10 6} . 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 increase the pressing pressure. However, when high-precision patterns or high-aspect-ratio patterns are formed on a large area, the resin is insufficiently filled in the mold, resulting in transfer accuracy. This is not preferable because of a decrease in image quality, a pressure imbalance in 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 when forming a high-definition pattern or a large aspect ratio pattern in a large area. be able to.

Moreover, the easily surface-shaped formable sheet used in the present invention has a dynamic storage elastic modulus E1 ′ at 25 ° C. obtained by DMA measurement under the above conditions of 0.1 × 10 ^{9 to} 2.5 × 10 ^9. It is Pa, and dynamic storage elastic modulus E2 'in Tg + 30 degreeC is 1 * 10 < ⁴ > -5.0 * 10 < ⁶ > Pa, It is characterized by the above-mentioned. 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 1.0 × 10 ⁴ to 2 It is good that it is × 10 ⁶ Pa. By doing so, 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.

Further, the easily surface-shaped sheet used in the present invention preferably has a dynamic loss elastic modulus E2 ″ obtained by DMA of Tg + 30 ° C. of 1 × 10 ^{3 to} 1.8 × 10 ⁶ Pa. It is preferably 1 × 10 ^{3 to} 1.5 × 10 ⁶ Pa, and most preferably 0.1 × 10 ^{6 to} 1.5 × 10 ^6. The dynamic loss elastic modulus E2 ″ at Tg + 30 ° C. is higher than this value. Then, deformation of the sheet is less likely to occur when shaping. For this reason, it is necessary to increase the load and increase the pressing pressure. However, when high-precision patterns or high-aspect-ratio patterns are formed on a large area, the resin is insufficiently filled in the mold, resulting in transfer accuracy. This is not preferable because of a decrease in image quality, a pressure imbalance in 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 high-definition pattern or a large aspect ratio pattern in a large area. be able to.

Moreover, it is preferable that the photoelastic coefficient k in 25 ^degreeC is 50 * 10 <^-12> Pa <^-1> or less as for the easily surface shapeable sheet | seat used for this invention. More preferably, it is 40 × 10 ⁻¹² Pa ⁻¹ or less, most preferably 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 is measured using a polarizing microscope equipped with crossed Nicols in a state where a tension of 1 kg / mm ² (9.81 × 10 ⁶ Pa) is applied to the film. Is performed using sodium D line (wavelength 589 nm).

If the photoelastic coefficient k is larger than this value, optical distortion remains during processing, and the optical characteristics may change within the surface of the molded product, resulting in uneven color tone and the like. In the easily surface-shaped formable sheet used in the present invention , by setting the photoelastic coefficient k to the above-described range, uniform optical characteristics can be obtained within the surface of the molded product without any optical distortion remaining during processing.

The glass transition temperature Tg of the easy-surface formable sheet used in the present invention is preferably in the range of 100 to 160 ° C. More preferably, it is 110-150 degreeC. If the glass transition temperature Tg falls below this range, the pattern may be deformed at the time of mold release of a high-definition pattern or a high aspect ratio pattern. Since it changes, it 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 used in the present invention, good transferability and releasability can be obtained by setting the glass transition temperature Tg of the sheet within this range.

The glass transition temperature Tg, the dynamic storage elastic modulus E ′, the dynamic loss elastic modulus E ″, the photoelastic coefficient, etc. of the easily surface-shaped formable sheet used in the present invention can be selected from the monomer species 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 Tg and the dynamic storage elastic modulus E ′ are increased. In addition, when a flexible skeleton such as polyethylene glycol is introduced, the glass transition temperature Tg and the dynamic storage elastic modulus E ′ are lowered.

Further, the glass transition temperature Tg, dynamic storage elastic modulus E ′, dynamic loss elastic modulus E ″, etc. can be controlled by introducing a plasticizer, a crosslinking agent, etc. In the case of a plasticizer, its type, 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 E ″ increase as the amount of the plasticizer increases. It lowers 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 taking these into consideration, the sheet can be formed so as to satisfy the above-mentioned condition range by appropriately adjusting and adding.

Moreover, you may add the component etc. which harden | cure by electromagnetic wave irradiation etc. to the easily surface formable sheet | seat used for 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-to-surface formable sheet used in 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.

Easy surface formability sheet used in the present invention, it is necessary to provide an easy surface shaping sheet described above on at least the surface of the laminate. In the case of such a laminate, it is possible to impart surface properties such as slipperiness and friction resistance, mechanical strength, and heat resistance as compared with a single sheet. 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. However, even if the entire sheet does not satisfy the above-mentioned requirements, a layer satisfying at least the above-mentioned requirements is present. If it is formed on the surface layer, the surface can be easily shaped.

Moreover, the easy-surface-formable sheet used in 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 one in which the easy-surface-formable sheet is provided as a surface layer on at least one side of the surface of a base material to be a support . Since the easily surface-shaped sheet is formed as a surface layer, the surface can be easily shaped.

The base material used as the support is a sheet-like material whose shape does not change during shaping, and preferably the glass transition temperature (hereinafter referred to as Tg1) + 30 ° C. of the surface layer of the easily surface-formable sheet. In the above, E3 ′ of the base material obtained by dynamic viscoelasticity measurement (hereinafter referred to as DMA) is preferably 5 × 10 ⁷ Pa or more, more preferably 1.0 × 10 ⁸ Pa or more. If the E3 ′ of the base material obtained by DMA is less than this value, when pressure is applied for molding, the support is also deformed so that no sufficient pressure is applied to the surface layer, and the pattern accuracy is low. Therefore, it is not preferable. In the easily surface-shaped sheet laminate of the present invention, a group obtained by dynamic viscoelasticity measurement (hereinafter referred to as DMA) at the glass transition temperature (hereinafter referred to as Tg1) + 30 ° C. of the surface layer of the easily surface-shaped sheet. By setting E3 ′ of the material within the above range, a surface layer can be formed into a sheet that can be accurately formed.

Moreover, it is preferable that the peeling strength F of this base material and a surface layer is 50 mN / cm or more as for the easily surface formable sheet laminated body of this invention. More preferably, it is 70 mN / cm or more, and most preferably 100 mN / cm or more.

The peel strength F here is the peel strength F when the surface layer of the easy-surface-formable sheet laminate of the present invention is peeled in the direction of 180 ° with respect to the substrate, and the rise of the SS curve of the peel force. From the average peel force T (N) with a peel length of 50 mm or more excluding the part, peel strength F (N / cm) = T / W (where T (N): average peel force, W (cm): sample (Width).
When the peel strength between the base material and the surface layer is less than this value, the mold is pressed against the surface of the surface-shaped sheet laminate of the present invention, and then the base material and the surface layer are separated. Is unfavorable because peeling occurs and release is impossible. In the easy-surface formable sheet laminate of the present invention, by setting the peel strength between the substrate and the surface layer to be equal to or higher than the above value, the substrate can be formed even at the time of forming a high-definition pattern or a pattern with a high aspect ratio. And can be released without peeling between the surface layers.

Examples of the base material used in the easy-surface formable sheet laminate of the present invention include organic film base materials such as polyester resin, biaxially stretched polyester film, polyolefin resin, acrylic resin, silicon, stainless steel, aluminum, and aluminum alloy. Metal base materials such as iron, steel, and titanium, and inorganic base materials such as concrete are applicable. However, it is more preferable to use a flexible base material in terms of handling and weight reduction. Good. 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 configuration as a composite with a base material having other functions is also a preferable configuration.

In the easy-surface formable sheet laminate 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 is preferably as small as possible, preferably the refractive index difference ΔN is It is 0-0.10, More preferably, it is 0-0.08, More preferably, it is 0-0.06. 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 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 base material is in the above-described range, thereby providing excellent color uniformity. It can be a sheet. Specifically, when a biaxially stretched polyester film is used as the base material of the easily surface-shaped sheet laminate, the refractive index N1 of the surface layer is preferably 1.58 to 1.7, more preferably 1. 59 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. In the easy-to-surface formable sheet used in the present invention , a sheet having good color uniformity can be obtained by setting the refractive index N1 of the surface layer in the above range.

Various additives can be added to such a substrate 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 preferred thickness (thickness, film thickness) of the easy-surface formable sheet used in the present invention is preferably in the range of 10 μm to 5 mm. More preferably, it is 20 μm to 2 mm. In the case of an easily surface-shaped sheet laminate, it is preferable to provide a sheet having a thickness in the range of 0.1 μm to 5 mm on the substrate. More preferably, it is 0.2 μm to 2 mm. In this case, the thickness of the substrate is not particularly limited.

As a method of forming the easy surface formability sheet used in the present invention, for example, in the case of single sheets, heating and melting the sheet forming material in an extruder and extruded onto a cast drum cooled from a die processed into a sheet And a method (melt cast 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. A method of processing into a solution (solution casting method) or the like can also be used.

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 forming a single film, thermocompression bonding with a heated group of rolls (thermal laminating method), laminating with an adhesive (adhesion method), and other materials for sheet formation are dissolved in a solvent. A method of applying the solution on the sheet (coating method) or the like can be used.

Moreover, as a manufacturing method of the easily surface formable sheet | seat laminated body of this invention, the above-mentioned melt laminating method, the heat laminating method, the adhesion | attachment method, the coating method, etc. can be used. As such a base material, a base-adjusting material such as an easy-adhesion layer or a material such as an undercoat material that has been treated is preferably used in terms of adhesive strength with the surface layer. In this case, the base preparation and undercoat are appropriately selected according to the base material to be used, such as acrylic, polyester, urethane, etc., but if a biaxially stretched polyester film is used as the base, it is bonded. From the viewpoint of properties, a polyester system is preferably used. Examples of the method for treating the substrate with the substrate preparation material and the undercoat material include an in-line coating method that is applied during film formation of the substrate and an offline coating method that is applied to 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 film formation of the base material and the adhesiveness of the base preparation material or the undercoat material to the base material is high. Further, when coating, corona treatment is preferably performed from the viewpoint of improving wettability and adhesion.

In addition, when a biaxially stretched polyester film is selected as the base material of the easy-surface-formable sheet laminate of the present invention, as a production method, in addition to the above-described melt lamination method, thermal lamination method, coating method, and the like, A sheet forming material and a base material polyester material are respectively charged into two extruders, co-extruded on a cast drum that has been melted and cooled from a die, biaxially stretched, and then subjected to heat treatment (both An extrusion 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.

An example of a method for forming a pattern using the easy-surface-shaped sheet and the easy-surface-shaped sheet laminate used in the present invention will be described with reference to FIG.

The easy-surface-formable sheet (or easy-surface-formable sheet laminate) 1 used in the present invention and the mold 2 having irregularities reversed from the pattern to be transferred are transferred to the glass transition temperature Tg (or easy) of the sheet. The glass transition temperature Tg1 of the surface layer of the surface-shaped sheet laminate, hereinafter referred to as “Tg”) is heated to a temperature range of not less than the melting point Tm (FIG. 1 (a)) and can be used in the present invention. The surface-shaped sheet (or easy-surface-shaped sheet laminate) 1 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. 1B). 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, even if the sheet is bitten into the mold and cannot be released, or even if the sheet is released, it is not preferable because the accuracy of the pattern is reduced or the pattern is partially missing. In the shaping method, 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 dynamic storage elastic modulus E ′ and 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 large and the durability of repeated 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 degreeC. 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. As the shape of the mold convex portion 11 observed in the cross section of FIG. 2, a rectangle (FIG. 2A), a trapezoid (FIG. 2B), a triangle (FIG. 2C), and these are deformed. (Figs. 2 (d), (e), (f)) and a mixture thereof are preferably used, but shapes other than these can also be used. That is, in the cross-sectional view, in addition to FIG. 2 (a) in which the side surface of the mold convex portion 11 is substantially perpendicular to the sheet surface, the forms as shown in 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 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.

3A to 3H 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. 3A to 3H, 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. 3A to 3C show a case where the mold recess 12 has a stripe shape, FIG. 3D shows a case where the mold recess 12 has a circular cross section, and FIG. 3E shows a triangle shape. 3 (f) to 3 (g) exemplify a case where the shape is a quadrangle, and FIG. 3 (h) 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. Further, as shown in FIGS. 4A to 4D, the shape of the mold protrusion 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 200 μm, more preferably 0.005 to 100 μm, and most preferably 0.01 to 50 μm. The height H is preferably 0.001 to 200 μm, more preferably 0.005 to 100 μm, and most preferably 0.01 to 50 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 the unit length of the mold protrusion 11 as illustrated in FIG. In the case of the striped pattern of FIG. 3, the measurement is performed in the direction in which the unit length is short. In the case of FIGS. 3D to 3H, the width S is defined as the shortest unit length. Further, when the mold convex portion 11 is circular as shown in FIG. 4 (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 thickness direction of the mold 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 convex portion 11 and the width of the mold 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. The repeating unit (pitch) of the unevenness is represented by the sum of the width S of the mold convex portion and the width t of the mold concave portion, and the pitch of the mold convex portion 11 is preferably 0.002 to 300 μm, more preferably. It is 0.01-200 micrometers, Most preferably, it is 0.02-100 micrometers.

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. 5 (a) shows a molded product formed on the easily surface-shaped sheet used in the present invention , and FIG. 5 (b) shows a molded product formed on the easily surface-shaped sheet laminate of the present invention. It is a cross-sectional view schematically showing a product. 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. 6 (a) to (f). To do. As the shape of the convex portion 22 of the molded product observed in the cross section of FIG. 6, a rectangle (FIG. 6A), a trapezoid (FIG. 6B), a triangle (FIG. 6C), these are Deformed ones (FIGS. 6D, 6E and 6F) and a mixture thereof are preferably used, but shapes other than these can also be used. That is, in the cross-sectional view, the side surface of the convex portion 22 of the molded product is substantially perpendicular to the sheet surface as shown in FIG. 6 (a) and the like, as shown in FIGS. 6 (b) to 6 (e). It is. 6 shows an example in which the flat portion is formed between the convex portions 22 of the adjacent molded products, the gap 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.

7 (a) to 7 (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. 7A to 7H, 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. 7A to 7C show a case where the concave portion 21 of the molded product has a stripe shape, FIG. 7D shows a case where the cross section of the concave portion 21 of the molded product has a circular shape, and FIG. 7 (f) to (g) exemplify a rectangular shape, and FIG. 7 (h) illustrates 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. 8A to 8D, 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 shape of the convex portion 22 is preferably such that the width S ′ of the convex portion 22 is 0.001 to 200 μm, more preferably 0.005 to 100 μm, and most preferably 0.01 to 50 μm. The height H ′ of the convex portion 22 is preferably 0.001 to 200 μm, more preferably 0.005 to 100 μm, and most preferably 0.01 to 50 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 pattern shown in FIGS. 7A to 7C, the measurement is performed in the direction in which the unit length is short. In the case of FIGS. 7D to 7H, the place where the unit length is the shortest is the width S ′. Further, when the convex portion 22 of the molded product is circular as shown in FIG. 8 (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. 6.

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 the lengths S ′ and t ′ in the case of FIG. In addition, when the length unit changes with positions like FIG.6 (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 -300 micrometers, More preferably, it is 0.01-200 micrometers, Most preferably, it is 0.02-100 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. 5B, 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 portion of the molded product and the cross-sectional area A of the concave portion of the mold. Good transferability indicates that the ratio A ′ / A is preferably 0.90 or more, more preferably 0.95 or more.
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. In the case of an easily surface-shaped sheet laminate, the surface layer of the laminate 1 was scraped off with a cutter, and the resulting product was measured by the method described above to determine the crystallization enthalpy ΔHcc of the surface layer. Note that the crystallization enthalpy ΔHcc here is a value at the first temperature increase without erasing the history.

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. In addition, in the case of the easily surface formable sheet laminate, a single film was prepared using the material of each of the surface layer and the base material layer, and measurement was performed according to the method described above.

C. The resin was dissolved in 100 ml of intrinsic viscosity 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. Photoelastic coefficient k
A sheet (thickness d (nm)) cut into 3 cm × 5 cm is subjected to retardation Γ1 (nm) at a wavelength of 589 nm using a cell gap inspection device RETS-1200 manufactured by Otsuka Electronics Co., Ltd. in an atmosphere of 23 ° C. and 65 RH%. ) Subsequently, a tension of F = 1 kg / mm ² (9.81 × 10 ⁶ Pa) was applied in the long side direction of the sheet to obtain a phase difference Γ2 (nm) at a wavelength of 589 nm in this state. The photoelastic coefficient k (Pa ⁻¹ ) was determined from the obtained value according to the following formula.
k = (Γ2-Γ1) / (d × F).

E. The peel strength laminate was cut into a 2 cm wide x 12 cm long strip, the substrate side was attached to a 2 mm thick smooth acrylic board with double-sided tape, and a 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. Refractive Index Surface layer refractive index N1 and refractive index N2 of the substrate were measured at 20 ° C. using an Abbe refractometer manufactured by Atago Co., Ltd. according to JIS-K7105 (1999).

G. After cutting out the cross section of the cross-section structure mold and 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 determined to be 0. 90 or more: ○
0.85-0.90: △
Less than 0.85: ×
It was. If the evaluation result is ○ or Δ, it is good.

H. When a molded product is placed between two polarizing plates of a molded product optical strain distortion tester (TYPE 20, manufactured by Shinto Kagaku Co., Ltd.) and the optical distortion is observed with the naked eye, the absorption axes of the two polarizing plates are parallel. Optical distortion is hardly observed in both vertical and vertical directions: ○
When the absorption axes of the two polarizing plates are parallel, almost no optical distortion is observed, but when they are perpendicular, some optical distortion is observed: Δ
Optical distortion is clearly observed both in the parallel and perpendicular absorption axes of the two polarizing plates: ×
It was.

I. A laminated body having a surface layer film thickness of 4 μm is prepared, and the spectral transmittance is measured every 1 nm in a wavelength range of 400 nm to 800 nm using a spectrophotometer U-3410 (manufactured by Hitachi, Ltd.). The total light transmittance was determined and plotted with the wavelength on the horizontal axis and the transmittance on the vertical axis. When the obtained spectral curve is enlarged and observed, a fine wave (ripple) is hardly observed, or the amplitude is 0.3% or less:
When the amplitude is 0.3% or more and 0.4% or less: △
Amplitude is 0.4% or more: ×
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 four types (refer FIG. 9).

"Mold 1" (Figure 9 (a))
Material: Silicon, Size: 30 mm Square pattern: Lattice shape Pitch: 10 μm, Convex width: 2 μm, Convex height: 15 μm
Cross-sectional shape: rectangular shape.

“Mold 2” (FIG. 9B)
Material: Nickel, Size: 30 mm Square pattern: Stripe pitch: 10 μm, Convex width: 5 μm, Convex height: 10 μm
Cross-sectional shape: rectangular shape.

“Mold 3” (FIG. 9C)
Material: Nickel, Size: 30 mm Square pattern: Stripe pitch: 1000 nm, Convex width: 500 nm, Convex height: 1000 nm
Cross-sectional shape: rectangular shape.

“Mold 4” (FIG. 9D)
Material: Nickel, Size: 30 mm Square pattern: Stripe pitch: 200 nm, Convex width: 100 nm, Convex height: 200 nm
Cross-sectional shape: rectangular shape.

"Mold 5" (Figure 9 (e))
Material: Nickel, Size: 30 mm Square pattern: Stripe pitch: 100 nm, convex width: 50 nm, convex height: 100 nm
Cross-sectional shape: rectangular shape.

( Reference Example 1)
Polyester (inherent viscosity C = 0.43 dl / g) copolymerized with cyclohexanedicarboxylic acid as dicarboxylic acid component, 80 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 20 mol% of ethylene glycol as diol component at 100 ° C. And then dried 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 Tg, room temperature and dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and photoelastic coefficient k at 25 ° C. Table 1 shows.

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 135 ° 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, it was confirmed that the shape was sufficiently transferred in any mold (mold 1: A ′ / A = 0.954, gold Mold 2: A ′ / A = 0.980, Mold 3: A ′ / A = 0.961, Mold 4: A ′ / A = 0.945, Mold 5: A ′ / A = 0.931 ). Further, when the optical distortion of the molded product was confirmed, almost no optical distortion was observed in both the parallel and vertical absorption axes of the two polarizing plates. The results are shown in Table 2.

( Reference Example 2)
Cyclohexanedicarboxylic acid as the dicarboxylic acid component, 9,9′-bis (4-hydroxyethoxyphenyl) fluorene 60 mol% as the diol component, and a copolymerized ethylene glycol 40 mol% (inherent viscosity C = 0.61 dl / g) at 90 ° C. And then dried 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 Tg, room temperature and dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and photoelastic coefficient k at 25 ° C. Table 1 shows.

A resin molded product was obtained in the same manner as in Reference Example 1 except that the press temperature was 175 ° C. and the press release temperature was 140 ° 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 2: A ′ / A = 0.949, Mold 2: A ′ / A = 0.777, Mold 3: A ′ / A = 0.952, Mold 4: A ′ / A = 0 930, mold 5: A ′ / A = 0.923). Further, when the optical distortion of the molded product was confirmed, almost no optical distortion was observed in both the parallel and vertical absorption axes of the two polarizing plates. The results are shown in Table 2.

( Reference Example 3)
Polyester obtained by copolymerization of 50 mol% of cyclohexanedicarboxylic acid as a dicarboxylic acid component, 50 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. 57 dl / g) 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 Tg, room temperature and dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and photoelastic coefficient k at 25 ° C. Table 1 shows.

A resin molded product was obtained in the same manner as in Reference Example 1 except that the press temperature was 160 ° C. and the press release temperature was 120 ° 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 = 0.951, Mold 2: A ′ / A = 0.964, Mold 3: A ′ / A = 0.940, Mold 4: A ′ / A = 0 928, mold 5: A ′ / A = 0.912). Further, when the optical distortion of the molded product was confirmed, almost no optical distortion was observed in both the parallel and vertical absorption axes of the two polarizing plates. The results are shown in Table 2.

( Reference Example 4)
Polyester (inherent viscosity C = 0.56 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 at 130 ° C. After vacuum drying for 4 hours, it 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 Tg, room temperature and dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and photoelastic coefficient k at 25 ° C. Table 1 shows.

A resin molded product was obtained in the same manner as in Reference Example 1 except that the press temperature was 165 ° C and the press release temperature was 120 ° 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 = 0.842, Mold 2: A ′ / A = 0.962, Mold 3: A ′ / A = 0.944, Mold 4: A ′ / A = 0 925, Mold 5: A ′ / A = 0.909). Further, when the optical distortion of the molded product was confirmed, almost no optical distortion was observed when the absorption axes of the two polarizing plates were parallel, but slight optical distortion was observed when it was vertical. The results are shown in Table 2.

(Example 5)
As a surface layer, a polyester obtained by vacuum drying at 110 ° C. for 4 hours, copolymerized with terephthalic acid as a dicarboxylic acid component, 40 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene as a diol component, and 60 mol% of ethylene glycol (inherent) Viscosity C = 0.56 dl / g) Polyethylene terephthalate (PET) vacuum-dried at 170 ° C. for 2 hours as a base material layer was melted at 280 ° C. in a separate extruder, and PET was applied to one side by a predetermined method. A two-layer laminated sheet was prepared by co-extrusion on a cast drum from a molten two-layer coextrusion die having 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. in the width direction 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 20 μm.
The peel strength between the surface layer and the base material layer of the obtained laminated sheet was determined. The results are shown in Table 3.

Further, a laminated sheet having a surface layer thickness of 4 μm was produced by the same method. The spectral transmittance of the obtained laminated sheet was measured to evaluate the optical characteristics. 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 glass transition temperature Tg of the obtained single-layer sheet, the dynamic storage elastic modulus E ′ at room temperature and Tg + 30 ° C., the dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., the photoelastic coefficient k at 25 ° C., at 20 ° C. The refractive index N1 was measured and the results are shown in Table 3.

In addition, a single film sheet obtained by extruding a base film on a cast drum and cooling the base material is heated to 84 ° C., stretched 3.3 times in the longitudinal direction, and then a preheating zone at 85 ° C. with a tenter. Then, the film was stretched 3 times in the width direction at 90 ° C., and then heat-treated at 90 ° C. for 20 seconds and at 220 ° C. for 30 seconds to obtain a single film sheet having a film thickness of 80 μm. The dynamic storage elastic modulus E3 ′ at Tg1 + 30 ° C. and the refractive index N2 at 20 ° C. of the obtained single layer sheet were measured. The results are shown in Table 3.

Further, the obtained laminated sheet having a surface layer thickness of 20 μm and a mold were heated to 165 ° C., the surface layer of the sheet and the uneven surface of the mold were brought into contact, pressed at 20 MPa, and held for 2 minutes. Thereafter, the press was released after cooling to 125 ° 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, it was confirmed that the shape was sufficiently transferred in any mold (mold 1: A ′ / A = 0.919, gold Mold 2: A ′ / A = 0.924, Mold 3: A ′ / A = 0.911, Mold 4: A ′ / A = 0.908, Mold 5: A ′ / A = 0.895 ). The results are shown in Table 4.

(Example 6)
Polyester (inherent viscosity C = 0.43 dl / g) copolymerized with cyclohexanedicarboxylic acid as dicarboxylic acid component, 80 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 20 mol% of ethylene glycol as diol component at 35 ° C. Of cyclohexanone / methyl ethyl ketone = 1/1 solution was dissolved to a concentration of 25% by weight. The obtained solution was applied to a 125 μm thick polyester film “Lumirror” U12 (manufactured by Toray Industries, Inc.) using an applicator, dried at 100 ° C. for 30 minutes, and a laminate having a surface layer having a dry film thickness of 30 μm. Was made.
The peel strength between the surface layer and the base material layer of the obtained laminated sheet was determined. The results are shown in Table 3.

Further, a laminated sheet having a surface layer thickness of 4 μm was produced by the same method. The spectral transmittance of the obtained laminated sheet was measured to evaluate the optical characteristics. The results are shown in Table 3.

Moreover, about a surface layer, a solution is apply | coated using an applicator on the polyester film 'Lumirror' T60 (made by Toray Industries, Inc.) of 100 micrometer thickness, and after drying for 30 minutes at 100 degreeC, it peels and single layer A sheet was obtained. The glass transition temperature Tg of the obtained single membrane sheet, the dynamic storage elastic modulus E ′ at room temperature and Tg + 30 ° C., the dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., the photoelastic coefficient k at 25 ° C., at 20 ° C. In addition, the dynamic storage elastic modulus E3 ′ at Tg1 + 30 ° C. and the refractive index N2 at 20 ° C. of the base polyester film were measured, and the results are shown in Table 3.

Further, a resin molded product was obtained in the same manner as in Example 5, except that the mold was pressed on the surface layer side, the pressing temperature was 165 ° C., and the press release temperature was 125 ° 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 = 0.963, Mold 2: A ′ / A = 0.970, Mold 3: A ′ / A = 0.954, Mold 4: A ′ / A = 0 939, mold 5: A ′ / A = 0.924). The results are shown in Table 4.

(Example 7)
As a surface layer, cyclohexanedicarboxylic acid as a dicarboxylic acid component, 9,9′-bis (4-hydroxyethoxyphenyl) fluorene as a diol component, 60 mol%, ethylene glycol 40 mol% copolymerized polyester (intrinsic viscosity C = 0.61 dl / g) A laminated body and a single film sheet were produced in the same manner as in Example 6 except that was used.
The peel strength and optical properties of the surface layer and the base material layer of the obtained laminated sheet were determined. The results are shown in Table 3. Further, the obtained single film sheet has a glass transition temperature Tg, a dynamic storage elastic modulus E ′ at room temperature and Tg + 30 ° C., a dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., a photoelastic coefficient k at 25 ° C., The refractive index N1 at 20 ° C. was measured, the dynamic storage elastic modulus E3 ′ of the base polyester film at Tg1 + 30 ° C., and the refractive index N2 at 20 ° C. were measured, and 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 175 ° C. and the press release temperature was 140 ° 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 = 0.946, gold Mold 2: A ′ / A = 0.967, Mold 3: A ′ / A = 0.952, Mold 4: A ′ / A = 0.931, Mold 5: A ′ / A = 0.919 ). The results are shown in Table 4.

(Example 8)
As a surface layer, as a dicarboxylic acid component, 50 mol% of cyclohexanedicarboxylic acid, 50 mol% of terephthalic acid, 9,9′-bis (4-hydroxyethoxyphenyl) fluorene as a diol component, 50 mol% of ethylene glycol, and 50% ethylene glycol (inherent viscosity C) = 0.57 dl / g), a laminate and a single film sheet were produced in the same manner as in Example 6.
The peel strength and optical properties of the surface layer and the base material layer of the obtained laminated sheet were determined. The results are shown in Table 3. Further, the obtained single film sheet has a glass transition temperature Tg, a room temperature and a dynamic storage elastic modulus E ′ at Tg + 30 ° C., a dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., a photoelastic coefficient k at 25 ° C., The refractive index N1 at 20 ° C. was measured, the dynamic storage elastic modulus E3 ′ of the base polyester film at Tg1 + 30 ° C., and the refractive index N2 at 20 ° C. were measured, and the results are shown in Table 3.

Further, a resin molded product was obtained in the same manner as in Example 6 except that the press temperature was 160 ° C. and the press release temperature was 120 ° C.
When the cross section of the obtained molded article was observed with a scanning electron microscope, it was confirmed that the shape was sufficiently transferred in any mold (mold 1: A ′ / A = 0.938, gold Mold 2: A ′ / A = 0.916, Mold 3: A ′ / A = 0.945, Mold 4: A ′ / A = 0.828, Mold 5: A ′ / A = 0.916 ). The results are shown in Table 4.

(Comparative Example 1)
Spiroglycol 30 mol% copolymer polyester S-PET30 (Mitsubishi Gas Chemical Co., Ltd., fluorene skeleton not contained, intrinsic viscosity C = 0.68 dl / g) vacuum-dried at 90 ° C. for 4 hours in an extruder at 280 ° C. And was extruded onto a cast drum from the die 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 photoelastic coefficient k at 25 ° C. Table 1 shows.

A resin molded product was obtained in the same manner as in Reference Example 1 except that the press temperature was 140 ° 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, 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 = 0.945, Mold 2: A ′ / A = 0.960, Mold 3: A ′ / A = 0.929, Mold 4: A ′ / A = 0.763, mold 5: A '/ A = 0.697). Further, when the optical distortion of the molded product was observed, the optical distortion was clearly observed in both the parallel and vertical absorption axes of the two polarizing plates. The results are shown in Table 2.

(Comparative Example 2)
Isophthalic acid 17.5 mol% copolymerized PET (fluorene skeleton not contained, intrinsic viscosity C = 0.65 dl / g) was vacuum dried at 150 ° C. for 2 hours, then melted at 250 ° C. in an extruder, The sheet was extruded 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 Tg, room temperature and dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and photoelastic coefficient k at 25 ° C. Table 1 shows.

A resin molded product was obtained in the same manner as in Reference Example 1 except that the press temperature was 110 ° C. and the press release temperature was 80 ° C.
When the cross section of the obtained molded product was observed with a scanning electron microscope, molds 1 and 2 were sufficiently molded, but molds 2 and 3 had rounded vertices and could be molded sufficiently. (Mold 1: A ′ / A = 0.914, Mold 2: A ′ / A = 929, Mold 3: A ′ / A = 0.863, Mold 4: A ′ / A = 0.756, mold 5: A ′ / A = 0.661). Further, when the optical distortion of the molded product was observed, the optical distortion was clearly observed in both the parallel and vertical absorption axes of the two polarizing plates. The results are shown in Table 2.

(Comparative Example 3)
Polyester (inherent viscosity C = 0.63 dl / g) obtained by copolymerization of terephthalic acid as a dicarboxylic acid component, 5 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene and 95 mol% of ethylene glycol as a diol component at 90 ° C. After vacuum drying for 4 hours, it 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 Tg, room temperature and dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and photoelastic coefficient k at 25 ° C. Table 1 shows.

A resin molded product was obtained in the same manner as in Reference Example 1 except that the press temperature was 130 ° C. and the press release temperature was 90 ° 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. 870, mold 2: A ′ / A = 0.833, mold 3: A ′ / A = 0.716, mold 4: A ′ / A = 0.631, mold 5: A ′ / A = 0.540). Further, when the optical distortion of the molded product was observed, the optical distortion was clearly observed in both the parallel and vertical absorption axes of the two polarizing plates. The results are shown in Table 2.

(Comparative Example 4)
25 mol% cyclohexanedimethanol copolymerized PET (containing no fluorene skeleton, intrinsic viscosity C = 0.74 dl / g) vacuum-dried at 70 ° C. for 4 hours in an extruder at 250 ° 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 photoelastic coefficient k at 25 ° C. Table 1 shows.

A resin molded product was obtained in the same manner as in Reference Example 1 except that the press temperature was 110 ° C. and the press release temperature was 70 ° C.
A resin molded product was obtained in the same manner as in Reference Example 1.
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. 831, Mold 2: A ′ / A = 0.856, Mold 3: A ′ / A = 0.727, Mold 4: A ′ / A = 0.619, Mold 5: A ′ / A = 0.551). Further, when the optical distortion of the molded product was observed, the optical distortion was clearly observed in both the parallel and vertical absorption axes of the two polarizing plates. The results are shown in Table 2.

(Comparative Example 5)
Dimer acid 15 mol%, 1,4-butanediol 62 mol% copolymerized PET (containing no fluorene skeleton, intrinsic viscosity C = 0.74 dl / g) was dried at 120 ° C. for 2 hours, and then in an extruder at 250 ° C. After melting, the sheet was 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 Tg, room temperature and dynamic storage elastic modulus E ′ at Tg + 30 ° C., dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., and photoelastic coefficient k at 25 ° C. Table 1 shows.

A resin molded product was obtained in the same manner as in Reference 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. 339, mold 2: A ′ / A = 0.350, mold 3: A ′ / A = 0.278, mold 4: A ′ / A = 0.115, mold 5: A ′ / A = 0.102). Further, when the optical distortion of the molded product was confirmed, almost no optical distortion was observed when the absorption axes of the two polarizing plates were parallel, but slight optical distortion was observed when it was vertical. The results are shown in Table 2.

(Comparative Example 6)
30 parts by weight of polymethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., containing no fluorene skeleton, intrinsic viscosity C = 0.78 dl / g) 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 dried under reduced pressure at 80 ° C. for 4 hours 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 photoelastic coefficient k at 25 ° C. Table 1 shows.

Further, except that the press temperature was set to 150 ° C. and the press release temperature was set to 130 ° C., an attempt was made to obtain a resin molded product by the same method as in Reference Example 1, but the mold 1 can be released from the mold. In addition, in the molds 4 and 5, the convex portion was broken at the time of mold release, and neither could obtain a resin molded product. It was confirmed that the molds 2 and 3 were sufficiently molded (mold 2: A ′ / A = 0.953, mold 3: A ′ / A = 0.927). The results are shown in Table 2.

(Comparative Example 7)
Other than using as a surface layer, spiroglycol 30 mol% copolymer polyester S-PET30 (Mitsubishi Gas Chemical Co., Ltd., fluorene skeleton-free, intrinsic viscosity C = 0.68 dl / g) vacuum-dried at 90 ° C. for 4 hours. A laminate and a single film sheet were produced in the same manner as in Example 5.
The peel strength and optical properties of the surface layer and the base material layer of the obtained laminated sheet were determined. The results are shown in Table 3. Further, the obtained single film sheet has a glass transition temperature Tg, a room temperature and a dynamic storage elastic modulus E ′ at Tg + 30 ° C., a dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., a photoelastic coefficient k at 25 ° C., The refractive index N1 at 20 ° C. was measured, and the dynamic storage elastic modulus E3 ′ at Tg1 + 30 ° C. and the refractive index N2 at 20 ° C. were measured for the substrate single film sheet.

A resin molded product was obtained in the same manner as in Example 5 except that the press temperature was 140 ° 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, molds 1, 2, and 3 were sufficiently molded, but mold 4.5 was rounded and the mold was sufficiently molded. (Mold 1: A ′ / A = 0.934, Mold 2: A ′ / A = 0.926, Mold 3: A ′ / A = 0.902, Mold 4: A '/A=0.835, mold 5: A' / A = 0.722). The results are shown in Table 4.

(Comparative Example 8)
As a surface layer, a laminate was obtained in the same manner as in Example 5 except that 17.5 mol% copolymerized PET (containing no fluorene skeleton, intrinsic viscosity C = 0.65 dl / g) of isophthalic acid vacuum-dried at 150 ° C. for 2 hours was used. A single film sheet was prepared.
The peel strength and optical properties of the surface layer and the base material layer of the obtained laminated sheet were determined. The results are shown in Table 3. Further, the obtained single film sheet has a glass transition temperature Tg, a room temperature and a dynamic storage elastic modulus E ′ at Tg + 30 ° C., a dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., a photoelastic coefficient k at 25 ° C., The refractive index N1 at 20 ° C. was measured, and the dynamic storage elastic modulus E3 ′ at Tg1 + 30 ° C. and the refractive index N2 at 20 ° C. were measured for the substrate single film sheet.

A resin molded product was obtained in the same manner as in Example 5 except that the press temperature was 110 ° C. and the press release temperature was 80 ° 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. 863, mold 2: A ′ / A = 0.877, mold 3: A ′ / A = 0.857, mold 4: A ′ / A = 0.634, mold 5: A ′ / A = 0.521). The results are shown in Table 4.

(Comparative Example 9)
As a surface layer, polyester dried by vacuum drying at 90 ° C. for 4 hours, terephthalic acid as a dicarboxylic acid component, 5 mol% of 9,9′-bis (4-hydroxyethoxyphenyl) fluorene as a diol component, and 95 mol% of ethylene glycol (inherent) A laminate and a single film sheet were produced in the same manner as in Example 5 except that the viscosity C = 0.63 dl / g) was used.
The peel strength and optical properties of the surface layer and the base material layer of the obtained laminated sheet were determined. The results are shown in Table 3. Further, the obtained single film sheet has a glass transition temperature Tg, a room temperature and a dynamic storage elastic modulus E ′ at Tg + 30 ° C., a dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., a photoelastic coefficient k at 25 ° C., The refractive index N1 at 20 ° C. was measured, and the dynamic storage elastic modulus E3 ′ at Tg1 + 30 ° C. and the refractive index N2 at 20 ° C. were measured for the substrate single film sheet.

A resin molded product was obtained in the same manner as in Example 5 except that the press temperature was 130 ° C. and the press release temperature was 90 ° 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. 977, mold 2: A ′ / A = 0.873, mold 3: A ′ / A = 0.702, mold 4: A ′ / A = 0.560, mold 5: A ′ / A = 0.467). The results are shown in Table 4.

(Comparative Example 10)
As a surface layer, a laminated body in the same manner as in Example 5, except that 25 mol% cyclohexanedimethanol copolymerized PET (containing no fluorene skeleton, intrinsic viscosity C = 0.74 dl / g) was vacuum-dried at 70 ° C. for 4 hours. A single film sheet was produced.
The peel strength and optical properties of the surface layer and the base material layer of the obtained laminated sheet were determined. The results are shown in Table 3. Further, the obtained single film sheet has a glass transition temperature Tg, a room temperature and a dynamic storage elastic modulus E ′ at Tg + 30 ° C., a dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., a photoelastic coefficient k at 25 ° C., The refractive index N1 at 20 ° C. was measured, and the dynamic storage elastic modulus E3 ′ at Tg1 + 30 ° C. and the refractive index N2 at 20 ° C. were measured for the substrate single film sheet.

A resin molded product was obtained in the same manner as in Example 5 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, the vertex was rounded in any mold, and the molding was not sufficiently performed (mold 1: A ′ / A = 0. 761 Mold 2: A ′ / A = 0.629, Mold 3: A ′ / A = 0.684, Mold 4: A ′ / A = 0.508, Mold 5: A ′ / A = 0 419). The results are shown in Table 4.

(Comparative Example 11)
A laminate and a single film sheet were produced in the same manner as in Example 6 except that polymethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., fluorene skeleton not contained, intrinsic viscosity C = 0.78 dl / g) was used as the surface layer. did.
The peel strength and optical properties of the surface layer and the base material layer of the obtained laminated sheet were determined. The results are shown in Table 3. Further, the obtained single film sheet has a glass transition temperature Tg, a room temperature and a dynamic storage elastic modulus E ′ at Tg + 30 ° C., a dynamic loss elastic modulus E2 ″ at Tg + 30 ° C., a photoelastic coefficient k at 25 ° C., The refractive index N2 at 20 ° C. was measured, the dynamic storage elastic modulus E3 ′ at Tg1 + 30 ° C. of the base polyester film, and the refractive index N2 at 20 ° C. were measured.

Further, except that the press temperature was 150 ° C. and the press release temperature was 130 ° C., an attempt was made to obtain a resin molded product by the same method as in Example 6, 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.

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 3H 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. . 4A to 4D 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. 5 (a) shows a molded product formed on the easily surface-shaped sheet used in the present invention , and FIG. 6 (b) shows the molded product formed on the easily surface-shaped sheet laminate of the present invention. It is a cross-sectional view schematically showing a product. FIGS. 6A to 6F 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. 7A to 7H 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. 8A to 8D 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. 9A to 9E are perspective views schematically showing a part of a mold used in Examples and Comparative Examples.

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 portion t Width of concave portion of mold S 'Width of convex portion of molded product H' Height of convex portion of molded product l 'Thickness of base of molded product t' Width of concave portion of molded product

Claims (6)

A base material which is a sheet mainly composed of a polyester resin containing at least a repeating unit having a fluorene skeleton as a copolymer component, and which serves as a support, satisfying the following requirements (A) to ( E ) An easily surface formable sheet laminate formed by laminating at least one side of the surface of the sheet.
(A) The crystallization enthalpy ΔHcc in the heating process (heating rate: 2 ° C./min) obtained by differential scanning calorimetry (hereinafter, DSC) is 1 J / g or less.
(B) 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.
(C) The dynamic storage elastic modulus E2 ′ obtained by DMA at a glass transition temperature (hereinafter referred to as Tg) + 30 ° C. is 1 × 10 ^{4 to} 5 × 10 ⁶ Pa.
(D) The dicarboxylic acid component of the polyester resin is composed of terephthalic acid and / or cyclohexanedicarboxylic acid.
(E) The diol component of the polyester resin is composed of a diol having a fluorene skeleton and ethylene glycol, and the diol having the fluorene skeleton is 40 to 80 mol% in 100 mol% of all diol components. 2. The easy surface shaping according to claim 1 , wherein the difference ΔN = | N1−N2 | between the refractive index N1 of the easy surface shaping sheet and the refractive index N2 of the substrate is 0 to 0.10. Sheet laminate. The easily surface-shaped sheet laminate according to claim 1 , wherein the substrate is a biaxially stretched polyester film. A surface layer composed of at least the easy-surface-formable sheet of the easy-surface-formable sheet laminate according to any one of claims 1 to 3 is heated (heating temperature: T1) and pressed using a mold (press Temperature: T1) and then cooling to release the press pressure (press pressure release temperature: T2), and then releasing the mold (mold release temperature: T3) to form a molded product to which the mold shape is transferred A surface shaping method, wherein the T1, T2 and T3 satisfy the following formulas (1) to (5).
Tg1 ≦ T1 ≦ Tg1 + 50 ° C. (1)
T1 <Tm (2)
Tg1-20 ≦ T2 ≦ Tg1 + 20 ° C. (3)
T2 <T1 (4)
20 ° C. ≦ T3 ≦ T2 (5)
(Where, Tm is the melting point of the surface layer of the easily surface-shaped sheet, and Tg1 is the glass transition temperature of the surface layer of the easily surface-shaped sheet ) The mold has a concavo-convex shape on the surface, the ratio H / S (hereinafter, aspect ratio) of the height H and width S of the convex section of the mold is 1 to 20, and the width S of the convex section is S The surface shaping method according to claim 4 , wherein the surface shaping method is 0.01 to 200 μm, the height H is 0.01 to 200 μm, and the pitch is 0.02 to 300 μm. A molded article having an uneven shape on the surface obtained by the surface shaping method according to any one of claims 4-5, the aspect ratio H '/ S' 1 to 10 of the convex portion of the concavo-convex shape, a convex A molded product having a width S ′ of 0.01 to 200 μm, a height H ′ of 0.01 to 200 μm, and a pitch of 0.02 to 300 μm.

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