JP2006137083A - Method for producing polymer molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polymer molding, especially an optical member, which is high in accuracy without needing photocuring and thermosetting properties. <P>SOLUTION: In the method for producing the polymer molding, a polymer solution is applied on a support in an optional shape and dried while being held on the support. The molding of an aromatic polymer or an alicyclic polymer is produced, in which the amount of remaining volatile substances is 10 wt% or below when it is peeled off from the support. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a polymer molded body capable of easily imparting an arbitrary shape, and in particular, an optical member that requires a fine and precise shape such as an optical waveguide, a microlens array, a prism sheet, an optical filter, or a film. It relates to a manufacturing method.

  An optical member such as a microlens array has a problem that light is bent in an unintended direction due to a slight error in dimensions, or light loss becomes large, and extremely precise molding is required. Conventionally, as a method for molding such a precision optical member, as disclosed in Patent Documents 1 and 2, a method in which a curable resin is poured into a mold and cured by light or heat has been used.

However, since the photo-curing or thermosetting resin needs to impart curing performance, it has a problem that it is expensive and the types of resins that can be used are limited.
JP 2004-4233 A JP 2004-163695 A

  The present invention has been achieved as a result of studying the solution of the problems in the prior art described above as an issue. That is, an object of the present invention is to provide a method for producing a polymer molded body, particularly an optical member, having high accuracy without requiring photocurability or thermosetting.

  In order to achieve the above-described object, the present invention applies a solution containing a polymer on a support having a predetermined surface shape, and the solution is formed on the support until the volatile component of the solution is 10% by weight or less. The method is characterized in that it is a method for producing a polymer molded body in which the molded body on which the surface shape on the support is transferred is peeled off after drying. Here, it is also preferable to perform the drying in two or more steps having different temperatures. Further, as the polymer, at least one polymer selected from the group consisting of polyimide, polyamide, polyether ketone, polyether ether ketone, polycarbonate, cyclic polyolefin, acrylic, polyester, fluororesin, and polyether sulfone may be used. preferable. Furthermore, it is also preferable that the light transmittance of light of all wavelengths from 450 nm to 700 nm of the polymer is 80% or more.

  It is possible to provide a method for producing a polymer molded body, particularly an optical member, with high accuracy without requiring photocurability or thermosetting.

  In the present invention, a support containing a predetermined surface shape is coated with a solution containing a polymer, dried on the support until the volatile component of the solution is 10% by weight or less, and then supported. A polymer molded body is obtained by peeling off a molded body to which the surface shape on the body is transferred. In general, when a molded body such as a polymer film is produced by a solution casting method, that is, a method in which a polymer solution is applied to a support and dried, the polymer is removed from the support in an insufficiently dried state in which about 50% by weight of volatile matter remains. A method of further drying the molded body by itself after peeling is used. In this method, since the solvent is dried from both sides of the molded body such as a film, there is an advantage that the drying speed is faster compared with the case of drying on the support. Since the shrinkage due to drying after the treatment is large, the shape of the support cannot be accurately transferred.

  It is preferable that the volatile matter remaining at the time of peeling from the support is 10% by weight or less because the drying shrinkage after peeling is small and the shape of the support can be accurately transferred. The volatile matter remaining at the time of peeling is more preferably 5% by weight or less, and most preferably 1% by weight or less. Since the remaining volatile matter is small, advantages such as small drying shrinkage after peeling and no problem due to volatile matter during use can be obtained. Moreover, although there is no lower limit to the amount of volatile matter, it is usually 0% by weight or more.

  The present invention is characterized in that the shape of the support is accurately transferred. When the maximum height of the surface shape of the support is Rz1, and the maximum height of the surface shape of the molded body is Rz2, Rz2 is 90 of Rz1. It is preferable that it is the value of% -110%. More preferably, Rz2 is 95% to 105% of Rz1.

  Moreover, it is also preferable that the surface shape has a predetermined period, and it is also preferable that a repeating pattern of dots, lines, and arbitrary figures is given. In this case, in the plane to which the shape is given, when the surface shape period in a specific direction on the surface is L1, and the period of the surface shape of the molded body in the direction corresponding to the specific direction is L2, L2 is preferably 90% to 110% of L1. More preferably, L2 is 95% or more and 105% or less of L1. If the shape of the molded body is accurately transferred from the shape of the support (when L2 = L1), the performance when used as a molded product or an optical member is extremely good.

  In the present invention, the measuring method of the periods L1 and L2 is not particularly limited, but in order to determine whether or not the shape of the support is accurately transferred, it is preferable to determine and measure the following reference points.

  (1) In the case of a microlens array, that is, a shape in which a hemisphere or a part of a sphere is arranged on a plane, the distance between the vertex of the hemisphere or sphere in the cross section and the vertex adjacent to the vertex is measured. It is preferable to obtain an average from the measured values of the distances greater than or equal to the point and set the periods L1 and L2. It is preferable to measure the part to be measured and the part of the molded body corresponding to the part to be measured. However, when using a support having a continuous similar shape, the above correspondence is always necessary. It does n’t mean. Moreover, in this invention, the said prescription | regulation regarding L1 and L2 should just be satisfied about the some place of a support body or a molded object. Note that the above method can also be used to measure shapes in which special lenses such as aspheric lenses, Fresnel lenses, and pyramid lenses are arranged on a plane.

  (2) In the case of a shaped body in which prism sheets, that is, triangular prisms or the like are arranged on a plane (for example, “BEFII” manufactured by Sumitomo 3M Limited), the distance between adjacent ridgelines is measured. Also in this case, it is preferable to obtain the average from the measured values of the distances of three or more points and set the periods L1 and L2. Also in this case, it is only necessary that the relationship between L1 and L2 described above is satisfied at some point on the support and the molded body.

  The method for producing a molded article of the present invention can be suitably used for producing a shape having no fixed period, such as a light guide plate, a diffuse reflector, a leather pattern, a film, and a sheet. In this case, it is preferable that the same relation as described above is satisfied for Ra measured according to the method described in JIS B0601-2001. That is, when the arithmetic average height of the surface shape of the support is Ra1 and the arithmetic average height of the surface shape of the molded body is Ra2, Ra2 is preferably a value of 90% to 110% of Ra1.

  In the present invention, the drying process is preferably performed in two or more processes having different temperatures. Of course, it is also preferable to perform drying in three or more different steps (temperatures). In this case, when the drying temperature is set to T1, T2, T3,... Sequentially from the start of drying, the initial drying temperature T1 is preferably a temperature not higher than the boiling point of the solvent used. In the present invention, it is characterized in that it is sufficiently dried while holding the molded body on the support, but if it is heated from the first stage at a temperature exceeding the boiling point of the solvent, a bubble-like defect can be formed. There is. Furthermore, it is preferable that T2, T3,... Are sequentially heated up to an arbitrary temperature Tmax. Even if the temperature does not exceed the boiling point of the solvent, if the temperature of T1 is high, a dried part of the film is formed on the surface of the molded body, and this film prevents the solvent from evaporating, so the inside is sufficiently dried. There are things that cannot be done.

  Tmax is not particularly limited, but is preferably a temperature equal to or higher than the boiling point of the solvent at the atmospheric pressure of the process. In order to perform drying at a temperature below the boiling point of the solvent until the final step and to reduce the remaining volatile content to 10% by weight or less, a considerably long drying time may be required, resulting in an increase in production cost. By heating at a temperature equal to or higher than the boiling point of the solvent, the solvent can be sufficiently dried even when one side of the molded body is in close contact with the support. More preferably, Tmax is a temperature higher than the glass transition temperature of the polymer. By heating at a temperature equal to or higher than the glass transition temperature, the molecules easily move and the solvent easily evaporates.

  After Tmax, the temperature is gradually lowered and the formed body is peeled off from the support, but may be peeled off at Tmax as long as Tmax is equal to or lower than the glass transition temperature of the polymer.

  Moreover, about a drying process, it is also preferable to dry under reduced pressure at 0.1 Mpa or less. By reducing the pressure, the boiling point of the solvent can be lowered, and the temperature of the heater requiring a large amount of electric energy can be lowered, so that the cost can be reduced. Moreover, although it is necessary that the optical member is not colored, coloring can be reduced because it can be dried at a low temperature.

  The support used in the production method of the present invention is not particularly limited and is selected from metals, glasses, polymers, etc., but has resistance to the solvent used, and the dimensional change at the boiling point of the solvent + 50 ° C. It is important that is small. The support may be a simple substance such as metal, glass, polymer, or a composite material. For the purpose of satisfying both adhesiveness at the time of drying and subsequent peelability, those whose surfaces are processed are also preferable.

  The polymer applied in a solution state needs to be in close contact with the support until the remaining volatile components are dried to 10% by weight or less. On the other hand, after drying, the polymer needs to be peeled off from the support. For this reason, it is useful to provide a release agent on the surface of the support where the surface shape is provided or to add a release agent to the polymer solution. There are no particular limitations on the release agent used, but for example, those sold under the names of lubricants, surfactants, surface modifiers, release agents, etc. can be used. For example, Recommont FN901 manufactured by Clariant Japan Co., Ltd. Wax Composite G431L, Wax Composite G432L, Daikin Industries Co., Ltd. Unidyne DS403, Zeffle GH700, Dainippon Ink Co., Ltd. MegaFuck F479, MegaFuck F1405, MegaFus ESM1, Neos Co., Ltd. Footage, Toray Dow Corning Silicone Silicone mold release agent, Sakai Kogyo Co., Ltd. mold with, Seimi Chemical Co., Ltd. Surflon, JSR Co., Ltd. dynacera, DuPont Japan Co., Ltd. zonyl, etc. are mentioned.

  Good transfer can be obtained by controlling the adhesion between the support and the polymer solution and the peelability of the polymer molded body by the release agent.

  The molded body produced by the method of the present invention is not particularly limited as long as it is a polymer that is soluble in a solvent, but is preferably an aromatic polymer or an alicyclic polymer, such as polyimide, polyamide, Polymers containing any one or more of polyether ketone, polyether ether ketone, polycarbonate, cyclic polyolefin, acrylic, and polyether sulfone are preferably used.

  Particularly preferred are aromatic polyamides, modified acrylics, and alicyclic polyolefins. Aromatic polyamide has a high refractive index of 1.6 or higher and a high glass transition temperature of 250 ° C. or higher. Therefore, when a microlens is used, a highly efficient lens can be produced.

  Since aramid has a unique structural unit, high transparency and refractive index can be realized. That is, the structural unit represented by the chemical formula (I), (II), (III) or (IV) is included (all of these structural units may be included, or only a part thereof may be included) and When the molar fractions of the structural units represented by chemical formulas (I), (II), (III), and (IV) are l, m, n, and o, respectively, the following formulas (2) to (4) are satisfied. It is preferable to use aramid.

50 <l + m + n ≦ 100 (2)
0 ≦ l, m, n, o ≦ 100 (3)
0 ≦ o ≦ 50 (4)

R ₁ : a group having at least one 5-membered ring, 6-membered ring or 7-membered ring R ₂ : any aromatic group X: hydrogen, halogen or a hydrocarbon group having 1 to 3 carbon atoms

R ₃ : —CF ₃ , —CCl ₃ , —CBr ₃ , —OH, —F, —Cl, —OCH ₃ (however, structural units having these groups may be mixed in the molecule)
R ₄ : any aromatic group

_{R 5: -SO 2 -, -} O -, - CH 2 -, - C (CF 3) 2 - group selected from or _{-SO 2, -, - O -} , - CH 2 -, - C (CF 3 ) Aromatic group containing one or more groups selected from ₂ − R ₆ : Arbitrary aromatic group X: Hydrogen, halogen or hydrocarbon group having 1 to 3 carbon atoms

R _7: any aromatic radical R _8: any aromatic group X: hydrogen, halogen or a hydrocarbon group formula of 1 to 3 carbon atoms (I), (II), (III) and (IV) each occurrence Or not, but when the molar fractions of the structural units represented by the chemical formulas (I), (II) and (III) are 1, m and n, respectively, l + m + n is 50. It is a preferable aspect to exceed. More preferably, l + m + n is 80 or more, and most preferably l + m + n is 100. When l + m + n is 50 or less, the contribution of the structural unit contributing to coloring becomes larger than these effects, and a colorless transparent film may not be obtained (inferior in light transmittance).

  The coloration of aramid is believed to be due to intramolecular and intermolecular charge transfer complexes, but chemical formulas (I), (II) and (III) all inhibit the formation of intramolecular and intermolecular charge transfer complexes. The aramid film is considered to be colorless and transparent (to improve light transmittance).

In Chemical Formula (I), R ₁ is preferably a group having at least one 5-membered ring, 6-membered ring or 7-membered ring, and more preferably a cyclic group represented by Chemical Formula (XI). Most preferred is a fluorene group.

In the chemical formula (II), R ₃ is —CF ₃ , —CCl ₃ , —CBr ₃ , —OH, —F, —Cl, —OCH ₃ (however, structural units having these groups are mixed in the molecule) Or the like may be suitably used. Most preferably -CF _3.

_R 5 _is, -SO 2 in Formula _{(III) -, - O -} , - CH 2 -, - C (CF 3) 2 - group selected from or _{-SO 2, -, - O -} , - CH 2 - An aromatic group containing one or more groups selected from —C (CF ₃ ) ₂ — is preferably used, and —SO ₂ — is most preferred.

  Modified acrylic refers to acrylic in general having a molecular structure of maleimide, glutarimide, lactone, glutaric anhydride, styrene or the like. Modified acrylic is preferable because it has both high light transmittance and a high glass transition temperature of 100 ° C. or higher. Examples of the alicyclic polyolefin include Arton manufactured by JSR Corporation, ZEONOR manufactured by ZEON Corporation, and APPEL manufactured by Mitsui Chemicals. These are preferable because they have high light transmittance and low water absorption.

  Furthermore, it is preferable that these polymers have a light transmittance of light of all wavelengths from 450 nm to 700 nm as 80% or more when used as an optical member. A high-performance optical member can be obtained when the light transmittance of light of all wavelengths from 450 nm to 700 nm is 80% or more.

  In addition, the polymer may contain an inorganic or organic additive for the purpose of controlling the refractive index, forming the surface, improving workability, and the like. Needless to say, the additive is selected according to the purpose. For example, the inorganic particles include, for example, aluminum complexes, aluminum oxide particles, tin oxide-aluminum oxide composite particles, silicon oxide-aluminum oxide composite particles, and zirconium oxide. -Aluminum oxide composite particles, tin oxide-silicon oxide composite particles, zirconium oxide-silicon oxide composite particles, etc., tin complexes, tin oxide particles, zirconium oxide-tin oxide composite particles, etc., titanium complexes, titanium oxide particles, tin oxide-oxidation Examples thereof include titanium composite particles, silicon oxide-titanium oxide composite particles, zirconium oxide-titanium oxide composite particles, zirconium complexes, and zirconium oxide particles. Of these, preferably, tin oxide-aluminum oxide composite particles, zirconium oxide-aluminum oxide composite particles, zirconium oxide-silicon oxide composite particles, etc., tin oxide particles, zirconium oxide-tin oxide composite particles, etc., titanium oxide particles, oxidation Examples thereof include tin-titanium oxide composite particles, silicon oxide-titanium oxide composite particles, zirconium oxide-titanium oxide composite particles, and zirconium oxide particles. Particularly preferred are tin oxide-titanium oxide composite particles, silicon oxide-titanium oxide composite particles, titanium oxide particles, zirconium oxide-tin oxide composite particles, zirconium oxide-silicon oxide composite particles, and zirconium oxide particles.

  These inorganic particles can be used as single particles or composite particles. Furthermore, these inorganic particles can be used by mixing one or more kinds.

  Commercially available compounds include “Op-trake TR-502” and “Op-trake TR-504” of tin oxide-titanium oxide composite particles, “Op-trake TR-503” of silicon oxide-titanium oxide composite particles, and titanium oxide. “OPTRAIK TR-505” (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.), zirconium oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), tin oxide-zirconium oxide composite particle sol (catalyst) Chemical Industry Co., Ltd.), tin oxide particles (manufactured by Kojundo Chemical Laboratory Co., Ltd.), and the like.

  The polymer used in the present invention preferably has a light transmittance of light of all wavelengths from 450 nm to 700 nm of 80% or more. More preferably, the light transmittance is 85% or more, and further preferably 90% or more. If the light transmittance of light of all wavelengths from 450 nm to 700 nm is 80% or more, it is useful as an optical member. There is no upper limit to the light transmittance, and it is possible to exceed 100% by adding, for example, a fluorescent brightening agent, but it is generally difficult to exceed 100%.

  Here, the total light transmittance and the light transmittance are measured by producing a film having a thickness of 10 μm.

  However, when it is difficult to produce a film having a thickness of 10 μm, the film is evaluated by converting to a thickness of 10 μm using the following formulas (1) and (2). Of course, even when only a sample exceeding 10 μm in thickness can be obtained, the following conversion method can be applied.

Light transmittance or total light transmittance (%) at 10 μm: T10
Film thickness (μm): L (Applicable range: 0.1 Å to 10 mm)
Light transmittance or total light transmittance (%) at thickness L: TL
Reflectance (%): R
Absorbance (% / μm): a
T10 = a × L + TL−a × 10 (1)
a = (100−R−TL) / L (2)
However, when the film thickness exceeds 10 μm and the light transmittance of light of all wavelengths from 450 nm to 700 nm is 80% or more, it is obvious that this condition is satisfied even at 10 μm. There is no need to convert the thickness to 10 μm.

  Next, examples of a method for producing an aromatic polyamide and a composition thereof suitably used in the present invention will be described below, but the present invention is not limited thereto.

  Various methods can be used to obtain an aromatic polyamide solution, that is, a film forming stock solution. For example, a low temperature solution polymerization method, an interfacial polymerization method, a melt polymerization method, a solid phase polymerization method, a vapor deposition polymerization method, or the like can be used. it can. When it is obtained from a low temperature solution polymerization method, that is, from carboxylic acid dichloride and diamine, it is synthesized in an aprotic organic polar solvent.

  Examples of the diamine include 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, and 2,2′-ditrifluoromethyl-4,4. '-Diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene 9,9-bis (4-amino-3-fluorophenyl) fluorene, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis (4-aminophenyl) hex Fluoropropane and the like can be mentioned, but 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 9,9-bis are preferable. (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene, 9,9-bis (4-amino) -3-fluorophenyl) fluorene.

  Examples of the carboxylic acid dichloride include terephthalic acid dichloride, 2chloro-terephthalic acid dichloride, 2-fluoro-terephthalic acid dichloride, isophthalic acid dichloride, orthophthalic acid dichloride, naphthalene dicarbonyl chloride, biphenyl dicarbonyl chloride, terphenyl dicarbonyl chloride, and the like. .

  In the aromatic polyamide solution, when acid dichloride and diamine are used as monomers, hydrogen chloride is by-produced. When neutralizing this, an inorganic neutralizing agent such as calcium hydroxide, calcium carbonate, lithium carbonate, Organic neutralizers such as ethylene oxide, propylene oxide, ammonia, triethylamine, triethanolamine, and diethanolamine are used. The reaction between isocyanate and carboxylic acid is carried out in an aprotic organic polar solvent in the presence of a catalyst.

  When performing polymerization using two or more kinds of diamines, diamines are added one by one, 10 to 99 mol% of acid dichloride is added to the diamine and reacted, and then another diamine is added, Further, a stepwise reaction method in which acid dichloride is added and reacted, a method in which all diamines are mixed and added, and then acid dichloride is added and reacted can be used. Similarly, when two or more kinds of acid dichlorides are used, a stepwise method, a method of simultaneously adding them, and the like can be used. In any case, the molar ratio of the total diamine to the total acid dichloride is preferably 95 to 105: 105 to 95, and if it is outside this value, it is difficult to obtain a polymer solution suitable for molding.

  Examples of the aprotic polar solvent used in the production of the aromatic polyamide of the present invention include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, and formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide. Solvents, acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-, m- or Phenolic solvents such as p-cresol, xylenol, halogenated phenol, and catechol, or hexamethylphosphoramide, γ-butyrolactone, and the like can be used. These are preferably used alone or as a mixture, but more preferably xylene, Toluene Using UNA aromatic hydrocarbons are also possible. Further, for the purpose of promoting the dissolution of the polymer, 50 wt% or less of an alkali metal or alkaline earth metal salt can be added to the solvent.

  In the polymer stock solution thus obtained, a salt is formed by a neutralization reaction between hydrogen chloride generated from acid dichloride and a neutralizing agent. This ratio becomes 5 to 20% by weight, and when this polymer stock solution is dried as it is, a salt is deposited. Therefore, it is preferable to remove the salt before the film formation or in the film formation process. The method for removing the salt is not particularly limited. For example, water is added to the polymer stock solution, and the polymer is reprecipitated and washed by stirring with a stirrer equipped with a cutter. The obtained polymer can be dried in a vacuum dryer and dissolved in a solvent at an arbitrary concentration to obtain a coating stock solution.

  In the present invention, the polymer molded body is produced by, for example, applying the above-described coating stock solution (solution containing an organic solvent) to a support having a predetermined surface shape and then removing the organic solvent. it can. The application method is not particularly limited, and examples thereof include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an ink jet method. be able to.

  The film thickness of the polymer molded body is not particularly limited, but when coating is used as the forming method, the film thickness is preferably 0.1 nm or more and 10 mm or less. If it is less than 0.1 nm, it may be difficult to apply uniformly, and if it exceeds 10 mm, it may be difficult to remove the solvent.

  The organic solvent used for coating is not particularly limited, but when the polymer is an aromatic polyamide, for example, dichloromethane, chloroform, benzene, toluene, methanol, ethanol, propanol, acetone, or sulfoxide such as dimethyl sulfoxide, diethyl sulfoxide, etc. Solvents, N, N-dimethylformamide, formamide solvents such as N, N-diethylformamide, N, N-dimethylacetamide, acetamide solvents such as N, N-diethylacetamide, N-methyl-2-pyrrolidone, N -Pyrrolidone solvents such as vinyl-2-pyrrolidone, phenol solvents such as phenol, o-, m- or p-cresol, xylenol, halogenated phenol, catechol, or hexamethylphosphoramide, γ-butyrolac Or the like can be mentioned down. These solvents may be used alone or in combination.

  When the polymer is acrylic, examples thereof include alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol, ketone solvents such as acetone and butanone, dichloromethane, chloroform, benzene, toluene and γ-butyrolactone. These solvents may be used alone or in combination.

  The present invention will be described more specifically with reference to the following examples.

    The physical property measurement method and the effect evaluation method in the examples were performed according to the following methods.

(1) Residual volatile matter The residual volatile matter (%) was determined by measurement using the following apparatus.

Apparatus: TGA-50 (manufactured by Shimadzu Corporation)
Temperature range: 30 ° C to 500 ° C
Temperature rising rate: 10 ° C./min (2) Height Ra, Rz and period of support and molded body The height and period (μm) of the support and molded body were determined by measurement using the following apparatus.

    The arithmetic average height Ra and the maximum height Rz were calculated by a method based on JIS B0601-2001.

Apparatus: Ultra deep color 3D shape measurement microscope VK-9500 (manufactured by Keyence Corporation)
Objective lens: x150
Measurement Mode: Color Ultra Depth Note that depending on the shape and / or refractive index, all laser beams are reflected, and there are samples whose height Ra, Rz and / or period cannot be measured accurately by the above method. In this case, it is possible to measure using a transmission electron microscope (so-called TEM method).

Equipment: H-7100FA manufactured by Hitachi, Ltd.
Acceleration voltage: 75 kV
Sample preparation: epoxy embedding, ultrathin section method (3) Light transmittance The transmittance (%) was determined by measurement using the following apparatus.

Apparatus: UV measuring instrument U-3410 (manufactured by Hitachi Instruments)
Wavelength range: 300 nm to 800 nm
Measurement speed: 120 nm / min Measurement mode: Transmission (Reference Example 1)
In a 200 ml four-necked flask equipped with a stirrer, 2.483 g of 4,4′-diaminodiphenylsulfone, 2.483 g of 3,3′-diaminodiphenylsulfone, and 63.1 ml of N-methyl-2-pyrrolidone were placed under a nitrogen atmosphere. The mixture was stirred under ice cooling. After 10 to 30 minutes, 4.060 g of terephthalic acid dichloride was added in 5 portions. After further stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with 1.426 g of lithium carbonate to obtain a transparent polymer solution 1.

  The obtained polymer solution 1 was ground in water using a mixer, collected by filtration and dried to isolate the polymer. The isolated polymer was dissolved in NN ′ dimethylacetamide so that the solid content concentration was 20% by weight to obtain a polymer solution A.

(Reference Example 2)
A 300 ml four-necked flask equipped with a stirrer was charged with 4,080 g of 4,4′-diaminodiphenyl sulfone, 6.2080 g of 3,3′-diaminodiphenyl sulfone, and 194 ml of N-methyl-2-pyrrolidone, and cooled with ice in a nitrogen atmosphere. Stirred under. 0.021 g of benzoyl chloride was added, and 9.6435 g of terephthalic acid dichloride was added in 5 portions over 10 to 30 minutes. After further stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with 2.6852 g of propylene oxide to obtain a transparent polymer solution 2.

  The obtained polymer solution 2 was ground in water using a mixer, filtered and dried to isolate the polymer. The isolated polymer was dissolved in γ-butyrolactone so that the solid content concentration was 20% by weight to obtain a polymer solution B.

(Reference Example 3)
In a 200 ml four-necked flask equipped with a stirrer, 6.969 g of 9,9 bis (4-aminophenyl) fluorene and 80.64 ml of N-methyl-2-pyrrolidone were placed and stirred under a nitrogen atmosphere under ice cooling. After 10 to 30 minutes, 4.060 g of terephthalic acid dichloride was added in 5 portions. After further stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with 1.426 g of lithium carbonate to obtain a transparent polymer solution 3.

  The obtained polymer solution 3 was pulverized in water using a mixer, collected by filtration and dried to isolate the polymer. The isolated polymer was dissolved in NN ′ dimethylacetamide so that the solid content concentration was 25% by weight to obtain a polymer solution C.

(Reference Example 4)
In a 200 ml four-necked flask equipped with a stirrer, 7.684 g of 9,9 bis (3-fluoro-4-aminophenyl) fluorene and 37.6 ml of N-methyl-2-pyrrolidone were placed and stirred under ice-cooling in a nitrogen atmosphere. . After 10 to 30 minutes, 4.7494 g of 2-chloroterephthalic acid dichloride was added in five portions. After further stirring for 1 hour, hydrogen chloride generated by the reaction was neutralized with 1.4261 g of lithium carbonate to obtain a transparent polymer solution 4.

  The obtained polymer solution 4 was pulverized in water using a mixer, filtered and dried to isolate the polymer. The isolated polymer was dissolved in NN ′ dimethylacetamide so that the solid content concentration was 20% by weight to obtain a polymer solution D.

Example 1
A suspension of 0.1 g of ZONYL® UR (manufactured by DuPont) dissolved in 100 g of N-methyl-2-pyrrolidone was applied to a stainless microlens mold (lens height 15 μm, period 50 μm), 120 ° C. For 5 minutes. It was washed with dryness, N-methyl-2-pyrrolidone and acetone to remove excess ZONYL (R) UR. The polymer solution A obtained in Reference Example 1 was applied with a bar coater to a coating thickness of 600 μm and dried at 120 ° C. for 60 minutes and 280 ° C. for 3 minutes to obtain a microlens array having a thickness of 110 μm. The obtained molded article had a lens height of 14.5 μm, a period of 50 μm, and a residual volatile content of 3% by weight.

(Example 2)
A microlens array having a film thickness of 105 μm was obtained under the same conditions as in Example 1 except that the polymer solution used was polymer B. The obtained molded product had a lens height of 14.8 μm, a period of 50 μm, and a residual volatile content of 3% by weight.

(Example 3)
A suspension obtained by dissolving 0.1 g of ZONYL® UR (manufactured by DuPont) in 100 g of N-methyl-2-pyrrolidone was applied to a stainless steel plate (Ra = 0.8 nm, Rz = 52 nm) at 120 ° C. Dry for 5 minutes. It was washed with dryness, N-methyl-2-pyrrolidone and acetone to remove excess ZONYL (R) UR. The polymer solution A obtained in Reference Example 3 was coated with a bar coater so as to have a coating thickness of 300 μm, and dried at 120 ° C. for 10 minutes and 280 ° C. for 3 minutes to obtain a molded body having a film thickness of 55 μm. The obtained molded product had an Ra of 0.8 nm, an Rz of 50 nm, and a residual volatile content of 6% by weight.

Example 4
A molded body having a film thickness of 53 μm was obtained under the same conditions as in Example 1 except that the polymer solution used was polymer D. The obtained molded product had an Ra of 0.9 nm, an Rz of 53 nm, and a residual volatile content of 7% by weight.

(Example 5)
A suspension of 0.1 g of ZONYL® UR (manufactured by DuPont) dissolved in 100 g of N-methyl-2-pyrrolidone was applied to a stainless microlens mold (lens height 15 μm, period 50 μm), 120 ° C. For 5 minutes. It was washed with dryness, N-methyl-2-pyrrolidone and acetone to remove excess ZONYL (R) UR.

  25% by weight of a copolymer consisting of 61.5% by weight of methyl methacrylate unit, 0.5% by weight of methacrylic acid unit, 19% by weight of styrene unit and 19% by weight of glutaric anhydride unit was dissolved in 2-butanone, It was coated with a bar coater to a coating thickness of 200 μm, dried at 50 ° C. for 5 minutes, 80 ° C. for 10 minutes, 120 ° C. for 10 minutes, and 170 ° C. for 10 minutes to obtain a microlens array with a film thickness of 50 μm. The obtained molded article had a lens height of 14.8 μm, a period of 51 μm, and a residual volatile content of 5% by weight.

(Example 6)
A suspension of 0.1 g of ZONYL® UR (manufactured by DuPont) dissolved in 100 g of N-methyl-2-pyrrolidone was applied to a stainless microlens mold (lens height 15 μm, period 50 μm), 120 ° C. For 5 minutes. It was washed with dryness, N-methyl-2-pyrrolidone and acetone to remove excess ZONYL (R) UR.

  A copolymer consisting of 72% by weight of methyl methacrylate unit and 28% by weight of glutaric anhydride unit was dissolved in 2-butanone by 25% by weight and coated with a bar coater to a coating thickness of 200 μm, at 50 ° C. for 5 minutes. And dried at 80 ° C. for 10 minutes, 120 ° C. for 10 minutes, and 170 ° C. for 10 minutes to obtain a microlens array having a film thickness of 50 μm. The obtained molded article had a lens height of 15.0 μm, a period of 49 μm, and a residual volatile content of 5% by weight.

(Comparative Example 1)
The polymer solution A obtained in Reference Example 1 was applied to a microlens array mold and dried under the same conditions as in Example 1 except that ZONYL® UR (manufactured by DuPont) was not applied. The molded product adhered firmly to the microlens array mold and could not be peeled off.

(Comparative Example 2)
The polymer solution A obtained in Reference Example 1 under the same conditions as in Example 1 except that the drying step was peeled off from the microlens array mold at 120 ° C for 45 minutes, dried at 120 ° C for 15 minutes, and 280 ° C for 3 minutes. Was applied to a microlens array mold and dried. The obtained molded body had a lens height of 9.3 μm and a period of 47 μm. The residual volatile content of the molded article immediately after peeling was 54% by weight.

Claims (13)

A solution containing a polymer is applied onto a support provided with a predetermined surface shape, dried on the support until the volatile component of the solution is 10% by weight or less, and then the surface on the support. A method for producing a polymer molded body in which a molded body having a transferred shape is peeled off. The height according to claim 1, wherein Rz2 is 90% to 110% of Rz1, where Rz1 is the maximum height of the surface shape of the support and Rz2 is the maximum height of the surface shape of the molded body. A method for producing a molecular compact. The manufacturing method of the polymer molded object of Claim 1 or 2 whose surface shape is a shape which has a predetermined period. When the period in a specific direction of the surface shape of the support is L1, and the period of the surface shape of the molded body in the direction corresponding to the specific direction is L2, L2 is a value of 90% to 110% of L1. The manufacturing method of the polymer molded object of Claim 3 which is these. Ra2 is a value of 90% to 110% of Ra1 when Ra1 is the arithmetic average height of the surface shape of the support and Ra2 is the arithmetic average height of the surface shape of the molded body. The manufacturing method of the polymer molded object in any one of. The manufacturing method of the polymer molded object in any one of Claims 1-5 which performs drying by two or more processes from which temperature differs. The manufacturing method of the polymer molded object in any one of Claims 1-6 which peels, after heating at the temperature higher than the boiling point of the solvent contained in a solution. The method for producing a polymer molded body according to any one of claims 1 to 7, wherein drying is performed under a reduced pressure atmosphere of 0.1 MPa or less. The manufacturing method of the polymer molded object in any one of Claims 1-8 which contains the peeling agent on the surface of the side in which the surface shape of the support body was provided, and / or in the solution. The polymer is at least one polymer selected from the group consisting of polyimide, polyamide, polyetherketone, polyetheretherketone, polycarbonate, cyclic polyolefin, acrylic, polyester, fluororesin, and polyethersulfone. The manufacturing method of the polymer molded object in any one of -9. As a polymer, a structural unit represented by chemical formula (I), (II), (III) or (IV) and represented by chemical formula (I), (II) (III) and (IV) The manufacturing method of the polymer molded object in any one of Claims 1-10 which satisfy | fills following Formula (1)-(3), when the molar fraction of each is l, m, n, and o .
50 <l + m + n ≦ 100 (1)
0 ≦ l, m, n, o ≦ 100 (2)
0 ≦ o ≦ 50 (3)

R ₁ : a group having at least one 5-membered ring, 6-membered ring or 7-membered ring R ₂ : any aromatic group X: hydrogen, halogen or a hydrocarbon group having 1 to 3 carbon atoms

R ₃ : —CF ₃ , —CCl ₃ , —CBr ₃ , —OH, —F, —Cl, —OCH ₃ (however, structural units having these groups may be mixed in the molecule)
R ₄ : any aromatic group

_{R 5: -SO 2 -, -} O -, - CH 2 -, - C (CF 3) 2 - group selected from or _{-SO 2, -, - O -} , - CH 2 -, - C (CF 3 ) Aromatic group containing one or more groups selected from ₂ − R ₆ : Arbitrary aromatic group X: Hydrogen, halogen or hydrocarbon group having 1 to 3 carbon atoms

R ₇ : Arbitrary aromatic group R ₈ : Arbitrary aromatic group X: Hydrogen, halogen or hydrocarbon group polymer having 1 to 3 carbon atoms The manufacturing method of the polymer molded object in any one of Claims 1-11 whose light transmittance of the light of all the wavelengths from 450 nm to 700 nm of a polymer is 80% or more. The optical molded object manufactured by the manufacturing method in any one of Claims 1-12.