KR101382442B1 - Thermoplastic resin composition for being pattern-formed by mold and patterned products - Google Patents

Abstract

A thermoplastic resin composition for a piecetamper member having excellent imprintability and transferability during thermal imprinting, and a resin molded body or a transparent resin molded body obtained by thermal imprinting using the resin composition and transferring various patterns.

The thermoplastic resin composition for a piece of tamper member has a high molecular weight thermoplastic resin (A) having a weight average molecular weight of 60 to 1.8 million and a molecular weight distribution coefficient (Mk / Mn) = 1.5 to 5, and a weight average molecular weight of 1 to 200,000. A molecular weight distribution diagram of the resin composition containing a low molecular weight thermoplastic resin (B) having a distribution coefficient (MV / Mn) of 1.1 to 5, which is represented by [JPC method], is [the molecular weight distribution peak amount of the resin (A)]: [Resin ( A peak molecular weight distribution peak of B)] = 7 to 9: 3 to 1 is achieved.

Description

Thermoplastic resin composition for piece tamper member and its molded object {THERMOPLASTIC RESIN COMPOSITION FOR BEING PATTERN-FORMED BY MOLD AND PATTERNED PRODUCTS}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition for use in a piece of tamper member, and more particularly, to thermal nanoimprint molding or injection compression molding. A piece tamper having excellent imprintability and transferability in transferring microstructures of various patterns in a thermocompression transfer process such as an extrusion process. It relates to a thermoplastic resin composition for a member.

The present invention also relates to a resin molded article obtained by transferring a microstructure of various patterns using a thermoplastic resin composition having such characteristics as a piece tamper member and useful as a functional part in various industrial fields. In addition, the present invention also provides a transparent resin molded article which is particularly excellent in optical transparency among thermoplastic resin compositions exhibiting such characteristics, and in which a microstructure useful as various optical parts (or optical elements) is transferred. It is about.

In recent years, the microstructures applied to the surface of device members such as optoelectro devices, optical devices, semiconductor devices, display devices, and optical recording media tend to be further miniaturized and / or densified. As various tip materials in such a technical area, for example, a semiconductor device having an ultra-fine structure, a semiconductor laser, a light emitting diode, a light receiving element, an optical connector, and an optical switch switches, diffraction grating optical filters, wavelength optical conversion elements, optical waveguide wavelength filters, optical waveguides as optical wiring for portable PCs , Optical or optoelectronic devices (or nonlinear optoelectronic devices), such as gain equalization filters used in amplifiers of wavelength-separated multiple communication systems. Etc. can be mentioned.

In addition, even in a pick-up lens for an optical disc such as a CD or a DVD, which is widely used as a recording medium for music or video, bit information in sub-micron units to be imprinted on a disc, which is a next-generation recording medium. ), Plastic aspherical objective lenses, etc., which play an important role in optical pick-up optical devices for reading laser beams, can also be said to be leading materials in the same technical field. In addition, optical recording media such as CD and DVD are optically transparent resin molded articles having microstructures transferred onto their surfaces. PS polymer resin etc. are used. In addition, these media are required to have higher density, and optical pickup lenses for reading the information signals are also required to be more highly detailed. Moreover, as a thermoplastic resin of an optical recording medium, conversion from PMA resin to cyclic polyolefin resin is also considered.

In order to form microstructures of sub-micron units or nano units on the surface of various device members, photolithography miniaturization technology, which has been developed as a manufacturing technology for semiconductor devices such as LSI, contributes enormously as a base technology. Has been. Various patterns such as lines, spaces, dots, and holes of the uneven microstructures formed on the surface of the device member are required to be formed more finely.

In order to cope with such a fine high technology area, a thermal nano-imprint transfer method is expected to replace lithography transfer as a base technology. In this thermal nanoimprint transfer method, a thermoplastic resin, which is a piece stamper member, is subjected to high-speed injection into a stamper material (or a mold) in which an ultrafine structure is applied under thermal melting. Or by pressing or stamping to transfer the ultrafine structure to the surface of the piece tamper member.

In addition, this nanoimprint transfer is said to be a transfer technique that has developed a hot emboss transfer technique, which is conventionally well known in optical disc production and the like, and has significantly increased the transfer resolution. That is, in the conventional hot embossing process, for example, a poly carbon substrate is heated to a temperature higher than the glass transition temperature and pressed by a nickel mold. A pattern of about 0.5 μm can be transferred to the substrate. On the other hand, if the irregularities of the mold are made small, the nanoimprint enables the ultra fine pattern transfer of 100 nm or less, especially several 10 nm or less. Therefore, it can be said that the introduction of nanoimprint technology is expected as a next-generation transcription technology that significantly reduces the transfer resolution.

In the expected nanoimprint transfer, the microstructure of the stamper (or mold) is transferred to the piecetamper material with high precision, and the piecetamper member is easily released from the stamper material. It is an important technical factor. As the stamper material, SiC, quartz, silicon and Si (semiconductor), and TA (a mold for processing micro plastic optical parts of a pickup lens for CD, CD) are used. In addition, in molds for display device antireflective materials such as mobile phones and PDAs, microimprint molds (fine metal molds) for nanoimprints having a fine pattern of 0.1 μm or less on substrate materials are used.

As a piece tamper member in the nanoimprint transfer method, [Patent Document 1] describes various organic polymer members. [Patent Document 1] also discloses an optical waveguide comprising an organic polymer such as fluorinated polyimide, polysilane, polymethylmethacrylate, polycarbonate, etc. as a piece of tamper member. There has been proposed an optical waveguide-type WMD combiner in which a grating portion, which has been micro-machined by a hot embossing method, is formed in a branching portion.

Further, in [Patent Document 2], a plurality of grooves having a depth of 0.5 to 500 µm are formed by hot pressing on a material sheet (piece tamper member) having a thickness of 1 to 5 mm made of a thermoplastic resin. A microstructured resin plate has been proposed in which the alignment pitch of the grooves is 1.5 times or more of the groove depth. As a press method for transferring the microstructure, a hot press method of 150 to 180 degrees and a press pressure of 40 to 60 mg / cm ² is described. In addition, the resin plate to which the microstructure has been transferred by the heat press method, which has good light transmittance and is easy to mix light diffusing materials, polymethyl methacrylate, methyl methacrylate-styrene, polycarbonate, polystyrene Phototransparent thermoplastic resins, such as (polystyrene), are described.

[Patent Document 3] also describes a method for producing a microstructure in which a fine pattern applied to a stamper is transferred onto a thermoplastic resin substrate having a thickness of 100 to 200 µm such as polycarbonate, polystyrene, and acrylic resin.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2005-331582

[Patent Document 2] Japanese Unexamined Patent Publication No. 2001-353777

[Patent Document 3] Japanese Unexamined Patent Publication No. 2003-094445

The technical challenges required for industrial members of inorganic and organic are increasingly in the direction of high performance and multifunction. Optical recording devices such as CDs and DVDs, light emitting diodes, light receiving devices, optical connectors, optical switches, diffraction grating optical filters, wavelength optical conversion devices, optical waveguide wavelength filters and other optical devices and optoelectronic devices may have dots, It is widely used as a structural member having various functions by forming ultrafine structures of various patterns such as lines and spaces.

The size of various patterns composed of dots, lines, and spaces applied to such nanotech structural members is usually 600 nm or less, depending on the function required as the structural member, and is 10 nm to 100 nm when a nano size region is required. . Therefore, the piecetamper member used for thermal nanoimprint in the ultrafine size region is required to be able to efficiently transfer with high precision without generating a transfer defect.

An object of the present invention is to provide a thermoplastic resin composition for a piece tamper member having excellent imprintability and transferability when transferring a microstructure of various patterns. Moreover, the objective of this invention is providing the resin molded object which transferred the microstructure of various patterns using the thermoplastic resin composition for piece tamper members which has such a characteristic as a piece tamper member. In addition, an object of the present invention is to provide a transparent resin molded article excellent in various optical properties and / or various optoelectronic properties by transferring a fine structure of various patterns, particularly to a thermoplastic resin composition for a piece tamper member having excellent light transparency.

The thermoplastic resin for piece-tamper member has excellent flexibility in thermocompression transfer, and after thermal imprinting, it is smoothly released or peeled off from the stamper material, and the pattern of the microstructure is clear. "Imprintability" which is formed with high precision and is stable is calculated | required. In addition, in the thermoplastic resin for piece tamper member, transfer is not unevenly distributed in the two-dimensional direction (the plane direction of the transfer surface) with respect to various patterns of the microstructure to be transferred, and in the three-dimensional direction (depth or height direction). "Transferability" which does not generate a transfer defect is calculated | required. In order to prevent such ubiquitous, defect, etc., it is preferable that the thermoplastic resin for piecetamper members has sufficient flexibility (or fluidity | liquidity) at the time of thermocompression transfer. Moreover, it is preferable that the thermoplastic resin for a piece stamper member is low heat fusion property with respect to a stamper material for the release or peeling from a stamper material.

Here, as a result of earnestly examining the said subject, this inventor contains the thermoplastic resin component (A) of a predetermined | prescribed high molecular weight body, and the thermoplastic resin component (B) of a predetermined | prescribed low molecular weight body. The thermoplastic resin composition was found to be excellent in "imprintability" and "transferability", and came to complete this invention.

<Thermoplastic Resin Composition for Piece Tamper Member Provided by the Present Invention>

The thermoplastic resin composition for a piece tamper member of the present invention can exhibit uniform thermocompression property under a heat flow state with respect to a pattern applied to a stamper material. Furthermore, after imprinting, good "imprintability" can be exerted smoothly from the microstructure pattern applied to the stamper material. Moreover, the thermoplastic resin composition for a piece tamper member of this invention can exhibit the outstanding "transcription property" which does not produce the transfer unevenness of a two-dimensional direction and the transfer defect of a three-dimensional direction in a transfer surface.

The thermoplastic resin composition for piece tamper members of the present invention has a weight average molecular weight (MV) by the PPC method in the range of 60 to 1.8 million (MW), and a molecular weight distribution coefficient (MV / Mn) = 1.5 to 5 in the range. Low molecular weight thermoplastic resin component (B) having a high molecular weight thermoplastic resin component (A) and a weight average molecular weight (MV) in the range of 1 to 200,000 and a molecular weight distribution coefficient (MV / Mn) = 1.1 to 5 It is characterized by containing.

In the thermoplastic resin composition for a piece of tamper member of the present invention, the molecular weight distribution diagram shown in the drawings on the basis of the weight by the BP method is characterized by a high molecular weight thermoplastic resin component (A) and a low molecular weight thermoplastic resin component (B). [The molecular weight distribution peak amount of the said thermoplastic resin (A)]: [The molecular weight distribution peak amount of the said thermoplastic resin (B)] = 7-9: The characteristic quantity ratio pattern of 3-1 (as an example, [ 1)).

The thermoplastic resin composition for a piecetamper member of the present invention, which forms a characteristic ratio pattern diagram of the high molecular weight resin component (A) and the low molecular weight resin component (B), has excellent "imprintability" during thermal imprinting. Excellent "transcription" can be exhibited.

<Resin molded article to which microstructure provided by this invention is transferred>

According to the present invention, excellent "imprintability" and "transcriptional property" are exhibited in the thermocompression transfer process such as thermal nanoimprint molding or injection compression molding, even for a piecetamper member resin surface having a thickness ranging from 50 nm to 500 µm. It is possible to provide a resin molded body of microstructure transfer, which can be free of transfer patterns in the two-dimensional direction, transfer defects in the three-dimensional direction, and the like.

<Functional transparent resin molded article for microstructure transfer provided by the present invention>

Moreover, according to this invention, the thermoplastic resin composition for piece tamper members containing a high molecular weight thermoplastic resin component (A) and a low molecular weight thermoplastic resin component (B) is a resin composition (or visible light transmittance of at least 85% which is excellent in light transparency). In the case of the above-described resin composition), a transparent resin molded body obtained by transferring a microstructure of various patterns by a thermocompression transfer process such as thermal nanoimprint molding or injection compression molding is provided.

Since the transparent resin molded article provided by the present invention is excellent in light transparency, it can exhibit various optical characteristics and / or various nonlinear optoelectronic characteristics with respect to the transferred microstructure, and thus is useful as various optical elements or various nonlinear optoelectronic devices. .

Since the molecular weight distribution coefficient (Mb / Mn) of the high molecular weight thermoplastic resin component (A) and the low molecular weight thermoplastic resin component (B) contained is very sharp, the thermoplastic resin composition for a piecetamper member of the present invention is a stamper. In the thermoplastic resin composition for members, there are two distinct peaks in the molecular weight distribution diagram obtained through the PPC method, and [the molecular weight distribution peak amount of the high molecular weight thermoplastic resin component (A)]: [molecular weight distribution of the low molecular weight thermoplastic resin component (B) Peak amount] = 7 to 9: 3 to 1.

Since the thermoplastic resin composition for a piece tamper member of the present invention has appropriate fluidity at the time of thermal imprinting, it has excellent "transferability" that does not cause transfer localization in the plane direction of the transfer surface or transfer defect in the vertical direction. Equipped. Moreover, it is excellent in the "imprintability" which can peel easily from a stamper material after thermal imprinting, and does not produce deformation of resin. Therefore, the resin molded body which was thermally imprinted using the thermoplastic resin composition for piecetamper members of this invention turns into the high precision molded object by which the microstructure of the stamper material was transferred with high precision.

[Example]

In a thermocompression transfer process such as thermal nanoimprint molding or injection compression molding, a thermoplastic resin composition for a piece tamper member according to the present invention which transfers microstructures of various patterns and a functional resin molded body to which the microstructures are transferred are carried out. An example is further demonstrated below.

The thermoplastic resin composition for a piece tamper member of the present invention contains a "high molecular weight thermoplastic resin component (A)" and a "low molecular weight thermoplastic resin component (B)" each having a very sharp molecular weight distribution coefficient (Mk / Mn). It is characterized by being.

The thermoplastic resin composition for a piece tamper member of the present invention has a high molecular weight thermoplastic resin having a weight average molecular weight (MV) in the range of 60 to 1.8 million and a molecular weight distribution coefficient (MV / Mn) = 1.5 to 5 by the WP method. The resin component (A) and the low molecular weight thermoplastic resin component (B) in which the weight average molecular weight (MV) is in the range of 1 to 200,000 and the molecular weight distribution coefficient (MV / Mn) = 1.1 to 5 are contained.

The "high molecular weight thermoplastic resin component (A)" has a weight average molecular weight (MV) by the PPC method in the range of 60 to 1.8 million, preferably 70 to 1.5 million, and more preferably 90 to 1.3 million. Moreover, although it exists in the range of the molecular weight distribution coefficient (Mk / Mn) = 1.5-5, Preferably it is the range of 1.5-4, More preferably, it is 1.5-3. When the weight average molecular weight and the molecular weight distribution coefficient of the high molecular weight thermoplastic resin component (A) deviate from a predetermined range, the peelability (or release property) during transfer after thermal imprinting is inferior.

The "low molecular weight thermoplastic resin component (B)" has a weight average molecular weight (MV) by the PPC method in the range of 1 to 200,000, preferably 3 to 150,000, and more preferably 5 to 100,000. Moreover, although the molecular weight distribution coefficient (Mk / Mn) is in the range of 1.1-5, Preferably it is the range of 1.1-4, More preferably, it is 1.1-3. When the weight average molecular weight and molecular weight distribution coefficient of the low molecular weight thermoplastic resin component (B) deviate from a predetermined range, the fluidity during thermal imprinting is poor, and transfer ubiquitous in the two-dimensional direction and transfer defects in the three-dimensional direction are likely to occur.

In addition, as shown in FIG. 1, in the thermoplastic resin composition for piece tamper members of the present invention, two distinct peaks are shown in the molecular weight distribution shown by the WP method by weight. The two peaks are peaks derived from the high molecular weight thermoplastic resin component (A) and peaks derived from the low molecular weight thermoplastic resin (B). The two peaks have a ratio of [molecular weight distribution peak amount of high molecular weight thermoplastic resin component (A)]: [molecular weight distribution peak amount of low molecular weight thermoplastic resin (B)] = 7 to 9: 3 to 1. More preferably, this ratio is 7.5-8.5: 2.5-1.5. If this ratio deviates from a predetermined range, the fluidity | liquidity at the time of thermal imprint and the peelability after thermal imprint will fall.

<Preparation of thermoplastic resin composition for piece tamper members provided by the present invention>

The thermoplastic resin composition for a piece of tamper member of the present invention has a "high molecular weight thermoplastic resin component (A)" and "low molecular weight thermoplastic resin (B) having a predetermined weight average molecular weight and a predetermined molecular weight distribution coefficient (Mk / Mn). ) Can be appropriately prepared.

The measurement of the molecular weight and the molecular weight distribution of the resin is measured by dissolving the resin under a predetermined temperature in an eluent developed in a PCC column under a predetermined temperature. For example, acrylic resins, such as PMMA, melt | dissolve at the temperature of 25-50 degreeC using THF as an eluent. Moreover, it melt | dissolves in polyolefin resins, such as PP and POE, at normal temperature of 100-145 degree using orthodichlorobenzene as an eluent. In the former case, a high speed PCC device (e.g., HLC-8220PCC manufactured by Tosoh Corporation) is used, and in the latter case, a high temperature PCC device (e.g., HLC-8121PCC / HT manufactured by Tosso Corporation) is used. ).

Resin which can be used as the thermoplastic resin composition for piece tamper members of this invention is excellent in transparency, for example, styrene resin (91%, 110 degree | times), PMA (93%, 107 degree | times), PEMA etc. Acrylic resin, polylactic acid (poly (PLA)), cyclic polyolefin (90-91%, 100-163 degree), polycarbonate (PC, 90%, 145-150 degree) is mentioned. The numerical values described in the parentheses are visible light transmittance% and Tg ° C, respectively. The molded article using these resins can be suitably used as various optical elements or various nonlinear optoelectronic devices in accordance with the optical properties of the resin.

Moreover, as resin which can be used for this invention, polyolefin resin, such as PE and PPS, acrylonitrile / styrene resin (AS), acrylonitrile / butadiene / styrene copolymer resin acrylonitrile / butadiene / styrene 共重合 樹脂; ABS, polyvinyl chloride (PCC), polyvinylidene chloride, polyamide (PA) such as nylon resin, ultra high molecular weight polyethylene (PHHPE), polybutylene terephthalate (polybutylene terephthalate) , 40-60 degrees), polyethylene terephthalate (PET, 70 degrees), modified polyphenylene ether (PE, 150 degrees), polyacetal (POM), polyphenylene sulfide (polyphenylene sulfide) PS, polyether ether ketone (PEE, 143 degrees), polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkylvinylether copolymer (PF), etc. Fluorocarbon resin, liquid crystal polymer (LCP), polyetherimide (PEI), polysulfone resin (po lysulfone series (PSV, 190 degrees), polyamide imide (PAI, 289 degrees), polyarylate (PAR, 193 degrees), polysulfone (PSF), polyethersulfone (PES, 225 degrees), epoxy Acrylate (epoxyacrylate), urethane acrylate (urethaneacrylate), polyester acrylate, polymethylpentene (PMP), polyarylate resin and the like. In addition, the numerical value described in the said parentheses represents Tg degreeC. These resins may be used alone or in combination of two or more thereof.

The glass transition temperature (Tg) of the thermoplastic resin used in the present invention is preferably from 40 to 290 degrees in view of handling properties in thermocompression transfer processes such as thermal nanoimprint molding or injection compression molding. More preferably, it is 60-210 degree.

The thermosetting resin composition for piecetamper members of this invention can contain the other additive mentioned later in the range which does not impair the imprintability or the transferability effect. When it contains an additive, the total amount of a high molecular weight thermoplastic resin component (A) and a low molecular weight thermoplastic resin component (B) is 95-100 mass parts with respect to 100 mass parts of thermoplastic resin compositions for piecetamper members, More preferably, it is 98 mass parts or more.

Moreover, as for the compounding quantity of a high molecular weight thermoplastic resin component (A) and a low molecular weight thermoplastic resin component (B), the low molecular weight thermoplastic resin component (B) is 12.5- per 100 mass parts of high molecular weight thermoplastic resin component (A). Although it may contain in the range of 37.5 mass parts, Especially from a viewpoint of improving the flexibility (or fluidity | liquidity) of resin, Preferably it is the range of 18.8-31.3 mass parts.

<Microstructure Transfer Method by Thermocompression Transfer Process>

The thermoplastic resin composition for a piece tamper member of the present invention can be used as a piece tamper member. As for the thickness of a piece tamper member, 50 nm-500 micrometers are preferable from a viewpoint of "imprintability" and "transferability." In a thermal transfer process such as thermal nanoimprint molding or injection compression molding, a resin molded body to which a microstructure pattern has been transferred is obtained by imprinting a stamper material having a predetermined microstructure pattern on a piece of taper member having a thickness of 50 nm to 500 μm. Can be. By this method, for example, a resin molded body having a convex or concave dot having a diameter of 50 to 1500 nm or a convex or concave line having a pitch of 60 nm to 2 μm can be produced. The depth of the concave portion or the height of the convex portion may be an ultrafine structure in the range of 20 nm to 3 μm.

The imprint temperature (TV) in the thermal transfer process such as thermal nanoimprint molding or injection compression molding is a temperature slightly higher than the glass transition temperature (Tg) of the thermoplastic resin composition for piecetamper members. Preferably, by setting it as Tg + 10 <T << Tg + 50, the outstanding "imprintability" and "transcriptional property" which the thermoplastic resin composition for a piece tamper member is equipped can be utilized effectively.

Examples of the thermal transfer process include extrusion molding, blow molding, vacuum molding, and the like, in addition to thermal imprint molding and injection compression molding.

In order to make the thermoplastic resin composition for a piece tamper member into a piece of taper member with a thickness of 50 nm-500 micrometers, the method of heat-melting and shape | molding the thermoplastic resin composition for piece tamper members, and the solution which melt | dissolved in the solvent are applied to various coating machines. There is a method of forming a sheet into a sheet and drying to remove the solvent. As a coating machine which can be used, a spin coat, a dip coat, a die coat, a gravure coat, etc. are mentioned. The solvent is selected in consideration of the solubility with the resin. For example, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as acetic acid ester, alcohols such as isobutanol and butanol, toluene, Aromatic type | system | groups, such as xylene, an ether type, a glycol type | system | group, etc. are mentioned.

<Use of functional resin molded article transferred to microstructure>

The resin molded body and the transparent resin molded body of the present invention are provided with irregularities of about 20 nm to 3 μm on the resin surface. The resin molded article and the transparent resin molded article of the present invention include a diffraction grating optical filter, a wavelength light conversion element, a polarizing film, a holographic diffuser, an optical waveguide wavelength filter, an optical waveguide as an optical wiring for a portable PC, and a transmission-bladed blade. Diffraction gratings, diffraction gratings for optical pickups, wavelength separation filters, gain equalization filters and polarization conversion elements used in amplifiers of wavelength separation multiple communication systems, fresnel lenses (solar condensing lenses) , OHP magnified projection lenses, microlens arrays, various aspherical lenses, injection molded aspherical lenses (field lenses, relay lenses), and fresnel sheets used for transmissive screens ( Lenticular sheet for vertical diffusion, optical recording medium such as CD or DVD, LED diffusion film, LED light collecting plate, fuel cell separator Grounds, external diagnostic chip, chip cell culture, organ substitute member (臟器 代用 部 材) may be used in various industrial fields such as.

<Other additives>

Furthermore, in the thermoplastic resin composition for piece tamper members according to the present invention, a known additive, for example, a heat stabilizer, is provided so long as it does not impair "imprintability" and "transferability" as the piece tamper member. Dispersants, preservatives, water repellents, viscosity modifiers, thixotropic agents, surface tension modifiers, antifoaming agents劑), antioxidants, antistatic agents, near-infrared absorbers, ultraviolet absorbers, antibacterial and mildew agents, fragrances, fluorescent agents ) May be suitably blended.

Although an Example demonstrates this invention below, this invention is not limited to these Examples.

(Reference Examples 1 to 6)

In order to prepare the thermoplastic resin composition for piece tamper members according to the present invention using PMA resin, which is a representative thermoplastic resin, as the high molecular weight thermoplastic resin component (A), (MW) = 800,000 and 1.13 million, low molecular weight resin component (B) As (MW) = 50,000, 100,000, and 140,000 PMMA were prepared (Reference Examples 1 to 5). In addition, as a comparative example, a low molecular weight and a small low molecular weight having a large molecular weight distribution coefficient of 140,000 and a large molecular weight distribution coefficient (MV / Mn) were prepared (Reference Example 6).

Reference Example 1 [High molecular weight thermoplastic resin component (A); (Ｍｗ) = 800,000 PMMA]

In a 1-liter four-neck flask equipped with a thermometer and a nitrogen inlet tube, 900 parts by mass of ion-exchanged water and an emulsifier dodecylbenzenesulfonate ammonium ) 1.5 parts by mass was added, and 0.5 parts by mass of ammonium peroxodisulfate (APS) was added while maintaining the temperature at 76 to 78 degrees. Subsequently, 100 mass parts of methyl methacrylate (MMA) and 1 mass part of emulsifiers dodecylbenzenesulfonic acid ammonium salt were dripped over 30 minutes. Furthermore, after hold | maintaining for 30 minutes at 76-78 degree, it heated up to 85 degree and maintained at that temperature for 1.5 hours. The polymerization rate of the obtained emulsion (E-1) was about 100%, and the weight average molecular weight was 84.4 million and the molecular weight distribution was 3.2 as a result of WPC measurement.

Reference Example 2 [High molecular weight thermoplastic resin component (A); (Ｍｗ) = 1.13 million PPM

Into a one-liter four-necked flask equipped with a thermometer and a nitrogen inlet tube, 900 parts by mass of ion-exchanged water and 1.5 parts by mass of ammonium dodecylbenzenesulfonic acid salt were added, and 0.25 parts by weight of ASP was added while maintaining the temperature at 76 to 78 degrees. . Then, 100 mass parts of MMA and 1 mass part of emulsifiers dodecylbenzenesulfonic acid ammonium salt were dripped over 30 minutes. Furthermore, after maintaining 30 minutes at 76-78 degree, it heated up to 85 degree and maintained at that temperature for 1.5 hours. The polymerization rate of the obtained emulsion (E-2) was about 100%, the weight average molecular weight was 1.130,000 and the molecular weight distribution was 3.0 as a result of WPC measurement.

Reference Example 3 [Low Molecular Weight Thermoplastic Resin Component (B); (Ｍｗ) = 50,000 PMMAA]

Into a one-liter four-necked flask equipped with a thermometer and a nitrogen inlet tube, 900 parts by mass of ion-exchanged water and 1.5 parts by mass of ammonium dodecylbenzenesulfonic acid salt were added, and 0.5 parts by weight of ASP was added while maintaining the temperature at 76 to 78 degrees. It was. Subsequently, 100 parts by weight of MMA, 5 parts by weight of N-dodecylmercaptan (NDM), and 1 part by weight of an ammonium dodecylbenzenesulfonate ammonium salt were added dropwise over 30 minutes, and further maintained at 76 to 78 degrees for 30 minutes, followed by 85 degrees. It heated up to and maintained the temperature for 1.5 hours. The polymerization rate of the obtained emulsion (E-3) was about 100%, the weight average molecular weight was 5.70,000 and the molecular weight distribution was 2.31 as a result of WPC measurement.

Reference Example 4 [Low molecular weight thermoplastic resin component (B); (Ｍｗ) = 100,000 PMMA]

Into a one-liter four-necked flask equipped with a thermometer and a nitrogen inlet tube, 900 parts by mass of ion-exchanged water and 1.5 parts by mass of ammonium dodecylbenzenesulfonic acid salt were added, and 0.5 parts by weight of ASP was added while maintaining the temperature at 76 to 78 degrees. . Subsequently, 100 parts by weight of MMA, 0.5 part by weight of NMD and 1 part by mass of the ammonium dodecylbenzenesulfonic acid ammonium salt were added dropwise over 30 minutes. Furthermore, after maintaining for 30 minutes at 76-78 degree, it heated up to 85 degree and maintained the temperature for 1.5 hours. The polymerization rate of the obtained emulsion (E-4) was about 100%, the weight average molecular weight was 100,000 and the molecular weight distribution was 2.7 as a result of WPC measurement.

Reference Example 5 [Low molecular weight thermoplastic resin component (B); (Ｍｗ) = 140,000 PMMA]

Into a one-liter four-necked flask equipped with a thermometer and a nitrogen inlet tube, 900 parts by mass of ion-exchanged water and 1.5 parts by weight of ammonium dodecylbenzenesulfonate emulsifier were added, and the temperature was raised to 85 ° C. 0.5 parts by weight was added. Subsequently, while maintaining the temperature at 76 to 78 degrees, 100 parts by weight of methyl methacrylate (MMA), 0.2 part by weight of N-dodecyl mercaptan (NMD) and 1 part by weight of an ammonium dodecylbenzenesulfonate ammonium salt were added dropwise over 30 minutes. Drop polymerization was carried out. Furthermore, after maintaining for 30 minutes at 76-78 degree, it heated up to 85 degree and maintained the temperature for 1.5 hours. The polymerization rate of the obtained emulsion (E-5) was about 100%, the weight average molecular weight was 13.9 million and the molecular weight distribution was 4.1 as a result of WPC measurement.

(Reference Example 6) [(MW) = 140,000 PMA, molecular weight distribution coefficient (MW) / (MN) >> 5]

Into a 1-liter four-necked flask equipped with a thermometer and a nitrogen inlet tube, 1.5 parts by mass of 900 parts by mass of ion-exchanged water emulsifier dodecylbenzenesulfonate ammonium salt was added, and 0.5 parts by weight of ASP was added while maintaining the temperature at 76 to 78 degrees. Subsequently, 100 weight part of MMA, 1 weight part of NMD, and 1 weight part of emulsifiers dodecylbenzenesulfonic acid ammonium salt were dripped over 30 minutes, and the drop polymerization was carried out. Furthermore, after maintaining for 30 minutes at 76-78 degree, it heated up to 85 degree and maintained the temperature for 1.5 hours. The polymerization rate of the obtained emulsion (E-6) was about 100%, the weight average molecular weight was 140,000 and the molecular weight distribution was 10.7 as a result of WPC measurement.

The glass transition temperatures (Tg) of the PMA resins prepared in Reference Examples 1 to 6 were all about 110 degrees (differential scanning calorimeter: Differential Scanning Calorimeter).

[Preparation of thermoplastic resin composition for piece tamper member and piece tamper member according to the present invention]

E-1-6 obtained by the reference examples 1-6 were each dried by spray dry, and particle | grains resin S-1-6 were obtained. Furthermore, S-1-6 were melt | dissolved in methyl ethyl ketone, and the resin solution SS-1-6 of 10 weight% of resin powder, respectively was obtained. Moreover, the visible light transmittance of resin S-1 and S-3 was 90% in all.

A resin sheet, that is, a "piece tamper member" was produced using resin solutions S-1 to 6 using a spin coater 1H-DX2 manufactured by Mica Corporation. The sheet film thickness was adjusted with the resin melt viscosity and the rotation speed of the coater (for example, the resin sheet of 10 micrometers in thickness was obtained on the conditions of 30 P of solution and 1200 rpm).

[Manufacture of Stamper Material]

A mold was produced by applying resist coating, silica irradiation, developing, and etching on a silica base. The produced mold used the pattern which the circular dot type, the pattern of diameter 10, 5, 2, and 1 micron regularly arranged, and the uneven | corrugated pattern of 0.15-1.5 micrometers of line width, and 300 nm of depth were used.

Condition: Resist: NV-22 (manufactured by Sumitomo Chemical)

Mold: 2inch diameter of about 5cm of SiO ₂ treatment on Si base about 5cm

ＥＢ ： ＥＬＩＯＮＩＸ ＥＬＳ7500M used

Etching: CHF ₃ gas (50SCCM, 2.0Pas, 100W, 15min )

Etching (removal of remaining resist): O ₂ gas (5 Pas, 100 W)

Mold surface treatment: Daikin Industries, Inc. 1% solution (Perfluorohexane Solv.)

[Investigation of Thermocompression Transfer Process 1; Evaluation of Transcription

The above-mentioned resin S-1 is used as a piece tamper member, and the stamper material having the above-described microstructure is transferred using Nm0401 manufactured by Myungchang Pore Co., Ltd. and ST50 manufactured by Toshiba Machine Co., Ltd. as a thermal transfer apparatus. It was. The transcription conditions and the transcription results are shown in [Table 1]. As a suitable transfer condition from the result of [Table 1], temperature 130 degree | times, weight 10 ｋN, transfer time 300 second shall be selected.

[Table 1]

Temperature (degrees)

Weighting (kN)
Time (sec)
Transcription Result
130

2
300
x Warrior Difficulty
130

7
300
x Warrior Difficulty
130

10
300
o Transferable
130

10
60
x Warrior Difficulty
130

10
500
o Transferable
130

15
300
o Transferable
130

19
300
x Warrior Difficulty
110

10
300
x Warrior Difficulty
150

10
300
o Transferable
180

10
300
x Warrior Difficulty

[Review of Thermocompression Transfer Process 2; Imprintability, Transferability Evaluation]

With the above apparatus, the transfer test was carried out by changing the type and thickness of the resin under conditions of a temperature of 130 degrees, a weight of 10 kN and a transfer time of 300 seconds. Peelability from the stamper material after thermal imprinting, transfer unevenness and transfer defect of the piece stamper material were evaluated from the SEM image image and the AF image image. The results are shown in Table 2. As is clearly shown in Table 2, the resins of S-1 to 6 cause poor peelability or resin deformation and do not have good imprintability and transferability.

[Table 2]

Resin
(Piece tamper member)

Film thickness
(μm)
Transcription Result
S-1
S-1
S-1

4.5
10
50
x: No peeling defect, resin deformation
x: No peeling defect, resin deformation
x: No peeling defect, resin deformation
S-2

10
x: No peeling defect, resin deformation
S-3

10
xx: resin does not stick to mold
S-3

45
xx: Peeling defect, resin deformation
S-4

10
xx: Peeling defect, resin deformation
S-5

10
x: No peeling defect, resin deformation
S-6

10
xx: resin does not stick to mold

(Examples 1-3 and Comparative Examples 1-7)

[Evaluation of Imprintability and Transferability of a Piece Tamper Member According to the Present Invention]

Preparation of resin compositions E-1 to E-3 and H1 to H7 which changed the mixing ratio of S-1 (high molecular weight thermoplastic resin component (A)) and S-3 (low molecular weight thermoplastic resin component (B)) Then, a sheet-shaped piece of taper member having a thickness of 10 µm was all prepared, and thermal imprinting was performed under conditions of a temperature of 130 degrees, a weight of 10 Hz and a transfer time of 300 seconds. As the transfer, Nm0401 manufactured by Myeong Poong Co., Ltd. and ST50 manufactured by Toshiba Machine Co., Ltd. were used. "Imprintability" and "transcriptional property" were evaluated from the SEM photograph image and the AFM image image. The results are shown in [Table 3].

Table 4 shows the results of evaluation of the transfer accuracy at the time of thermal imprinting of the used piecetamper member from the AF photograph shown in FIG. 6. From Tables 3 and 4, it can be clearly seen that the resin composition for the piece tamper member of the present invention has excellent "imprintability" and "transferability" during thermal imprinting.

[Table 3]

High molecular weight (A) / low molecular weight (B)
Compounding mass ratio; Resin S-1: Resin S-3

[Imprintability] of Thermocompression Transfer Process
And evaluation of [transcriptionality]
(Examples 1-3)
E1 9: 1
E2 8: 2
E3 7: 3


o: No peeling defect, no resin deformation
o: No peeling defect, no resin deformation
o: No peeling defect, no resin deformation
(Comparative Examples 1-7)
H1 10: 0
H2 6: 4
H3 5: 5
H4 4: 6
H5 3: 7
H6 2: 8
H7 1: 9


x: No peeling defect, resin deformation
x: No peeling defect, resin deformation
xx: Peeling defect, resin deformation
xx: Peeling defect, resin deformation
xx: Peeling defect, resin deformation
xx: Peeling defect, resin deformation
xx: resin does not stick to mold

[Table 4]

Name of sample

Pitch width (nm)
Groove depth (nm)
Tilt angle of the pattern in degrees
Mold

410
309
85
H1

600
303
85
E2

403
294
84
H2

403
294
80

A SE photograph image and an AFM photograph image of a piece stamper member after a piece stamper member is made using the thermoplastic resin composition for a piece stamper member of the present invention and thermally imprinted with a stamper material having a parallel line shape and a dot pattern. 2 to 6 are shown. Fig. 2 (a), Fig. 3 (a), Fig. 4 (a), and (b) Fig. 5 (a) and Fig. 6 (c) are all examples 2 (E2). Fig. 2 (b), Fig. 3 (b), Fig. 4 (c), Fig. 5 (c), and Fig. 6 (d) are all comparative examples. (H2) is a photograph.

2 to 6 clearly show that the thermoplastic resin composition for a piece tamper member of the present invention is excellent in peelability, and thus there is no deformation of the resin, and excellent in fluidity of the resin, so that there is no transfer localization or transfer defect. .

The resin composition for a piece tamper member of the present invention has excellent "imprintability" and "transcriptional property" in thermocompression transfer processes such as thermal nanoimprint molding and injection compression molding. The resin molded article having a fine structure includes a diffraction grating optical filter, a wavelength light conversion element, a polarizing film, an optical waveguide type wavelength filter, an optical waveguide as an optical wiring for a portable PC, a transmission brazed diffraction grating, a diffraction grating of an optical pickup section, Optical components such as wavelength separation filter, Fresnel lens (solar condenser lens, OHP magnifying lens), microlens array, various aspherical lens, injection molded aspherical lens (field lens, relay lens), nonlinear optoelectronic parts, CD , Optical recording media such as DVD, LED diffusion film, LED light collecting plate, separator for fuel cell, external diagnosis , Cell culture may be used or the like chips, long substitute member.

1 shows a molecular weight distribution diagram obtained by a PCC in the thermoplastic resin composition for a piece tamper member of the present invention.

Fig. 2 shows a SEM image of a piece stamper member after a piece stamper member is made using the thermoplastic resin composition for a piece tamper member of the present invention and thermally imprinted with a parallel line stamper. In particular, the end of the imprint is shown.

Fig. 3 shows a SEM image of a piece stamper member after a piece stamper member is made using the thermoplastic resin composition for a piece stamper member of the present invention and thermally imprinted with a stamp pattern material of a dot pattern.

Fig. 4 shows a SEM image of a piece stamper member after a piece stamper member is made using the thermoplastic resin composition for a piece tamper member of the present invention and thermally imprinted with a parallel line stamper.

Fig. 5 shows an AF photographic image of a piece stamper member after a piece stamper member is made using the thermoplastic resin composition for a piece stamper member of the present invention and thermally imprinted with a parallel line stamper.

Fig. 6 shows an AF photographic image of a cross section of a piece stamper member after a piece stamper member is made using the thermoplastic resin composition for a piece stamper member of the present invention and thermally imprinted with a parallel line stamper.

Claims (7)

The weight average molecular weight (MV) by GPC method is in the range of 60-1.8 million, and the molecular weight distribution coefficient (MV / Mn) = 1.5-5 is high. The molecular weight thermoplastic resin component (A) and the weight average molecular weight (MV) by the GP method are in the range of 1-200,000, and the molecular weight distribution coefficient (MV / Mn) = 1.1-5 As a thermoplastic resin composition (B) containing a low molecular weight thermoplastic resin component (B) in the present invention, In the thermoplastic resin composition, the molecular weight distribution diagram based on the weight by the PPC method is [molecular weight distribution peak of the high molecular weight thermoplastic resin (A)]: [molecular weight distribution peak of the low molecular weight thermoplastic resin (B)] = 7 to 9: 3 Is -1, The high molecular weight thermoplastic resin component (A) and the low molecular weight thermoplastic resin component (B) include polyolefin resins, styrene resins, acrylic resins, and polylactic acid (poly PLA). , Cyclic polyolefin, polycarbonate, polybutylene terephthalate (PPT), polyethylene terephthalate (PET), modified polyphenylene ether (PE), polyether For piece tamper member, characterized in that any one or any two or more selected from the group of polyether ether ketone, polyarylate (PAA), polyethersulfone (PES) (被 stamper 部 材 用) Thermoplastic resin composition. delete The method according to claim 1, The high molecular weight thermoplastic resin (A) and the low molecular weight thermoplastic resin (B) have a visible light transmittance of 85% or more, characterized in that the thermoplastic resin composition for a piece tamper member. The microstructure of a stamper material in the piecestamp member resin in the range of 50 nm-500 micrometers of thickness formed at the time of thermal imprinting using the thermoplastic resin composition for piecestamp members of Claim 1 Is a resin molded product characterized by being transferred. A microstructure of a stamper material is transferred to a piece of tamper member resin having a thickness of 50 nm to 500 µm formed during thermal imprinting using the thermoplastic resin composition for piece stamper member of claim 3. 5. The method of claim 4, The microstructure of the stamper material is selected from a convex or concave dot having a diameter of 50 to 1500 nm, a convex or concave line having a pitch of 60 nm to 2 μm, and a pattern group of space. It is any single pattern or any combination of 2 or more types, and the depth or height of a pattern exists in 20 nm-3 micrometers, The resin molded object characterized by the above-mentioned. The method of claim 5, The single structure or any two or more combination patterns selected from the group consisting of concave or concave dots having a microstructure of the stamper material having a diameter of 50 to 1500 nm, convex or concave lines and spaces having a pitch of 60 to 2 μm. And the depth or height of the pattern is in the range of 20 nm to 3 μm.

Images