JP2010105210A - Method of forming pattern - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin layered body for very easily performing an photo (nano)imprint of a submicron pattern, continuously and in a high speed, even when thickness of the photosensitive resin layer is thin, and a method of forming a pattern using the same. <P>SOLUTION: The pattern is formed by an imprint process including a press step in which a mold 5 and a photosensitive resin layer 2 are pressed by using a heating body set at 35-130°C, exposure step in which the photosensitive resin layer is cured by exposure, and disengagement step in which the mold is disengaged. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pattern forming method using an imprint method.

  At present, the fine pattern processing in the manufacturing process of LSI or the like is mainly performed by lithography technology using light. This technique includes the steps of applying a photosensitive resist on a substrate to be processed, exposing, and developing to form a cured pattern. In the lithography technology, an LSI having a minimum line width of 100 nm has been manufactured using an ArF excimer laser (193 nm) by shortening the wavelength of an exposure light source. Although further miniaturization technology is expected to continue in the future, however, higher exposure equipment costs, lower throughput, and erosion of the developer into the cured pattern by the developer, will reduce the adhesion of the cured pattern. It is a problem.

A (nano) imprint technique is expected as a solution to this problem. This is a method of transferring a pattern by pressing a mold (mold) on which a fine pattern is formed against a resin layer on a substrate using an imprint apparatus, and high-throughput and fine pattern formation can be easily performed. Furthermore, the photo (nano) imprint technique forms a pattern by using a photosensitive resin and irradiating light from above the mold.
As a conventional general optical (nano) imprint technique, a liquid resin is used as a photosensitive resin, and it is applied to a substrate by spin coating and presses a mold. However, this method has a problem that it is difficult to adapt to a large area, and the mold release property between the cured photosensitive resin and the mold is poor. As a method capable of overcoming such a problem, attention has been paid to a technique using a photosensitive resin laminate in which a photosensitive resin layer is formed on a support. Patent Document 1 discloses a pattern forming method characterized by performing optical nanoimprint including pressing of a mold and light irradiation on a photosensitive resin laminate.

The photo (nano) imprint technology using the photosensitive resin laminate has the feature that it is easy to obtain excellent releasability compared to the case of using a liquid photosensitive resin, while the viscosity of the photosensitive resin layer Therefore, the desired pattern cannot be easily obtained without being sufficiently embedded in the mold. In particular, in order to sufficiently embed in a mold having a submicron width and a submicron depth, it is necessary to press the mold for a long time by applying a high pressure, and it is difficult to form a continuous pattern suitable for industrial production. In particular, when the thickness of the photosensitive resin layer was as thin as 5 μm or less, the tendency was remarkable.
JP 2007-73696 A

  The object of the present invention is to overcome the above-mentioned problems, and to perform submicron pattern light (nano) imprinting extremely easily and continuously even when the photosensitive resin layer is thin. An object of the present invention is to provide a pattern forming method using an imprint method.

The above object can be achieved by the following configuration of the present invention.
[1]
An imprint process including a pressing step of pressing the mold and the photosensitive resin layer using a heating body set at a temperature of 35 to 130 ° C., an exposure step of curing the photosensitive resin layer by exposure, and a release step of removing the mold A method of forming a pattern by
[2]
The pattern forming method according to [1], including a step of laminating a photosensitive resin layer on a substrate before the pressing step.
[3]
The method for forming the pattern according to [1] or [2], wherein the pressing step is a step of pressing the photosensitive resin layer and the mold using a roller.
[4]
The pattern forming method according to [3], wherein the rotation speed of the roller is 3 to 50 mm / sec.
[5]
The pattern forming method according to [3] or [4], wherein the pressure applied by the roller is 0.1 kN to 10 kN.
[6]
The pattern formation method according to any one of [1] to [5], wherein the photosensitive resin layer has a thickness of 0.1 to 7 μm.
[7]
The pattern formation method according to any one of [1] to [6], wherein the photosensitive resin layer has a viscosity at 20 ° C. of 10 ⁶ to 10 ¹¹ Pa · s.
[8]
The pattern forming method according to any one of [1] to [7], wherein the photosensitive resin layer includes a) radical polymerization type or b) chemical amplification type photosensitive resin.

  According to the present invention, even when the photosensitive resin layer is thin, it is possible to obtain an effect that it is possible to perform sub-micron pattern light (nano) imprinting very easily at a high speed continuously. .

Hereinafter, the present invention will be specifically described.
<UV imprint process>
The pattern forming method of the present invention includes a light (nano) imprint technique, a pressing step of pressing a photosensitive resin layer and a mold using a surface plate or a roller, an exposure step of curing the photosensitive resin layer by exposure, and a mold. A detachment process is included.
The pattern formation method by the imprint method using the photosensitive resin laminated body is demonstrated using FIGS. FIG. 1 and FIG. 2 are examples of a pattern forming method in a batch transfer method or a step-and-repeat method. 3 to 8 are examples of the pattern forming method in the roller type transfer method. 1 to 8 show examples of pattern forming methods, and the present invention is not limited to these methods.

-Lamination process In the case of the photosensitive resin laminated body comprised from the support body 1-photosensitive resin layer 2-protective film, the surface of the peeled photosensitive resin layer 2 and the base material 3 are peeled, peeling a protective film. Laminate with a laminator. At this time, it is preferable that the substrate is heated (preheating) immediately before the laminating step. The photosensitive resin layer in a laminator hot rolls and pressed at a pressure of about 0.1~1MPa the substrate while heating at about 70~130 ℃ (1~10kgf / cm ² or so). In the laminating step, it may be performed under reduced pressure using a vacuum laminator or the like for the purpose of suppressing micro air from entering between the base material and the photosensitive resin layer during lamination (vacuum or lamination under reduced pressure). Before lamination, a liquid such as water may be placed on the substrate and laminated (wet lamination). It is preferable to apply the lamination or wet lamination under vacuum or reduced pressure when the photosensitive resin layer itself is thin or when the unevenness of the surface of the substrate is larger than the thickness of the photosensitive resin layer.

-Peeling process A support body is peeled from the photosensitive resin layer. In this case, you may peel automatically using an auto peeler.
-Pressing process The mold and the photosensitive resin layer are pressed using a heating body set at a temperature of 35 to 130 ° C.
Examples of the imprint apparatus include a batch transfer system, a step-and-repeat system, and a roller transfer system (Nanoimprint Application Examples Chapter 3, Section 5, Information Technology Corporation).

  The batch transfer method is a method in which the mold is pressed against the photosensitive resin layer and pressed and held by two upper and lower surface plates to transfer the pattern ((3) in FIG. 1, (3) in FIG. 2). ). The step-and-repeat method is a method of transferring a pattern over the entire surface of the photosensitive resin layer by repeating batch transfer in order. The roller transfer method is a method in which a mold pattern is continuously transferred to a photosensitive resin layer using a roller. There are mainly three types of roller transfer systems. A) A method of transferring a pattern on the roller surface to the photosensitive resin layer by applying a load to the roller and applying pressure to the photosensitive resin layer using a roller having a fine pattern provided in advance on the roller surface (see FIG. 3). (3)) and B) a method in which a fine pattern is provided on a flat mold, and the flat mold is pressed onto the photosensitive resin layer by a roller to transfer the pattern to the photosensitive resin layer ((3 in FIG. 4). ) Or (3) in FIG. 5 and C) Using a flexible flat plate-shaped mold attached so as to be wound around the roller, a load is applied to the roller to pressurize the photosensitive resin layer. It is a method ((3) of FIG. 6) which transfers a pattern to the photosensitive resin layer.

In the pressing step, it is preferable to use a roller transfer type imprint apparatus, taking advantage of the film-like properties of the photosensitive resin laminate, so that high productivity can be easily obtained in a roll-to-roll production process. Among the roller transfer systems, the above A) is particularly preferable.
In the case of the roller transfer system, in addition to the upper roll related to the transfer, the lower roll has a press roll, but a stage may be provided between the upper roll and the press roll ((3) in FIG. 4 (3), FIG. 5 (3), FIG. 6 (3), FIG. 7 (1), and FIG. 8 (1)). In this case, it is preferable to heat this stage from the viewpoint of ensuring sufficient embedding of the photosensitive resin layer in the mold.

The temperature of the stage is preferably 40 ° C to 100 ° C, more preferably 40 to 80 ° C.
The mold can be made of various materials, but generally Si, SiC, Ni, Ta, GC (glassy carbon), quartz, polydimethylsiloxane (PDMS), or the like is used. In the optical nanoimprint process, a transparent mold is required and quartz is often used because light can be irradiated from the upper surface of the mold while the mold is pressurized. In addition, since it can be wound around a curved surface, a resin mold such as PDMS has recently been used.
The pressure applied by the mold is preferably 0.1 to 10 kN. It is 0.1 kN or more from the viewpoint of ensuring sufficient embedding property of the photosensitive resin layer in the mold, and 10 kN or less from the viewpoint of obtaining good releasability. More preferably, it is 0.1-5 kN, More preferably, it is 0.1-3 kN.

The heating body should just be what heats the photosensitive resin layer. For example, the said surface plate, a roller, a mold, and a stage can be used as a heating body. The temperature of the heating body is 35 to 130 ° C. The temperature is 35 ° C. or higher from the viewpoint of ensuring sufficient embedding property of the photosensitive resin layer in the mold, and 130 ° C. or lower from the viewpoint of preventing the photosensitive resin layer from being deteriorated by heat and obtaining good releasability. Preferably, it is 40-100 degreeC. More preferably, it is 40-80 degreeC. More preferably, the temperature of the mold is within the above temperature range.
In the case of the roller transfer method, the rotation speed of the roller is preferably 3 to 50 mm / second. It is 3 mm / second or more from the viewpoint of productivity, and 50 mm / second or less from the viewpoint of ensuring sufficient embedding of the photosensitive resin layer in the mold. More preferably, it is 5-40 mm / sec, More preferably, it is 10-40 mm / sec, Especially preferably, it is 10-30 mm / sec.

-Exposure process Next, the photosensitive resin layer is hardened by exposure of actinic rays.
As a light source of actinic light, a conventionally known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, or the like that effectively radiates ultraviolet rays, visible light, or the like is used. . Alternatively, a direct imaging exposure method using a semiconductor excitation solid laser, a semiconductor laser, an ultrahigh pressure mercury lamp, or the like may be used.

The exposure is performed before pressing the mold against the photosensitive resin layer (pressing process) and before the releasing process of separating the mold from the photosensitive resin layer ((4) in FIG. 1, (10) in FIG. 4), 10 in (4) in FIG. 5, 10 in (4) in FIG. 6, 10 in FIG. 7 (2), or immediately after the separation process (within 10 minutes) ((5) in FIG. 2, FIG. 3) It is preferable to carry out the process in 9 of (4), 9 in (4) of FIG. 6, and (4) of FIG.
The position of the light source is a batch exposure method or a step-and-repeat method, and when a mold transparent to actinic rays is used, it is preferably provided on the surface opposite to the surface on which the mold pattern is formed. . When using a mold that is opaque to actinic rays, it is preferably provided at a position adjacent to the press by a surface plate.

In the case of the roll transfer method, it is provided immediately below the roller on which the photosensitive resin layer is pressed against the roller (10 in FIG. 3 (4), 10 in FIG. 4 (4), 10 in FIG. 5 (4), FIG. 6 of (4), 10 of FIG. 7 (2), and provided at the position adjacent to the roller where the pressure on the photosensitive resin is released (9 of FIG. 3 of FIG. 4, FIG. 4). 9 of (4), 9 of (4) of FIG. 5, 9 of (4) of FIG. 6, 9 of (2) of FIG.
Although the exposure amount depends on the sensitivity of the photosensitive resin layer, it is usually about 1 to 300 mJ / cm ² . Preferably, a 1~150mJ / cm ^2, more preferably 1 to 100 mJ / cm ^2.

-Separation process As described in detail in the above-described exposure process, the separation process for removing the mold may be performed before the exposure process or after the exposure process.
-Residual film removal process After the mold detachment process, the residual film of the photosensitive resin layer may exist in the part where the convex part of the mold was pressed on the base material. In the case of removing the remaining film, a process for removing the remaining film as represented by dry etching is required.
Using a mold with UV-shielding material attached to the surface of the convex part as a mold, and making the photosensitive resin composition alkaline developable, residual film removal (wet etching) by conventional alkali development is possible. Become.

As an example of a method for forming a pattern, a laminating process can be performed before the pressing process (FIGS. 1 to 6). In this case, after the photosensitive resin layer and the base material are laminated together, the photosensitive resin layer and the mold are pressed, and the pattern is transferred to the photosensitive resin layer.
Moreover, in this invention, you may perform a lamination process after a press process (FIG. 7, FIG. 8). That is, a photosensitive resin layer and a mold are pressed in advance, a pattern is transferred to the photosensitive resin layer, and then the photosensitive resin layer and the substrate are bonded together by lamination. The exposure process may be performed before or after the laminating process. The exposure process is preferably performed before the laminating process from the viewpoint that the pattern after transfer is easily held accurately after laminating.

In the pattern forming method, the obtained pattern may be used as it is as a structure such as a device, or the obtained pattern may be used as a resist.
When used as a resist, for example, an etching process such as dry etching or wet etching, a plating process, a sputtering process, a vapor deposition process, a process of embedding various materials in a concave portion of a pattern, or the like can be provided.
Furthermore, in the pattern forming method, a step of finally removing the pattern from the substrate can be provided. In this step, an aqueous alkali solution such as sodium hydroxide, potassium hydroxide or an organic amine compound, a solvent, or the like can be used.

<Photosensitive resin laminate>
The photosensitive resin laminate includes a support and a photosensitive resin layer.
1) Support The support in the present invention may or may not transmit light. Specific examples of materials used for the support include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, poly Examples thereof include a methyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, a triacetyl cellulose film, and a polypropylene film. As the support, one stretched as necessary can be used.

Alternatively, an organic material or inorganic material previously formed on the support by a technique such as coating or sputtering may be used.
The maximum cross-sectional height (Pt) of the cross-sectional curve of the support is preferably 2 μm or less. From the viewpoint of the smoothness of the surface of the pattern to be obtained, the maximum sectional height (Pt) of the sectional curve is preferably 2 μm or less. More preferably, it is 0.01 μm or more and 1.0 μm or less.
The maximum cross-sectional height (Pt) of the cross-sectional curve of the support is measured with a non-contact optical shape measuring apparatus, for example, MM3200 manufactured by Ryoka System Co., Ltd., referring to JIS B0601: '01. Can do.
The thinner support is advantageous in terms of economy, but a thickness of 10 to 100 μm is preferable because the strength needs to be maintained.

2) Photosensitive resin layer <Photosensitive resin composition>
The photosensitive resin layer used in the present invention is preferably a negative photosensitive resin composition. Among negative photosensitive resin compositions, a) radical polymerization type or b) chemical amplification type photosensitive resin composition is preferable, and more preferable is radical polymerization type photosensitivity because high exposure sensitivity is easily obtained. It is a resin composition.

The viscosity at 20 ° C. of the photosensitive resin layer is preferably 10 ⁶ to 10 ¹¹ Pa · s. And the dry film exuding of the photosensitive resin from the end face of the roll of the (edge Fusion) from the viewpoint of obtaining a good releasability of the photosensitive resin layer from the viewpoint of preventing molded 10 6 ^Pa · s or more, mold In order to obtain sufficient embedding of the photosensitive resin layer in the film, it is 10 ¹¹ or less. More preferably, it is 10 ⁷ to 10 ⁹ Pa · s. More preferably, it is 10 ⁷ to 10 ⁸ Pa · s.

In addition, the viscosity of the photosensitive resin layer here is the value measured as follows.
・ Sample: Thickness 3mm
Size 8mmΦ
Humidity adjustment before measurement: 23 ° C, 50% atmosphere, 48 hours ・ Measurement device: ARES 2KFRTN1-FCO (Rheometric Scientific)
-Measurement conditions: Temperature 20-70 ° C
Temperature increase rate 5 ℃ / min
Load 2kg
Atmosphere Nitrogen atmosphere
Frequency 0.015915-15.915Hz
Data acquisition to give 40% distortion

a) Radical polymerization type photosensitive resin composition The radical polymerization type photosensitive resin composition is flexible to contain a polymer compound, a photopolymerizable compound having an ethylenic double bond, and a photopolymerization initiator. It is preferable from the viewpoint that a photosensitive resin layer can be obtained.
-High molecular compound As a high molecular compound, the acrylic resin which copolymerized the (meth) acrylic-type monomer and the epoxy resin which copolymerized the epoxy-type monomer are mentioned, An acrylic resin is more preferable. Among acrylic resins, it is possible to remove a pattern with an alkaline solution before exposure or when patterning by exposure is unsuccessful, adhesion with a substrate, etc. From the viewpoint, it is preferable that a monomer having a carboxyl group in the side chain and a (meth) acrylic monomer are copolymerized.

Examples of the monomer having a carboxyl group in the side chain include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, and maleic acid half ester.
Examples of (meth) acrylic monomers include benzyl (meth) acrylate, alkyl (meth) acrylate, (meth) acrylate having a hydroxyl group in the side chain, and (meth) acrylic side chain. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, sec-butyl ( Examples include (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Examples of (meth) acrylate having a hydroxyl group in the side chain include 2-hydroxyethyl (meth) acrylate. , 2-hydroxypropyl (meth) acrylate, glycidyl mono (meta Examples of the (meth) acrylate having an alicyclic side chain include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentadienyl ( Examples include meth) acrylate, adamantyl (meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, phenyl (meth) acrylate, glycidyl methacrylate, styrene, and derivatives thereof.

  The polymer compound preferably has a weight average molecular weight of 3,000 to 100,000. The molecular weight is preferably 100,000 or less from the viewpoint of embedding the photosensitive resin layer in the mold in the pressing step, and preferably 3,000 or more from the viewpoint of maintaining a flexible film property. More preferably, it is 3,000 to 50,000. More preferably, it is 10,000 to 40,000. The molecular weight was measured by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M). , KF-806M, KF-802.5) in series, moving bed solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve with Shodex STANDARD SM-105 manufactured by Showa Denko KK) weight average molecular weight (polystyrene conversion) As required.

The polymer compound is preferably an alkali-soluble polymer. The alkali-soluble polymer preferably has a carboxyl group amount of 100 to 2,000 in terms of acid equivalent. An acid equivalent shows the mass of the linear polymer which has a 1 equivalent carboxyl group. 100 or more are preferable from a viewpoint of adhesiveness with a base material. 200 to 900 are more preferable, and 300 to 800 are more preferable. In addition, the measurement of an acid equivalent uses Hiranuma Sangyo Co., Ltd. Hiranuma automatic titration apparatus (COM-555), and is measured by a potentiometric titration method using 0.1 mol / L sodium hydroxide.
The alkali-soluble polymer is prepared by adding a radical polymerization initiator such as benzoyl peroxide or azobisisobutyronitrile to a solution obtained by diluting a mixture of the above various monomers with a solvent such as acetone, methyl ethyl ketone or isopropanol. It is preferable to synthesize by adding an appropriate amount and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, and emulsion polymerization may be used in addition to solution polymerization.

  In addition to the polymer compound described above, the photosensitive resin laminate can contain other alkali-soluble polymers in consideration of heat resistance, chemical resistance, and the like. Other alkali-soluble polymers include, for example, carboxymethyl cellulose, carboxyethyl cellulose, carboxypropyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, cellulose resin obtained by reacting a hydroxyl group of hydroxypropyl cellulose with a polybasic acid anhydride, cellulose phthalate acetate ( CAP) and novolac resins.

-Photopolymerizable compound having an ethylenic double bond Examples of the photopolymerizable compound having an ethylenic double bond include compounds having one or more methacrylic groups, acrylic groups or vinyl groups in the molecule. Examples of such compounds include succinic acid-modified pentaerythritol tri (meth) acrylate, phthalic acid-modified pentaerythritol tri (meth) acrylate, isophthalic acid-modified pentaerythritol tri (meth) acrylate, and terephthalic acid-modified pentaerythritol tri (meth) acrylate. ) Dimethacrylate of polyalkylene glycol obtained by adding an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide to both ends of acrylate and bisphenol A, and an average of 5 mol of bisphenol A to both ends of bisphenol A, respectively. Polyethylene glycol dimethacrylate (NK ester BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol Rudi (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylo- Rupropanetri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri Glycidyl ether tertri (meth) acrylate, bisphenol A diglycidyl ether terdi (meth) acrylate, and β-hydroxypropyl-β ′-(acrylo Ilyloxy) propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyalkylene glycol (meth) acrylate, and polypropylene glycol mono (meth) acrylate.

-Photopolymerization initiator The photopolymerization initiator is not particularly limited as long as it has sensitivity to ultraviolet rays or visible light.

  Specific examples of the photopolymerization initiator include thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2-chlorothioxanthone, 2,4,5-triarylimidazole dimers, such as 2- (o- Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis- (m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) ) -4,5-diphenylimidazole dimer. Also, p-aminophenyl ketones such as p-aminobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p′-bis (ethylamino) benzophenone, p, p ′ -Bis (dimethylamino) benzophenone [Michler's ketone], p, p'-bis (diethylamino) benzophenone, p, p'-bis (dibutylamino) benzophenone. Also, quinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin and benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and acridine compounds such as 9 -Phenylacridine, triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s -Triazine, 2,4-bis (trichloromethyl) -6-styryl- -Triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -S-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine, benzyldimethylketal, benzyldiethylketal, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2-methyl-2-morpholino-1- (4- (Methylthiophenyl) -propan-1-one.

  Other examples of photopolymerization initiators include N-arylglycine, mercaptotriazole derivatives, mercaptotetrazole derivatives, mercaptothiadiazole derivatives, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1 , 4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercapto Butyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydride) Kishiechiru) isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto -s- triazine, 2-(N, N-dibutylamino) -4,6-dimercapto -s- triazine. Examples of oxime ester compounds include oxime esters such as 1-phenyl-1,2-propanedione-2-O-benzoyloxime and 1-phenyl-1,2-propanedione-2- (O-ethoxy). Carbonyl) oxime and compounds described in JP-T-2004-534797 can be raised.

  The preferable content of each of the polymer compound, the photopolymerizable compound having an ethylenic double bond, and the photopolymerizable initiator in the photosensitive resin composition is as follows. 20 mass%-80 mass% are preferable with respect to 100 mass% of photosensitive resin compositions, and, as for content of a high molecular compound, 30 mass%-70 mass% are more preferable. From the viewpoint of obtaining good film properties, it is 20% by mass or more, and from the viewpoint of obtaining a flexible photosensitive resin layer, it is 80% by mass or less. The content of the photopolymerizable compound having an ethylenic double bond is preferably 10% by mass to 70% by mass and more preferably 20% by mass to 60% by mass with respect to 100% by mass of the photosensitive resin composition. From the viewpoint of obtaining sufficient sensitivity to actinic rays, it is 10% by mass or more, and from the viewpoint of obtaining good film properties, it is 70% by mass or less. The content of the photopolymerizable initiator is preferably 0.1% by mass to 20% by mass and more preferably 0.5% by mass to 15% by mass with respect to 100% by mass of the photosensitive resin composition. From the viewpoint of obtaining sufficient sensitivity to actinic rays, it is 0.1% by mass or more, and from the viewpoint of obtaining good film properties, it is 20% by mass or less.

  The photosensitive resin composition may contain a plasticizer as necessary. Such plasticizers include phthalates such as diethyl phthalate, p-toluenesulfonamide, polypropylene glycol, polyethylene glycol monoalkyl ether, polyalkylene oxide-modified bisphenol A derivatives such as Examples include ethylene oxide adducts and propylene oxide adducts of bisphenol A. When the plasticizer is contained, the content is preferably 1% by mass or more and 20% by mass or less. From the viewpoint of obtaining a flexible photosensitive resin layer, it is 1% by mass or more, and from the viewpoint of obtaining good film properties, it is 20% by mass or less.

The photosensitive resin composition can contain a coupler component, for example, a silane coupling agent or a titanium coupling agent, if necessary. When the coupler component is contained, the content is preferably 0.1% by mass or more and 5% by mass or less.
If necessary, the photosensitive resin composition can contain a thermal radical generator having a one-hour half-life temperature of 120 ° C. or higher and 230 ° C. or lower. Thereby, higher heat resistance and chemical resistance can be obtained by heat treatment after pattern formation. The content in the photosensitive resin composition is preferably 0.01 to 2% by mass with respect to 100% by mass of the photosensitive resin composition. From the viewpoint of storage stability, the one-hour half-life temperature is preferably 120 ° C or higher, and more preferably 130 ° C or higher. Moreover, from a viewpoint of post-baking time, 230 degrees C or less is preferable and 220 degrees C or less is more preferable. Specific examples of such a thermal radical generator include perbutyl A, perhexa 22, perbutyl Z, perhexa V, perbutyl IF, perbutyl P, permill D, perhexa 25B, perbutyl C, perbutyl D, permenta H, perhexine 25B, per mill. P, perbutyl SM, perocta H, park mill H, perhexyl H, perbutyl H (manufactured by NOF Corporation).

If necessary, the photosensitive resin composition may contain a coloring substance. Examples of such coloring substances include leuco crystal violet, fluoran dye, fuchsin, phthalocyanine green, auramine base, paramadienta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green (Eizen manufactured by Hodogaya Chemical Co., Ltd.) (Registered Trademark) MALACHITE GREEN), Basic Blue 20, Diamond Green (Eizen (Registered Trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.).
It is preferable that the addition amount in the case of containing the said coloring substance contains 0.001-1 mass% in 100 mass% of photosensitive resin compositions. When the content is 0.001% by mass or more, the handleability is improved, and when the content is 1% by mass or less, the storage stability is improved.

  Moreover, in order to improve the thermal stability and storage stability of the photosensitive resin composition, a stabilizer can be added to the photosensitive resin composition. Examples of such stabilizers include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), diphenylnitrosamine. In addition, a compound in which propylene oxide is further added to both sides of polypropylene glycol with an average of 1 mol of propylene oxide added to both sides of bisphenol A, benzotriazole, carboxybenzotriazole, 1- (2-dialkylamino) carboxybenzotriazole, penta Mention may also be made of erythritol-3,5-di-tert-butyl-4-hydroxyphenylpropionic acid tetraester.

  The addition amount in the case of containing the stabilizer is preferably 0.01 to 3% by mass, more preferably 0.05 to 1% by mass in 100% by mass of the photosensitive resin composition. When the content is 0.01% by mass or more, storage stability is imparted to the photosensitive resin composition, and when the content is 3% by mass or less, the sensitivity is maintained.

b) Chemical amplification type photosensitive resin composition The chemical amplification type photosensitive resin composition contains an alkali-soluble resin having a phenolic hydroxyl group, a photoacid generator, a compound having a group capable of crosslinking by the action of an acid, and a plasticizer. It is preferable to do. Hereinafter, these will be described in order.
-Alkali-soluble resin having phenolic hydroxyl group Examples of the alkali-soluble resin having a phenolic hydroxyl group include novolak resins and polyhydroxystyrene resins.

  As the novolak resin, those conventionally used as a film-forming substance in a conventional positive photoresist composition can be used. The novolak resin can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter also simply referred to as “phenols”) and an aldehyde under an acid catalyst. Examples of the phenols used in this case include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3 , 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol The Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid are used as the acid catalyst. As this alkali-soluble novolak resin, those having a weight average molecular weight in the range of 2,000 to 20,000 obtained by cutting a low molecular region are preferable. From the viewpoint of the flexibility of the film, it is 2,000 or more, and from the viewpoint of obtaining good embedding in the mold, 20,000 or less is preferable.

  When considering the profile shape of the resist pattern, those obtained using a phenolic compound containing 30% by mass or more of m-cresol with respect to 100% by mass of the photosensitive resin composition, in particular, m-cresol Mixed phenol containing 55 to 75% by mass and containing 45 to 25% by mass of at least one selected from p-cresol, 2,5-xylenol and 3,5-xylenol as the remaining component What was obtained from the ionic compound is preferable.

  Examples of the polyhydroxystyrene resin include polyhydroxystyrene, modified polyhydroxystyrene, hydrogenated polyhydroxystyrene, copolymers of hydroxystyrene and styrene, (meth) acrylic acid ester, maleic acid ester, and the like. Examples of the modified polyhydroxystyrene include those obtained by reacting polyhydroxystyrene with a benzenesulfonyl chloride derivative, a naphthalenesulfonyl chloride derivative, a benzenecarbonyl chloride derivative, a naphthalenecarbonyl chloride derivative, etc. in the presence of a basic catalyst. It is done. Specific examples of the aforementioned sulfonyl chloride derivative and carbonyl chloride derivative include p-acetaminobenzenesulfonyl chloride, benzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, naphthylbenzenesulfonyl chloride, p-acetaminobenzenecarbonyl chloride, benzenecarbonyl chloride, Examples thereof include p-chlorobenzenecarbonyl chloride and naphthylbenzenecarbonyl chloride. In this case, the sulfonyl chloride derivative or the carbonyl chloride derivative is usually used in a proportion of 10 to 30 parts by weight, preferably 15 to 25 parts by weight, with respect to 100 parts by weight of polyhydroxystyrene. Such modified polyhydroxystyrene may have a weight average molecular weight in the range of 3,000 to 50,000, preferably 5,000 to 30,000. From the viewpoint of the flexibility of the film, it is 3,000 or more, and from the viewpoint of obtaining good embedding in the mold, 30,000 or less is preferable.

Hydrogenated polyhydroxystyrene is obtained by hydrogenating a part of the benzene ring of polyhydroxystyrene and a modified polyhydroxystyrene in which a part of the benzene ring is modified by a substituent. The weight average molecular weight of the hydrogenated polyhydroxystyrene is usually selected in the range of 3,000 to 30,000, preferably 5,000 to 25,000. From the viewpoint of mechanical properties and dry etching resistance, the weight average molecular weight is preferably 3,000 or more, and preferably 30,000 or less from the viewpoint of compatibility.
The alkali-soluble resin having a phenolic hydroxyl group is preferably blended in an amount of 20 to 90% by mass with respect to 100% by mass of the photosensitive resin composition. More preferably, it is 30-70 mass%. 20 mass% or more is preferable from a viewpoint of film property maintenance of the photosensitive resin layer, and 90 mass% or less is preferable from a viewpoint of sufficient embedding to a mold.

-Photoacid generator A photoacid generator is a compound which generates an acid directly or indirectly by light. Specifically, 2,4-bis (trichloromethyl) -6- [2- (2- Furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-Ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl] -s- Triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3 5-diethoxyphenyl) ethenyl] -s-to Liazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3 -Methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) ) -S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2- Lomo-4methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3 -Bromo-4methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4 , 6-Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-Methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl]- , 6-Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine ,

2- (3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4-trichloromethyl (piperonyl) -6-triazine, tris (1,3 -Dibromopropyl) -1,3,5-triazine, halogen-containing triazine compounds such as tris (2,3-dibromopropyl) -1,3,5-triazine and tris (2,3-dibromopropyl) isocyanurate Examples thereof include halogen-containing isocyanurate compounds.

  Further, as a photoacid generator, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6 -Dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, or a compound represented by the following general formula (I):

{Wherein R ³ represents a monovalent to trivalent organic group, R ⁴ represents a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group; and n is 1 A natural number of ~ 3 is shown. }.
Here, the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, a furyl group, Examples include aromatic heterocyclic groups such as thienyl groups. These may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like.

R ³ is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. In particular, in the compounds of formula (I), R ³ is an aromatic compound group, a compound wherein R ⁴ is a lower alkyl group is preferred. As the photoacid generator represented by the general formula (I), when n = 1, R ³ is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ⁴ is a methyl group Specifically, α- (methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- ( p-methoxyphenyl) acetonitrile.

  Examples of the photoacid generator include bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (2,4-dimethylphenylsulfonyl) diazomethane. Bissulfonyldiazomethanes; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate Nitrobenzyl derivatives such as pyrogallol trimesylate, pyrgallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromedium Sulfonic acid esters such as rusulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methylsulfonyloxyphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butyl) Onium salts such as (phenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate; benzoin tosylate, α -Benzoin tosylates such as methylbenzoin tosylate; other diphs Sulfonyl iodonium salts, triphenyl sulfonium salts, phenyl diazonium salts, benzyl carbonate and the like.

In particular, triazine compounds are preferably used because of their high performance as a photoacid generator and good solubility even when a solvent is used. Among these, the following general formula (II):

, A bromo-containing triazine compound, especially 2,4-bis-trichloromethyl-6- (3-bromo-4methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- ( 3-Bromo-4-methoxy) styryl-s-triazine and tris (2,3-dibromopropyl) isocyanurate can be preferably used.
The photoacid generator is 0.01 to 5% by mass, preferably 0.05 to 1% by mass, and more preferably 0.1 to 0.5% by mass with respect to 100% by mass of the photosensitive resin composition. Can be contained. 0.01 mass% or more is preferable from the viewpoint of sensitivity, and 5 mass% or less is preferable from the viewpoint of storage stability.

Compound having a group that crosslinks by the action of an acid As a compound having a group that crosslinks by the action of an acid, for example, a melamine resin, urea resin, guanamine resin, glycoluril-formaldehyde resin, succinamide-formaldehyde resin, An ethylene urea-formaldehyde resin can be used, and in particular, an alkoxymethylated amino resin such as an alkoxymethylated melamine resin or an alkoxymethylated urea resin can be suitably used. The alkoxymethylated amino resin, for example, reacts a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution with lower alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, and isopropyl alcohol. To form an ether, and then the reaction solution is cooled and precipitated. Specific examples of the alkoxymethylated amino resin include methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin, butoxymethylated melamine resin, methoxymethylated urea resin, ethoxymethylated urea resin, and propoxymethyl. And urea-oxygenated resin, butoxymethylated urea resin, and the like. The said alkoxymethylated amino resin can be used individually or in combination of 2 or more types. In particular, an alkoxymethylated melamine resin is preferable because a dimensional change amount of the resist pattern with respect to a change in radiation dose is small and a stable resist pattern can be formed. Among these, methoxymethylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin or butoxymethylated melamine resin is preferable.

Examples of the alkoxymethylated melamine resin include Nicarak MX-750, Nicarax MX-706, Nicarak MX-101, Nicarak MX-032, Nicarax MX-708, Nicarac MX-40, Nicarac MX-31, Nicarac MS-11, Nicarac MW -22, Nicarak MW-30, MW-30HM, MW-100LM, Nicarac MW-390 (all manufactured by Sanwa Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more species. MX-290 (manufactured by Sanwa Chemical Co., Ltd.) is exemplified as the alkoxymethylated urea resin.
The compound having a group that crosslinks by the action of an acid can be contained in an amount of 1 to 40% by mass, preferably 5 to 20% by mass with respect to 100% by mass of the photosensitive resin composition. The compound having a group that crosslinks by the action of an acid in the photosensitive resin composition is preferably 1% by mass or more from the viewpoint of sensitivity and etching resistance, and preferably 40% by mass or less from the viewpoint of storage stability.

Plasticizer Plasticizers include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri-n -Propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, polyethylene glycol polypropylene glycol block copolymer (also called pluronic type) and its dialkyl ether, monoalkyl Examples include ether.
Furthermore, a plasticizer represented by the following general formula (III) can be preferably used.

{Wherein R ¹ and R ² are an ethylene group or a propylene group, and R ¹ and R ² are different from each other, m1, n1, m2, and n2 are each 0 or more, and m1 + n1 + m2 + n2 is 2 to 30, and - ^{(O-R 1)} - and - ^{(O-R 2)} - repeating structure may be a block be a random, and, - ^(O-R 1) - And the repeating structure of-(O-R ² )-may be on the bisphenyl group side. }

The compound represented by the general formula (III) is synthesized by adding ethylene oxide or propylene oxide to both ends of bisphenol A. m1 + n1 + m2 + n2 is 30 or less in order to obtain sufficient sensitivity and adhesion, and is 2 or more from the viewpoint of compatibility in the photosensitive resin composition and an increase in viscosity. m1 + n1 + m2 + n2 is preferably 2 to 20 and more preferably 2 to 10 from the viewpoint of adhesion. Furthermore, from the viewpoints of adhesion and cohesiveness, R ³ is an ethylene group, R ⁴ is a propylene group, m1 + m2 is 0, and n1 + n2 is 2 to 10 and is represented by the general formula (III). Are more preferred.

Specific examples of the compound represented by the general formula (III) include Adecanol (trademark) SDX-1569 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 0, n1 = n2 = 1]. , Adekanol (TM) SDX-1570 ^{[R 1:} an ethylene group, ^{R 2:} a propylene group, m1 = m2 = 0, n1 = n2 = 3], Adekanol (TM) SDX-1571 ^{[R 1:} an ethylene group, ^{R 2} = Propylene group, m1 = m2 = 0, n1 = n2 = 5], Adecanol (trademark) SDX-479 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 5, n1 = n2 = 0] ( Asahi Denka Co., Ltd.)

Newpol ™ BP-23P [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 0, n1 = n2 = 1], Newpol ™ BP-3P [R ¹ : ethylene group, R ² : Propylene group, m1 = m2 = 0, n1 = n2 = 1.5], Newpol ™ BP-5P [R ¹ : Ethylene group, R ² : Propylene group, m1 = m2 = 0, n1 = n2 = 2.5], New Pole ™ BPE-20T [R ¹ = ethylene group, R ² = propylene group, m1 = m2 = 1, n1 = n2 = 0], New Pole ™ BPE-60 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 3, n1 = n2 = 0], Newpol ™ BPE-100 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 5 , N1 = n2 = 0], new Lumpur (TM) BPE-180 (all manufactured by Sanyo Chemical Industries (Ltd.)) ^{[R 1::} ethylene group, ^{R 2} a propylene group, m1 = m2 = 9, n1 = n2 = 0],

UNIOL (TM) DB-400 ^{[R 1:} an ethylene radical, ^{R 2:} a propylene group, m1 = m2 = 0, n1 = n2 = 1.5], UNIOL (TM) DAB-800 ^{[R 1:} an ethylene radical, R ^2: a propylene group, m1 = m2 = 6, n1 = n2 = 4.5, - (R 1 -O) - and - ^(R 2 -O) - random, UNIOL (TM) DA-350F ^{[R 1} : Ethylene group, R ² : propylene group, m1 = m2 = 1.1, n1 = n2 = 0], Uniol (trademark) DA-400 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 2 , N1 = n2 = 0], Uniol (trademark) DA-700 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 5, n1 = n2 = 0] (manufactured by NOF Corporation),

BA-P4U [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 0, n1 = n2 = 2] glycol, BA-P8 [R ¹ : ethylene group, R ² : propylene group, m1 = m2 = 0, n1 = n2 = 4] glycol (made by Nippon Emulsifier Co., Ltd.) and the like.
The content of the plasticizer is preferably 1% by mass or more and 40% by mass or less in 100% by mass of the photosensitive resin composition. 1 mass% or more is preferable from a viewpoint of the flexible film property maintenance of the photosensitive resin layer, and 40 mass% or less is preferable from a viewpoint of resin adhesiveness and adhesiveness. More preferably, it is 5 mass% or more and 30 weight% or less.
It is preferable that the weight average molecular weight of a plasticizer is 100-5000. It is 100 or more from the viewpoint of sublimation, and 5000 or less from the viewpoint of developability. More preferably, it is 100-3000.

<Method for producing photosensitive resin laminate>
The photosensitive resin layer of the photosensitive resin laminate can be formed by applying the photosensitive resin composition of the present embodiment in a liquid state on a support.
When coating the photosensitive resin composition on the support, if necessary, the coating solution is obtained by dissolving the photosensitive resin composition in a predetermined solvent to obtain a solution having a solid content of 5 to 60% by mass. It may be used as Examples of such solvents include methanol, ethanol, propanol, ethylene glycol, propylene glycol, octane, decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, toluene, xylene. , Tetramethylbenzene, N, N-dimethylformamide, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene Glycol mono Chill ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate , Organic solvents such as dipropylene glycol monomethyl ether acetate, or a mixed solvent thereof.

Examples of the coating method include a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, a reverse coater, and a bar coater. The solvent can be removed, for example, by heating. In this case, the heating temperature is preferably about 70 to 150 ° C., and the heating time is preferably about 5 to about 30 minutes.
The amount of the remaining organic solvent in the photosensitive resin layer thus formed is preferably 2% by mass or less from the viewpoint of preventing diffusion of the organic solvent in the subsequent step.
The thickness of the photosensitive resin layer is preferably 0.1 to 7 μm (100 to 7000 nm). 0.1 μm or more is preferable from the viewpoint that the photosensitive resin layer can be satisfactorily embedded in the mold during the pressing process, and 7 μm or less is preferable from the viewpoint of easy dry or wet etching in the remaining film removal process of the photosensitive resin layer. . More preferably, it is 0.1-5 micrometers, More preferably, it is 0.1-3 micrometers, Most preferably, it is 0.1-1 micrometer, Most preferably, it is 0.1-0.5 micrometer.

In the support and the photosensitive resin layer, the surface opposite to the support side of the photosensitive resin layer may be covered with a protective film as necessary.
Examples of the protective film include a polyethylene film, a polyethylene terephthalate film, a polypropylene film, a stretched polypropylene film (for example, E-200C manufactured by Oji Paper Co., Ltd.), and a release-treated polyethylene terephthalate film. The protective film is preferably a low fish eye film. Further, the adhesive force between the protective film and the photosensitive resin layer may be smaller than the adhesive force between the photosensitive resin layer and the support so that the protective film can be easily peeled from the photosensitive resin layer. preferable. The thickness of the protective film is preferably 10 to 100 μm.

Further, an intermediate layer such as a cushion layer, a gas barrier layer, a release agent layer, an adhesive layer, a light absorbing layer, etc., between the support and the photosensitive resin layer and / or between the photosensitive resin layer and the protective film. Alternatively, a protective layer may be further provided.
As the cushion layer, a thermoplastic resin is preferable. As the thermoplastic resin used for the cushion layer, a compound having a glass transition temperature equal to or lower than the roll temperature at the time of lamination is preferable, and specifically, a thermoplastic resin having a glass transition temperature of 10 ° C. or higher and 120 ° C. or lower is preferable. A thermoplastic resin having a glass transition temperature of 20 ° C. or higher and 100 ° C. or lower, particularly preferably 30 ° C. or higher and about 80 ° C. or lower is preferable. This is because the glass transition temperature is equal to or lower than the roll temperature at the time of lamination, so that the unevenness of the substrate surface is completely absorbed when the photosensitive layer is transferred onto the uneven substrate with heat and pressure (when laminating). This is because laminating can be performed in a state where there is no remaining bubble.

  Further, the glass transition temperature of the thermoplastic resin used in the cushion layer is preferably 10 ° C. or higher from the viewpoint of preventing the thermoplastic resin from protruding from the roll end surface when stored in a roll form as the photosensitive resin laminate. More preferably, it is 20 degreeC or more, More preferably, it is 30 degreeC or more.

  Examples of the thermoplastic resin having a glass transition temperature of 120 ° C. or lower include polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylate esters or saponified products thereof, and polyvinyl chloride. , Vinyl chloride copolymers such as vinyl chloride and vinyl acetate and saponified products thereof, polyvinylidene chloride, vinylidene chloride copolymers, polystyrene, styrene copolymers such as styrene and (meth) acrylic acid esters or saponified products thereof , Polyvinyltoluene, vinyltoluene copolymer such as vinyltoluene and (meth) acrylic acid ester or saponified product thereof, poly (meth) acrylic acid ester, (meth) acrylic acid such as butyl (meth) acrylate and vinyl acetate Ester copolymer, vinyl acetate It is preferable to select at least one thermoplastic resin such as a copolymer, nylon, copolymer nylon, N-alkoxymethylated nylon, polyamide resin such as N-dimethylaminated nylon. A thermoplastic resin having a glass transition temperature of 120 ° C. or lower and 10 ° C. or higher can be used as described in (edited by the Japan Plastics Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, issued on October 25, 1968). .

The content of the thermoplastic resin is preferably 50 to 100% by mass, particularly 65 to 100% by mass, in 100% by mass of the cushion layer.
In addition to the thermoplastic resin described above, various plasticizers compatible with the thermoplastic resin may be added to the cushion layer to lower the substantial glass transition temperature. In order to adjust the adhesion between the cushion layer and the gas barrier layer described later, additives such as various polymers, supercooling substances, adhesion improvers or interfaces within a range where the substantial glass transition temperature does not exceed 120 ° C. An activator or a release agent can be added in the range of 5 to 50% by mass. More preferably, it is 35 mass% or less.

Examples of the plasticizer include phthalates such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and acetyl tricitrate tri-n-. Examples include propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and phthalates. Phthalate esters include dibutyl phthalate.
In addition, polyalkylene glycols such as polyethylene glycol and polypropylene glycol and polyalkylene glycol methyl ethers can be added.

The thickness of the cushion layer is preferably 10 μm or more. The reason for this is that when the thickness of the cushion layer is 10 μm or more, it is possible to completely absorb the unevenness of the substrate surface of 1 μm or more. The upper limit is not particularly limited in terms of performance, but is about 100 μm or less, preferably about 50 μm or less, more preferably 30 μm or less, from the viewpoint of production suitability.
The gas barrier layer contains A) 100% by mass of polyvinyl alcohol, or B) polyvinyl alcohol: 75 to 99% by mass, a compound represented by the following general formula (IV) and the following general formula (V). It is preferable to contain 1 to 25% by mass of at least one compound selected from the group consisting of the following compounds in 100% by mass of the gas barrier layer.

(R ₅ and R ₆ are H or CH ₃ , which may be the same or different, and n ₃ is an integer of 3 to 25.)

(R ₇ is H or an alkyl group having 1 to 6 carbon atoms, and n ₄ is an integer of 9 to 10,000.)
In the case of B), the blending ratio of the polyvinyl alcohol in the gas barrier layer is preferably 75% by mass or more and 99% by mass or less with respect to 100% by mass of the gas barrier layer from the viewpoint of developability and cost. More preferably, it is 85 mass% or more and 95 mass% or less.
Polyvinyl alcohol is generally produced by alkali saponifying polyvinyl acetate. The weight average molecular weight of polyvinyl alcohol is preferably 1,000 to 100,000. From the viewpoint of oxygen barrier properties, a more preferred weight average molecular weight is 5,000 to 50,000. Further, the saponification degree is preferably 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more.

  The weight average molecular weight of polyvinyl alcohol was measured by Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (trademark) manufactured by Showa Denko KK (HFIP-805, HFIP-803) 2 in series, moving bed solvent: hexafluoroisopropanol, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) is determined as a weight average molecular weight (polystyrene conversion).

In the compound represented by the general formula (IV), n ₅ is preferably 3 or more from the viewpoint of odor, and n ₅ is preferably 25 or less from the viewpoint of compatibility with polyvinyl alcohol and developability. n ₅ is more preferably 5 or more and 20 or less, and still more preferably 7 or more and 15 or less. Specific examples of the compound represented by the general formula (IV) include polyethylene glycol having an average molecular weight of 200 (PEG 200 manufactured by NOF Corporation), polyethylene glycol having an average molecular weight of 300 (PEG 300 manufactured by NOF Corporation, average) Polyethylene glycol having a molecular weight of 400 (PEG 400 manufactured by NOF Corporation), polyethylene glycol having an average molecular weight of 600 (PEG 600 manufactured by NOF Corporation), polyethylene glycol having an average molecular weight of 1000 (PEG 1000 manufactured by NOF Corporation), Polyethylene glycol monomethyl ether having an average molecular weight of 400 (Uniox M-400 manufactured by NOF Corporation), polyethylene glycol monomethyl ether having an average molecular weight of 550 (Uniox manufactured by NOF Corporation) -550), polyethylene glycol monomethyl ether is the average molecular weight of 1000 (manufactured by NOF CORPORATION Uniox M-1000) and the like.

The compound represented by the general formula (V), _{n 4} is preferably 9 or more, _{n 4} from the viewpoint of developability is preferably 10,000 or less. n ₄ is more preferably 20 or more and 2,000 or less, and still more preferably 30 or more and 1,500 or less. Specific examples of the compound represented by the general formula (V) include polyvinyl pyrrolidone. Specific examples include K-15 with a weight average molecular weight of 40,000 manufactured by Nippon Shokubai Co., Ltd., K-30 with a weight average molecular weight of 100,000, K-85 with a weight average molecular weight of 900,000, and K with a weight average molecular weight of 1,000,000. -90 etc.

  The content in the gas barrier layer of at least one compound selected from the group consisting of the compound represented by the general formula (IV) and the compound represented by the general formula (V) is based on 100% by mass of the gas barrier layer. 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more. Further, from the viewpoint of sensitivity, it is 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.

In addition to the above, the gas barrier layer includes a known water-soluble polymer such as polyvinyl ether-maleic anhydride water-soluble salts, carboxyalkyl starch water-soluble salts, polyacrylamide, polyamide, polyacrylic acid water-soluble salts, gelatin, Polypropylene glycol or the like can be contained.
The thickness of the gas barrier layer is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less from the viewpoint of not affecting the transferability of the photosensitive resin layer. Further, from the viewpoint of oxygen barrier properties, the thickness of the gas barrier layer is preferably 0.05 μm or more, and more preferably 0.1 μm or more.

The release agent layer preferably contains at least one compound selected from the group consisting of silicone compounds and fluorine-containing compounds.
Examples of the silicone compound include silicone resins.
Fluorine-containing compounds include amorphous fluororesins, copolymer oligomers containing perfluoroalkyl group-containing acrylates or methacrylates, fluorine-based coating agents, fluorine-based surface treatment agents containing electron beam or UV-curing components, and thermosetting components Preferred are fluorine-based surface treatment agents, fluorine-based surfactants, and the like. Specifically, Lumiflon manufactured by Asahi Glass Co., Ltd., Cytop, Modiper F series manufactured by Nippon Oil & Fats Co., Ltd. Unidyne manufactured by Daikin Industries, Ltd. EGC1700 from Omnova Solutions, Polyfox PF-3320 from Omninova Solutions, Cheminox FAMAC-8 from Unimatec, EGC1720 from Sumitomo 3M, MegaFuck F114 from Dainippon Ink and Chemicals, F410 series, F440 series, F450, Examples include the F490 series.

Of these, silicone resins are particularly preferable in terms of transferability. Specific examples of the silicone resin include KM, KS, and KF series manufactured by Shin-Etsu Chemical Co., Ltd.
As a method for forming the release agent layer, the release agent is applied to the above-mentioned organic polymer film by using a known application method such as Mayer coating, gravure coating, doctor coating, or air knife coating, and then heat treatment or Examples thereof include a method of drying or curing by a known method suitable for a release agent such as ultraviolet irradiation.
Although there is no restriction | limiting in particular in the thickness of a mold release agent layer, 0.001 micrometer-1.0 micrometer are preferable. From the viewpoint of expressing the effect of improving releasability, 0.001 μm or more is preferable, and from the viewpoint of preventing blocking when the organic polymer films with a release agent layer are stacked, 1.0 μm or less is preferable.

  The photosensitive resin laminate can be stored, for example, in the form of a flat plate as it is, or wound around a cylindrical core or the like and rolled. The core is not particularly limited as long as it is conventionally used. For example, plastic such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, ABS resin (acrylonitrile-butadiene-styrene copolymer), etc. Etc. At the time of storage, it is preferable that the support is wound up so as to be the outermost side. Moreover, it is preferable to install an end face separator from the viewpoint of protecting the end face on the end face of the photosensitive resin laminate wound in a roll shape, and in addition, it is preferable to install a moisture-proof end face separator from the viewpoint of edge fusion resistance. . Moreover, when packaging the photosensitive resin laminate, it is preferable to wrap and package it in a black sheet with low moisture permeability.

EXAMPLES The present invention will be described more specifically with reference to examples below, but the present invention is not limited to these examples.
First, molds, imprint apparatuses and photosensitive resin compositions used in Examples and Comparative Examples will be described, and then an evaluation method and evaluation results will be shown.
1. Mold A commercially available silicon nanoimprint mold was used.
Dimensions 50mm x 100mm x 0.6mm
Pattern dimensions: 100 nm to 1000 nm
Depth: 100nm to 350nm
2. Roller transfer type imprint apparatus Thermal roller type nanoimprinter NM-0606R (manufactured by Myeongchang Kiko Co., Ltd.) was used.

3. Preparation of photosensitive resin composition The compounds shown below were mixed to prepare a photosensitive resin composition.
A-1: Methyl ethyl ketone solution of benzyl methacrylate / methacrylic acid copolymer (weight ratio 85/15, weight average molecular weight 30000, solid content concentration 40% by mass, acid equivalent 573) 120 parts by mass B-1: triethoxymethylol Propane triacrylate (SR-454D manufactured by Sartomer Co., Ltd.) 10 parts by mass B-2: Bisphenol A ethylene oxide 10 mol adduct dimethacrylate (NK Nakamura Chemical Co., Ltd. NK ester BPE-500) 20 parts by mass B- 3: Bisphenol A ethylene oxide 4 mol adduct dimethacrylate (NK Nakamura Chemical Co., Ltd. NK ester BPE-200) 10 parts by mass C-1: 2- (o-chlorophenyl) -4,5-diphenylimidazole 3-mer (made by Kuroki Kasei) C-2: p, p'-bis (diethylamino) ) Benzophenone 0.2 parts by weight
D-1: 0.2 parts by mass of leuco crystal violet
D-2: Diamond green 0.1 part by mass

4). Production of photosensitive resin laminate As a support, polyethylene terephthalate film R340 (manufactured by Mitsubishi Chemical Polyester Co., Ltd., thickness 16 μm, cross-sectional curve maximum cross-sectional height (Pt) 0.3 μm), the photosensitive resin composition, It apply | coated uniformly using the bar coater, and it dried for 3 minutes in 95 degreeC drying machine, and obtained the photosensitive resin laminated body. The thickness of the photosensitive resin layer was 0.5 to 7 μm. The viscosity of the photosensitive resin layer was 5 × 10 ⁷ Pa · s.

5). [Examples 1-5, Comparative Examples 1-5]
Various patterns were formed by the following method according to the procedure described in FIG.
The photosensitive resin laminate was laminated on a substrate made of a polyethylene terephthalate film having a thickness of 100 μm. Thereafter, the support of the photosensitive resin laminate was peeled and removed, placed so that the photosensitive resin layer was in contact with the mold pattern, and pressurized using a roller of a roller transfer type imprint apparatus. The applied pressure, roller speed, and roller temperature at this time were changed as shown in Table 1. After pressing, with no left the mold was exposed with an exposure amount 100 mJ / cm ² with a UV lamp that came with the device (illuminance 50 mW). Thereafter, the mold was detached from the substrate, and the transferability of the pattern formed on the photosensitive resin layer and the releasability from the mold were determined.

6). Results The Examples and Comparative Examples were evaluated as follows.
-Transferability The formed pattern was observed by a microscope, SEM, and cross section, and judged as follows.
○: The mold shape can be accurately transferred.
Δ: Part of the shape of the mold cannot be accurately transferred. Although it is embedded in the mold, the cross-sectional shape of the pattern is rounded.
X: The shape of the mold cannot be accurately transferred. Almost not embedded in the mold,
The shape of the pattern is completely broken.

-Releasability When the photosensitive resin was removed from the mold, it was observed whether or not the photosensitive resin layer remained on the mold surface, and the following determination was made.
○: No photosensitive resin layer remains on the mold surface.
(Triangle | delta): The photosensitive resin layer remains in a part of mold surface.
X: The photosensitive resin layer remains on the entire mold surface.
The results of the evaluation are shown in Table 1 below.

  The photosensitive resin laminate for imprinting of the present invention and a pattern forming method using the same can be applied to pattern formation in recording media, optical devices, circuit elements (such as LSI), biodevices, and the like.

These are the schematic diagrams of a cross section which show an example of the pattern formation method by this invention. These are the schematic diagrams of the cross section which show the other example of the pattern formation method by this invention. These are the schematic diagrams of the cross section which show the other example of the pattern formation method by this invention. These are the schematic diagrams of the cross section which show the other example of the pattern formation method by this invention. These are the schematic diagrams of the cross section which show the other example of the pattern formation method by this invention. These are the schematic diagrams of the cross section which show the other example of the pattern formation method by this invention. These are the schematic diagrams of the cross section which show the other example of the pattern formation method by this invention. These are the schematic diagrams of the cross section which show the other example of the pattern formation method by this invention. 4 is an electron micrograph of a pattern formed by the method of Example 4. These are the electron micrographs of the pattern formed by the method of Example 4.

Explanation of symbols

1. Support 2. 2. Photosensitive resin layer Base material 4. Surface plate 5. Mold 6. Roller mold 7. Stage 8 Press roll 9. Actinic ray irradiation device (when placed downstream of the roller)
10. Actinic ray irradiation device (when placed directly under the roller)
11. Roller 12. Flexible flat plate mold

Claims (8)

  An imprint process including a pressing step of pressing the mold and the photosensitive resin layer using a heating body set at a temperature of 35 to 130 ° C., an exposure step of curing the photosensitive resin layer by exposure, and a release step of removing the mold A method of forming a pattern by   The pattern formation method of Claim 1 including the process of laminating the photosensitive resin layer to a base material before the said press process. The method for forming a pattern according to claim 1 or 2, wherein the pressing step is a step of pressing the photosensitive resin layer and the mold using a roller.   The pattern formation method of Claim 3 whose rotation speed of the said roller is 3-50 mm / sec.   The pattern forming method according to claim 3 or 4, wherein the pressure applied by the roller is 0.1 kN to 10 kN. The pattern formation method of any one of Claims 1-5 whose thickness of the said photosensitive resin layer is 0.1-7 micrometers. The pattern formation method of any one of Claims 1-6 whose viscosity in 20 degreeC of the said photosensitive resin layer is 10 < ⁶ > -10 < ¹¹ > Pa * s. The pattern forming method according to claim 1, wherein the photosensitive resin layer includes a) radical polymerization type or b) chemically amplified type photosensitive resin.