JP2013042096A - Photosensitive resin composition for optical imprint, hardened material, resist substrate, and manufacturing method of semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin for an optical imprint containing a photoinitiator highly sensitive to light and having high compatibility with a chemical compound or high solubility to a chemical compound.SOLUTION: The photosensitive resin composition for an optical imprint contains: (A) a photoinitiator represented by the general formula (I); and (B) a compound having one or more polymerizable reactive group. The viscosity of the composition at 25°C is 25 cPs or less.

Description

  The present invention relates to a photosensitive resin composition for photoimprinting, a cured product obtained by exposing the photosensitive resin composition, a resist substrate, and a method for manufacturing a semiconductor device. More specifically, it contains a photopolymerization initiator that is highly compatible with a compound having one or more polymerizable reactive groups or highly soluble in a compound having one or more polymerizable reactive groups and has high sensitivity to light. It is a photosensitive resin composition having excellent deep-part curability, and has a high filling property into the recesses of the template, while the cured product after exposure has excellent peelability from the template and excellent adhesion to the substrate. Photosensitive resin composition for photoimprint having extremely low unevenness and curvature, chipping shrinkage, and excellent dry etching resistance, a cured product obtained by exposing the photosensitive resin composition, and The present invention relates to a resist substrate and a method for manufacturing a semiconductor device.

Imprinting is one of the techniques used when forming uneven shapes of several tens of nm to several hundreds of μm.
Among them, the method of transferring the concavo-convex shape using light is referred to as optical imprint, and since a fine concavo-convex shape can be produced at low cost without using an expensive process device such as an exposure apparatus or an electron beam drawing apparatus, Has attracted attention in recent years. In optical imprinting, a mold member (generally referred to as a template, stamper, mold, or the like) having a fine concavo-convex shape is brought into contact with a photocurable resin composition applied or dripped onto a substrate surface to form a concavo-convex concave portion. Is a concavo-convex forming technique in which after the photosensitive resin composition is filled, the filled resin composition is cured with light, the template is released from the cured resin, and the fine shape is transferred at the same magnification. The case of nm (nanometer) size is particularly called optical nanoimprint.
In optical imprinting, it is necessary to increase the filling property of the photosensitive resin composition into the recesses of the template, and it is necessary to improve the releasability from the template and to improve the adhesion to the substrate. In particular, when the concavo-convex shape is nm (nanometer) size, high performance is required for these. Various studies have been made on improving the adhesion between the cured resin and the substrate in the imprint process. For example, a method for improving substrate adhesion by incorporating a silane coupling agent into a photosensitive resin composition is known (see Patent Documents 1 and 2). In addition, troubles related to the adhesion between the cured resin and the substrate in the imprint process are also closely related to the peeling force (release property) between the cured resin and the template. With respect to improvement in mold release properties, it has been reported that fluorine-based materials or silicon-based materials are used as mold release agents (see Patent Documents 3 and 4). Since these methods are improved methods as additives, they have a wide range of applications, but fluorine atoms and silicon atoms cannot be used depending on applications such as adhesion to coating devices and contamination of devices during etching of cured films. There is a case.
As described above, it is not easy to increase the filling property of the photosensitive resin composition into the recesses of the template, to be excellent in releasability from the template, and to improve the adhesion to the substrate. There is still a study of how resolution can be achieved. Here, using a oxime ester compound as a photoinitiator is proposed as a method of obtaining the photosensitive resin composition which can achieve high sensitivity, high resolution, etc. (refer patent documents 5-9).

JP 2007-84625 A JP 2008-105414 A JP 2007-1250 A JP-A-2005-84561 Japanese Patent No. 3860170 JP 2006-36750 A Japanese Patent No. 3993725 JP 2010-37542 A Korean Published Patent No. 2009-0046108

  In the photopolymerization initiators described in Patent Documents 5 to 9, compatibility with a compound having one or more polymerizable reactive groups or solubility in a compound having one or more polymerizable reactive groups is insufficient, and the use conditions There are limitations. Further, these photopolymerization initiators still have room for improvement in sensitivity to light. Therefore, it is meaningful to provide a photosensitive resin composition containing a photopolymerization initiator having a novel structure capable of solving the conventional problems, and is also required in the technical field.

  Accordingly, an object of the present invention is to contain a photopolymerization initiator that is highly compatible with a compound having one or more polymerizable reactive groups or highly soluble in a compound having one or more polymerizable reactive groups and has high sensitivity to light. The photosensitive resin composition is excellent in resolution and deep part curability, and has a high filling property in the recesses of the template, while the cured product after the exposure has excellent peelability from the template and excellent adhesion to the substrate. , A photosensitive resin composition for photoimprinting, which has very little unevenness or curvature or chipping in a cured product, has a low cure shrinkage, and is excellent in dry etching resistance, and is obtained by exposing the photosensitive resin composition. It is providing the manufacturing method of hardened | cured material, a resist substrate, and a semiconductor device.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor is a photosensitive resin composition containing a photopolymerization initiator having a specific structure represented by the general formula (I) described later, We found that the problem could be solved.
That is, the present invention relates to the following [1] to [8].
[1] (A) a photopolymerization initiator represented by the following general formula (I) and (B) a photoimprint having a compound having one or more polymerizable reactive groups and having a viscosity at 25 ° C. of 25 cPs or less Photosensitive resin composition.
Wherein R ^{1 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, Or an unsubstituted cycloalkyl group having 3 to 10 ring atoms, a substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or Unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted ring forming carbon number .R ³ showing a 6-14 aryl group, or a substituted or unsubstituted heterocyclic group ring atoms 3-14, to form a ring together with R ⁴ or R ⁵ Good .R ⁴ may form a ring together with R ^5.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
W represents a single bond or an oxygen atom. Z represents a single bond, an oxygen atom, or> NR ³ ′ (R ³ ′ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ³ ′ is connected to R ³ together with a nitrogen atom. Forming a ring).
n represents an integer of 1 to 10. When n is an integer of 2 to 10, a plurality of R ⁴ and R ⁵ may be the same or different. )
[2] The photosensitive resin composition for photoimprints according to [1] above, wherein the photosensitive resin composition is placed on a substrate having 1.5 μl of pure water contact angle of 112 ° ± 5 ° and 40 ±. A photosensitive resin composition for photoimprinting, in which the change in the diameter of the droplets is within 15% when dropped as 5 pl (picoliter) droplets and left at 1 atmosphere and 25 ° C. for 1 minute.
[3] In the general formula (I), [1] or [1] above, wherein Z is an oxygen atom, and R ³ is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms. The photosensitive resin composition for photoimprints according to [2].
[4] The photosensitive resin composition for photoimprints according to any one of [1] to [3], further comprising a surfactant as the component (C).
[5] The photosensitive resin composition for photoimprints according to any one of [1] to [4], wherein the component (B) is a compound having a (meth) acryloyl group.
[6] A cured product obtained by exposing the photosensitive resin composition for photoimprints according to any one of [1] to [5] above.
[7] A method for manufacturing a resist substrate, comprising the following steps (1) to (4) in this order.
(1) A step of attaching the photosensitive resin composition according to any one of the above [1] to [5] to the substrate or an adhesion layer laminated on the substrate by an inkjet method.
(2) From above the photosensitive resin composition attached in the step (1), a template having a concavo-convex shape is brought into contact with the substrate or an adhesion layer laminated on the substrate, and the concavo-convex shape is brought into contact with the substrate. A step of filling a photosensitive resin composition.
(3) The process which hardens the said photosensitive resin composition by exposure, and forms a resist uneven | corrugated shape on the contact | adherence layer laminated | stacked on the board | substrate or the board | substrate.
(4) The process of peeling a template from the board | substrate with which the resist uneven | corrugated shape was formed.
[8] A method for manufacturing a semiconductor device, comprising the following steps (5) to (7) in this order.
(5) In the resist substrate obtained by the manufacturing method according to the above [7], a step of dry etching the resist concave-convex recess until the substrate is exposed.
(6) A step of further subjecting the exposed portion of the substrate appearing in the step (5) to dry etching to form a recess in the substrate itself.
(7) A step of removing the resist on the substrate, or a step of removing both the adhesion layer and the resist when the adhesion layer is laminated on the substrate.

  The photosensitive resin composition for photoimprinting of the present invention is highly compatible with a compound having one or more polymerizable reactive groups or highly soluble in a compound having one or more polymerizable reactive groups, and has high sensitivity to light. It is the photosensitive resin composition which is excellent in the resolution and deep part sclerosis | hardenability containing a photoinitiator. And while the filling property of the concave portion of the template is high, the cured product after the exposure is excellent in the peelability from the template and the adhesiveness with the substrate, and the cured product has very little unevenness in the shape and curvature of the cured product and cure shrinkage. The rate is low and the dry etching resistance is excellent. In addition, since it has a low viscosity (25 cPs or less), it can be applied by inkjet.

7 is a SEM photograph of a resist pattern obtained in Example 6 and having a line width of 24 nm. 7 is a SEM photograph of a resist pattern obtained in Example 6 and having a line line width of 32 nm.

[Photosensitive resin composition for photoimprint]
The photosensitive resin composition for photoimprinting of the present invention comprises (A) a photopolymerization initiator represented by the following general formula (I) and (B) a compound having one or more polymerizable reactive groups, and 25 A photosensitive resin composition for photoimprinting having a viscosity at 25 ° C. of 25 cPs or less.
Wherein R ^{1 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, Or an unsubstituted cycloalkyl group having 3 to 10 ring atoms, a substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or Unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted ring forming carbon number .R ³ showing a 6-14 aryl group, or a substituted or unsubstituted heterocyclic group ring atoms 3-14, to form a ring together with R ⁴ or R ⁵ Good .R ⁴ may form a ring together with R ^5.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
W represents a single bond or an oxygen atom. Z represents a single bond, an oxygen atom, or> NR ³ ′ (R ³ ′ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ³ ′ is connected to R ³ together with a nitrogen atom. Forming a ring).
n represents an integer of 1 to 10. When n is an integer of 2 to 10, a plurality of R ⁴ and R ⁵ may be the same or different. )

[(A) Photopolymerization initiator]
The photopolymerization initiator (A) used in the present invention is represented by the general formula (I).
Among the photopolymerization initiators represented by the general formula (I), from the viewpoint of the effect of the present invention, Z is an oxygen atom (O), and R ³ is substituted with an alkoxy group having 1 to 18 carbon atoms. What is a C1-C20 alkyl group is preferable. From the same viewpoint, the photopolymerization initiator represented by the following general formula (Ia) (W: corresponds to a single bond, Z: an oxygen atom) and the following general formula (Ib) Preferred is a photopolymerization initiator (corresponding to the case where n is 1).

In the above formulae, R ^{1 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, and a substituted group. Or an unsubstituted cycloalkyl group having 3 to 10 ring atoms, a substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or Unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 14 ring carbon atoms A group or a substituted or unsubstituted heterocyclic group having 3 to 14 ring atoms; In the general formula (Ia), R ³ may be combined with R ⁴ or R ⁵ to form a ring, and R ⁴ is combined with R ⁵ to form a ring. It may be formed.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
W in the general formula (Ib) represents a single bond or an oxygen atom. Z in the general formula (Ib) represents a single bond, an oxygen atom, or> NR ³ ′ (R ³ ′ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ³ 'Is connected to R ³ to form a ring together with the nitrogen atom.
N in general formula (Ia) shows the integer of 1-10. When n is an integer of 2 to 10, a plurality of R ⁴ and R ⁵ may be the same or different.

(About each group in general formula (I), (Ia) and (Ib))
n is a compatibility with a compound having one or more polymerizable reactive groups described later (hereinafter sometimes simply referred to as “compatible”) or a solubility in a compound having one or more polymerizable reactive groups (hereinafter referred to as “compatibility”). From the viewpoint of simple solubility, and the ease of production, an integer of 2 to 8 is preferable, an integer of 2 to 4 is more preferable, and 2 is more preferable.
As a halogen atom which R < ¹ > -R < ¹¹ > shows each independently, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
The alkyl group having 1 to 20 carbon atoms independently represented by R ^{1 to} R ¹¹ may be linear or branched. For example, methyl, ethyl, n-propyl, isopropyl, n-butyl Group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-octyl group, 2-ethyl-n-octyl group, n-decyl group, n-dodecyl group and the like. . Among these, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable from the viewpoints of compatibility or solubility and ease of production.
The alkenyl group having 2 to 20 carbon atoms independently represented by R ^{1 to} R ¹¹ may be linear or branched, and examples thereof include a vinyl group, an allyl group, and a 7-octenyl group. Among these, an alkenyl group having 2 to 10 carbon atoms is preferable and an alkenyl group having 2 to 6 carbon atoms is more preferable from the viewpoints of compatibility or solubility and ease of production.
Examples of the cycloalkyl group having 3 to 10 ring atoms independently represented by R ^{1 to} R ¹¹ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Among these, a cycloalkyl group having 3 to 6 ring atoms is preferable from the viewpoints of compatibility or solubility and ease of production.
Examples of the C 4-20 cycloalkenyl group independently represented by R ^{1 to} R ¹¹ include a cyclopentenyl group, a cyclohexenyl group, a cyclohexadienyl group, a cyclooctenyl group, and the like. Among these, a C4-C10 cycloalkenyl group is preferable and a C4-C6 cycloalkenyl group is more preferable from the viewpoints of compatibility or solubility and ease of production.

As C1-C20 alkoxy group which R < ¹ > -R < ¹¹ > shows each independently, what an alkyl group site | part is an above-described C1-C20 alkyl group is mentioned. Among these, an alkoxy group having 1 to 10 carbon atoms is preferable and an alkoxy group having 1 to 5 carbon atoms is more preferable from the viewpoints of compatibility or solubility and ease of production.
Examples of the alkenyloxy group having 2 to 20 carbon atoms independently represented by R ^{1 to} R ¹¹ include those in which the alkenyl group moiety is the aforementioned alkenyl group having 2 to 20 carbon atoms. Among these, an alkenyloxy group having 2 to 10 carbon atoms is preferable and an alkenyloxy group having 2 to 6 carbon atoms is more preferable from the viewpoints of compatibility or solubility and ease of production.
The alkanoyl group having 1 to 20 carbon atoms independently represented by R ^{1 to} R ¹¹ may be linear or branched. For example, methanoyl group, ethanoyl group, n-propanoyl group, isopropanoyl group, n -Butanoyl group, t-butanoyl group, n-hexanoyl group, n-octanoyl group, n-decanoyl group, n-dodecanoyl group, etc. are mentioned. Among these, an alkanoyl group having 1 to 10 carbon atoms is preferable and an alkanoyl group having 1 to 5 carbon atoms is more preferable from the viewpoints of compatibility or solubility and ease of production.
The alkenoyl group having 2 to 20 carbon atoms independently represented by R ^{1 to} R ¹¹ may be linear or branched. For example, ethenoyl group, n-propenoyl group, isopropenoyl group, n-butenoyl group, t -Butenoyl group, n-hexenoyl group, n-octenoyl group, n-decenoyl group, n-dodecenoyl group, etc. are mentioned. Among these, an alkenoyl group having 2 to 10 carbon atoms is preferable and an alkenoyl group having 2 to 6 carbon atoms is more preferable from the viewpoints of compatibility or solubility and ease of production.

Examples of the aryl group having 6 to 14 ring carbon atoms independently represented by R ^{1 to} R ¹¹ include a phenyl group, a naphthyl group, and an anthryl group.
Examples of the heterocyclic group having 3 to 14 ring atoms independently represented by R ^{1 to} R ¹¹ include a 2-furanyl group, a 2-thiophenyl group, a 2-pyridinyl group, and the following formula (A). Group (hereinafter referred to as substituent (A))
An unsaturated heterocyclic group having 5 to 14 ring atoms such as 2-tetrahydrofuryl group, 3-tetrahydrofuryl group, pyrrolidinyl group, piperidinyl group, 2,2,6,6-trimethylpiperidin-4-yl group, etc. And a saturated heterocyclic group having 3 to 10 ring atoms. Among these, an unsaturated heterocyclic group having 5 to 6 ring atoms and a saturated heterocyclic group having 3 to 6 ring atoms are preferable from the viewpoints of compatibility or solubility and ease of production.

The above-mentioned “R ³ and R ⁴ or R ⁵ together form a ring” means that n = 2, W is a single bond, and Z is an oxygen atom. The ring illustrated in the right side and exemplified on the right side is given as a specific example.

Examples of the ring formed by combining R ⁴ and R ⁵ include rings having 3 to 10 (preferably 3 to 6) ring carbon atoms such as a cyclopentyl ring and a cyclooctyl ring.

The alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, alkoxy group, alkenyloxy group, alkanoyl group, alkenoyl group, aryl group and heterocyclic group, which R ^{1 to} R ¹¹ independently represent, It may have a substituent.
Examples of the substituent for the alkyl group and alkenyl group independently represented by R ^{1 to} R ¹¹ include a hydroxyl group; a carboxyl group; a linear or branched chain having 1 to 1 carbon atoms such as a methoxy group, an ethoxy group, and a propoxy group. 18 (preferably 1 to 10, more preferably 1 to 5) alkoxy group; linear or branched alkenyloxy group having 2 to 18 carbon atoms (preferably 2 to 10 and more preferably 2 to 6) Linear or branched alkenylthio group having 2 to 18 carbon atoms (preferably 2 to 10, more preferably 2 to 6 carbon atoms); linear or branched carbon number 1 to 18 (preferably 1) -10, more preferably 1-5) alkylthio group; C5-C18 (preferably 5-10) cycloalkenyl group; C3-C18 (preferably cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.) 3-10, more preferably 3-6) cycloalkyl group; aryloxy group having 6-10 ring-forming carbon atoms such as phenoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; Oxygen atom (= O); sulfur atom (= S); cyano group; nitro group; trialkylsilyl group such as trimethylsilyl group; trialkoxysilyl group such as trimethoxysilyl group; phenyl group, naphthyl group, anthryl group, etc. an aryl group ring carbon 6 to 14 (preferably ^{6~10); -COR 12; -OCOR 13} ; -NR 14 R 15; -NHCOR 16; -NHCOOR 17; -CONR 18 R 19; -COOR 20; _{^{-SO 3 NR 21 R 22; -SO}} 3 R 23; epoxy group and a tetrahydrofuranyl group ring atoms 3-6 cyclic ether groups such as, 2-thienyl, 2-pyridyl Group, a furyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a saturated or unsaturated heterocyclic group having 3 to 10 (preferably 3 to 6) ring atoms such as the substituent (A), and the like. .
In said general formula, R < ¹² > -R < ²³ > shows a C1-C20 linear or branched alkyl group and a C6-C14 aryl group each independently formed. Examples of the alkyl group and aryl group include the same groups as in R ^{1 to} R ¹¹ .

Examples of the substituent for the alkoxy group, alkenyloxy group, alkanoyl group, and alkenoyl group independently represented by R ^{1 to} R ¹¹ include hydroxyl group; carboxyl group; linear or branched such as methoxy group, ethoxy group, and propoxy group A linear alkoxy group having 1 to 18 carbon atoms (preferably 1 to 10, more preferably 1 to 5); linear or branched carbon atom having 2 to 18 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 2 carbon atoms) To 6) alkenyloxy group; linear or branched alkenylthio group having 2 to 18 carbon atoms (preferably 2 to 10, more preferably 2 to 6); linear or branched carbon number 1-18 (preferably 1-10, more preferably 1-5) alkylthio group; C5-C18 (preferably 5-10) cycloalkenyl group; cyclopropyl group, cyclopentyl group A cycloalkyl group having 3 to 18 carbon atoms (preferably 3 to 10, more preferably 3 to 6) such as a cyclohexyl group; an aryloxy group having 6 to 10 ring carbon atoms such as a phenoxy group; a fluorine atom, a chlorine atom, Halogen atoms such as bromine atom and iodine atom; oxygen atom (= O); sulfur atom (= S); cyano group; nitro group; trialkylsilyl group such as trimethylsilyl group; trialkoxysilyl group such as trimethoxysilyl group; phenyl group, a naphthyl group, an aryl group having 6 to 14 ring-forming carbon atoms, such as anthryl group (preferably ^{6~10); -COR 12; -OCOR 13} ; -NR 14 R 15; -NHCOR 16; -NHCOOR 17; ^{-CONR 18 R 19; -COOR 20;} -SO 3 NR 21 R 22; -SO 3 R 23; an epoxy group or a tetrahydrofuranyl group ring atoms 3-6 3 to 10 (preferably 3) saturated or unsaturated ring-forming atoms such as a cyclic ether group, 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group and the substituent (A) -6) and the like (wherein R ^{12 to} R ²³ are as defined above).

Examples of the substituent for the cycloalkyl group and cycloalkenyl group independently represented by R ^{1 to} R ¹¹ include a hydroxyl group; a carboxyl group; a linear or branched carbon number of 1 to 18 such as a methyl group and an ethyl group (preferably Is an alkyl group of 1 to 10, more preferably 1 to 5); linear or branched carbon number of 1 to 18 (preferably 1 to 10, more preferably 1) such as a methoxy group, an ethoxy group, or a propoxy group To 5) alkoxy group; linear or branched alkenyloxy group having 2 to 18 carbon atoms (preferably 2 to 10, more preferably 2 to 6); linear or branched carbon number 2 -18 (preferably 2 to 10, more preferably 2 to 6) alkenylthio group; straight chain having 2 to 18 carbon atoms (preferably 2 to 10, more preferably 2 to 6) such as vinyl group and allyl group Or branched alkeni A linear or branched alkylthio group having 1 to 18 (preferably 1 to 10, more preferably 1 to 5) carbon atoms; a cycloalkenyl group having 5 to 18 (preferably 5 to 10) carbon atoms; Aryloxy groups having 6 to 10 ring carbon atoms such as phenoxy group; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; oxygen atom (= O); sulfur atom (= S); cyano group; A trialkylsilyl group such as a trimethylsilyl group; a trialkoxysilyl group such as a trimethoxysilyl group; an aryl group having 6 to 14 (preferably 6 to 10) ring carbon atoms such as a phenyl group, a naphthyl group, and an anthryl group; ^{-COR 12; -OCOR 13; -NR 14} R 15; -NHCOR 16; -NHCOOR 17; -CONR 18 R 19; -COOR 20; -SO 3 NR 21 R 22; -SO 3 R 23 A cyclic ether group having 3 to 6 ring atoms such as an epoxy group and a tetrahydrofuranyl group, a 2-thienyl group, a 2-pyridyl group, a furyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, the substituent (A), etc. Examples thereof include a saturated or unsaturated heterocyclic group having 3 to 10 (preferably 3 to 6) ring-forming atoms (wherein R ^{12 to} R ²³ are as defined above).

Examples of the substituent for the aryl group and heterocyclic group independently represented by R ^{1 to} R ¹¹ include a hydroxyl group; a carboxyl group; a linear or branched C 1-18 (preferably a methyl group, an ethyl group, etc. 1-10, more preferably 1-5) alkyl group; linear or branched C1-C18 such as methoxy group, ethoxy group, propoxy group, etc. (preferably 1-10, more preferably 1-10) 5) an alkoxy group; a linear or branched alkenyloxy group having 2 to 18 (preferably 2 to 10, more preferably 2 to 6) carbon atoms; a linear or branched chain having 2 to 2 carbon atoms 18 (preferably 2 to 10, more preferably 2 to 6) alkenylthio group; linear or branched alkylthio group having 1 to 18 carbon atoms (preferably 1 to 10, more preferably 1 to 5 carbon atoms) ; Straight of vinyl group, allyl group, etc. Or a branched chain alkenyl group having 2 to 18 carbon atoms (preferably 2 to 10, more preferably 2 to 6); a cycloalkenyl group having 5 to 18 carbon atoms (preferably 5 to 10); a cyclopropyl group; A cycloalkyl group having 3 to 18 carbon atoms (preferably 3 to 10, more preferably 3 to 6) such as a cyclopentyl group and a cyclohexyl group; an aryloxy group having 6 to 10 ring carbon atoms such as a phenoxy group; a fluorine atom; trialkoxysilyl group such as trimethoxysilyl group; a trialkylsilyl group such as trimethylsilyl group; a cyano group; a nitro group chlorine atom, a bromine atom, a halogen atom such as iodine atom -COR ^12; -OCOR ^13; -NR ^{14 R 15; -NHCOR 16; -NHCOOR 17} ; -CONR 18 R 19; -COOR 20; -SO 3 NR 21 R 22; -SO 3 R 23; epoxy Saturation of a cyclic ether group having 3 to 6 ring atoms such as a group or a tetrahydrofuranyl group, a 2-thienyl group, a 2-pyridyl group, a furyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, or the substituent (A) Alternatively, an unsaturated heterocyclic group having 3 to 10 (preferably 3 to 6) unsaturated ring-forming atoms may be mentioned (wherein R ^{12 to} R ²³ are as defined above).

Examples of the aryl group having 6 to 14 ring carbon atoms represented by Ar include a phenyl group, a naphthyl group, an anthryl group, a chrycenyl group, a phenanthrenyl group, an azulenyl group, and an acenaphthylenyl group. Among these, an aryl group having 6 to 10 ring carbon atoms is preferable and a phenyl group is more preferable from the viewpoints of compatibility or solubility and ease of production. Examples of the heteroaryl group having 5 to 14 ring atoms represented by Ar include a 2-furanyl group, a 2-thiophenyl group, and a 2-pyridinyl group. Among these, a heteroaryl group having 5 to 6 ring atoms is preferable, and a 2-furanyl group and a 2-thiophenyl group are more preferable from the viewpoints of compatibility or solubility and ease of production.
These aryl groups and heteroaryl groups may have a substituent. Examples of the substituent include the same substituents as the aryl group independently represented by R ^{1 to} R ¹¹ described above, and among them, the number of carbon atoms is 1 to 18 (preferably 1 to 10, more preferably The alkyl group of 1-5) is preferable and a methyl group is more preferable.
In addition, when this substituent is an alkyl group or an alkenyl group, it may form a condensed ring with Ar, for example, a fluorene ring, an indene ring, or the like.

Z represents> NR ³ 'R ^3' in has, as described above, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ³ 'is connected to the R ^3, ring together with the nitrogen atom Is forming.
As the alkyl group of carbon number 1 to 20, it includes the same ones as in R ¹ to R ^11, preferably also the same thing can be mentioned those, a methyl group is particularly preferred.
Specific examples of the ring formed by connecting R ³ 'to R ³ together with the nitrogen atom include a morpholine ring, a pyrrolidine ring, a piperidine ring, a pipecoline ring, and a piperazine ring. Among these, a morpholine ring is preferable.
As a combination of W and Z, when W is a single bond, Z is preferably an oxygen atom or> Nr ³ ′, and when W is an oxygen atom, Z is preferably a single bond or an oxygen atom.

Furthermore, in the general formula (Ia), from the viewpoint of the effect of the present invention, (a) R ¹ , R ² and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. Yes, n is 2, each of R ⁴ and R ⁵ is independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and Ar is a substituted or unsubstituted ring. A photopolymerization initiator which is an aryl group having 6 to 14 carbon atoms, (b) R ¹ , R ² and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and n is A plurality of R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and Ar is a substituted or unsubstituted ring carbon number of 5 to 5; 14 photoinitiators which are 14 heteroaryl groups, (c) R ¹ and R ² is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R ³ is a substituted or unsubstituted cycloalkyl group having 3 to 18 carbon atoms, n is 2, R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, (d) R ¹ and R ² are each independently substituted Or an unsubstituted alkyl group having 1 to 20 carbon atoms, R ³ is an alkyl group having 1 to 20 carbon atoms substituted with a cyclic ether group having 3 to 6 ring atoms, and n is 2. A photopolymerization initiator in which a plurality of R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms is also preferred. Furthermore, from the viewpoint of reducing the content of the photopolymerization initiator in the photosensitive resin composition, in the case of (a) and (b) above, the molecular weight is preferably 515 or less, more preferably 500 or less. Preferably, in the cases (c) and (d), the molecular weight is preferably 550 or less.
Furthermore, from the viewpoint of the effect of the present invention and from the viewpoint of reducing contamination of the polymer by the decomposition product of the photopolymerization initiator and contamination of the apparatus, in the preferable photopolymerization initiator, R ^{4 to} R ¹¹ are each independently More preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. In addition, the preferable thing of each group is as above-mentioned.
Specific examples of the photopolymerization initiator (Ia) are shown below, but are not particularly limited thereto.

Furthermore, in general formula (Ib), from the viewpoint of the effect of the present invention, (e) R ¹ and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and W Is an oxygen atom, Z is a single bond or an oxygen atom, Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, (f) R ¹ and R ³ are , Each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ² is —OCOR ¹³ (R ¹³ is as defined above) or —COOR ²⁰ (R ²⁰ is An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 ring carbon atoms.) Is an alkyl group having 1 to 20 carbon atoms, and W is an oxygen atom. Is a single bond or an oxygen atom, and Ar is a substituted or unsubstituted ring Photoinitiator is an aryl group having 6 to 14 carbon atoms, (g) R ¹ and R ^3, each independently, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, W represents a single bond And Z is> NR ³ ′ (R ³ ′ is as defined above), and Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, (H) R ¹ and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ² is —OCOR ¹³ (R ¹³ is as defined above.) Or —COOR ²⁰ (R ²⁰ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 ring carbon atoms) and an alkyl group having 1 to 20 carbon atoms having an ester group. , W is a single bond, Z is> NR ³ '(R ^3' are as defined above.) There, Ar is, the photoinitiator is a substituted or unsubstituted ring forming aryl group having 6 to 14 carbon atoms, (i) R ¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, A photopolymerization initiator in which R ³ is a hydrogen atom, W is a single bond, Z is an oxygen atom, and Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms is also preferable.
In the above photopolymerization initiator (g), R ³ ′ in> NR ³ ′ is preferably connected to R ³ to form a ring with a nitrogen atom, and forms a morpholine ring. Is more preferable.
Furthermore, from the viewpoint of the effect of the present invention and from the viewpoint of reducing contamination of the polymer by the decomposition product of the photopolymerization initiator and contamination of the apparatus, in the preferable photopolymerization initiator, R ^{4 to} R ¹¹ are each independently More preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. In addition, the preferable thing of each group is as above-mentioned.
Specific examples of the photopolymerization initiator (Ib) are shown below, but are not particularly limited thereto.

In addition, as a photoinitiator used as (A) component, it is preferable that it is n = 2 in general formula (Ia) as above-mentioned, Specifically, it represents with the following general formula (I-a1). Preferred is a photopolymerization initiator.
In the above formula (I-a1), R ^{1 to} R ³ , R ^{6 to} R ¹¹ and Ar are as defined above. R ⁴ ′ and R ⁵ ′ have the same definitions as R ⁴ and R ⁵ , respectively, and preferred ones are also the same.

((A) Method for producing photopolymerization initiator)
(A) Although there is no restriction | limiting in particular in the manufacturing method of the photoinitiator (I) of a component, For example, the manufacturing method of the following photoinitiators (Ia) and manufacture of a photoinitiator (Ib) It can be easily manufactured by a method.
[1. Method for producing photopolymerization initiator (Ia)]
Although there is no restriction | limiting in particular in the manufacturing method of a photoinitiator (Ia), For example, it can manufacture easily by the following process 1-process 4.

(Process 1)
Step 1 includes, for example, the carbazole derivative (1) and Z (CR ⁴ R ⁵ ) _n COOR ³ (Z represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. R ³ , R ⁴ and R ⁵ are as defined above.) In the presence of a base. By this step, a carbonylalkyl group-introduced product represented by the following general formula (3a) is obtained.
(In the formula, R ^{3 to} R ¹¹ are as defined above, and preferred ones are also the same.)
Examples of the base include n-butyl lithium, t-butyl lithium, sodium hydroxide, potassium hydroxide and the like. The reaction temperature is usually preferably 0 to 200 ° C., and the reaction time is usually preferably 2 to 100 hours.

In addition, when manufacturing the photoinitiator of n = 2 in general formula (Ia), manufacture is easy and it is preferable that the process 1 is the following processes.
The following general formula (1)
(In the formula, R ^{6 to} R ¹¹ are as defined above, and preferred ones are also the same.)
[Hereinafter referred to as a carbazole derivative (1). And the following general formula (2a)

(In the formula, R ³ , R ⁴ ′ and R ⁵ ′ are as defined above, and preferred ones are also the same.)
An acrylate derivative represented by the formula [hereinafter referred to as an acrylate derivative (2a). And in the presence of a base, the following general formula (3a ′)

(In the formula, R ³ , R ⁴ ′, R ⁵ ′ and R ^{6 to} R ¹¹ are as defined above, and preferred ones are also the same.)
Embedded image [hereinafter referred to as carbonylalkyl group-introduced product (3a ′)]. The process of obtaining.
Hereinafter, this step 1 which is preferable when producing a photopolymerization initiator of n = 2 will be described in detail.

Although there is no restriction | limiting in particular in the usage-amount of the acrylate derivative (2a) used at the process 1, Preferably it is 0.5-2 mol with respect to 1 mol of carbazole derivatives (1), More preferably, it is 0.8-1.2. From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially equal amounts.
Step 1 is performed in the presence of a base. The base may be any base that can be used for the Michael addition reaction, and any of organic bases and inorganic bases can be used. Examples of the organic base include pyridine, diazabicycloundecene (DBU), diazabicyclononene (DBN), and the like. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; sodium hydroxide And alkali metal hydroxides such as potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide. Among these, alkali metal carbonates and alkaline earth metal carbonates are preferable, alkali metal carbonates are more preferable, and potassium carbonate is more preferable.
Although there is no restriction | limiting in particular in the usage-amount of this base, From a viewpoint of reaction efficiency and manufacturing cost, Preferably it is 0.5-2 mol with respect to 1 mol of carbazole derivative (1), More preferably, it is 0.8-1. More preferably, it is 2 moles and is used in an approximately equal amount.
Step 1 is preferably performed in the presence of a solvent. What is necessary is just to select suitably the solvent which can melt | dissolve a carbazole derivative (1), an acrylate derivative (2a), and a base as this solvent. Specific examples include dimethylformamide (DMF), dimethylsulfoxide (DMSO), methylene chloride and the like.

Although there is no restriction | limiting in particular in the reaction temperature of the process 1, Usually, it is preferably 10-50 degreeC, More preferably, it is 15-40 degreeC, More preferably, it implements at 15-30 degreeC. The reaction time varies depending on the kind and amount of the carbazole derivative (1), acrylate derivative (2a) and base, the reaction temperature, etc., but is usually about 2 to 48 hours.
The embodiment of Step 1 is not particularly limited, and for example, all of the carbazole derivative (1), the acrylate derivative (2a) and the base are added to a solvent, and preferably stirred at the above temperature to thereby introduce the carbonylalkyl group-introduced compound (3a ') Can get.

  After the completion of the reaction, the carbonylalkyl group-introduced product (3a) or (3a ′) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the carbonylalkyl group-introduced product (3a) or (3a ′) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

Hereinafter, Steps 2 to 4 using the carbonylalkyl group-introduced body (3a) or (3a ′) obtained in Step 1 will be described. For convenience, the carbonylalkyl group-introduced body (3a ′) corresponding to n = 2 is described. Will be omitted.
(Process 2)
In step 2, the carbonylalkyl group-introduced product (3a) obtained in step 1 and the following general formulas (4) and (5)
(In the formula, X represents a halogen atom or —OC (═O) Ar, and X ′ represents a halogen atom or —OC (═O) R ^2. Ar and R ² are as defined above. The preferred one is also the same.)
These are referred to as acylating agent (4) and acylating agent (5), respectively. In the presence of a Lewis acid, the following general formula (6a)

(Wherein R ^{2 to} R ¹¹ and Ar are as defined above, and preferred ones are also the same).
[Hereinafter referred to as a diketone body (6a). ] Is a step of obtaining.

In the above formula, examples of the halogen atom independently represented by X and X ′ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferred.
In step 2, the reaction of the carbonylalkyl group-introduced product (3a) with the acylating agents (4) and (5) is carried out from the viewpoint of the yield of the desired diketone product (6a). It is preferable to react the acylating agent (5) after reacting 3a) with the acylating agent (4).
The amount of the acylating agents (4) and (5) used is from the viewpoint of introducing one acyl group into the carbonylalkyl group-introduced product (3a), and 1 mole of the carbonylalkyl group-introduced product (3a). These are preferably 0.8 to 1.3 mol, more preferably 1 to 1.3 mol, respectively, and from the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially equal amounts. In particular, when the carbonyl alkyl group-introduced product (3a) and the acylating agent (4) are reacted and then the acylating agent (5) is reacted, the amount of the acylating agent (5) used is as described above. If it exceeds the range, there is no problem, but if it is too much, a yield corresponding to it will not be obtained, and the production cost may be unnecessarily high.
Step 2 is performed in the presence of a Lewis acid. As the Lewis acid, aluminum chloride and boron trifluoride diethyl ether complex are preferable. From the viewpoint of the yield of the diketone body (6a), the amount of Lewis acid used is usually preferably 0.8 to 2.5 moles, more preferably 1 mole per acylating agent (4) or (5). Is 1-2 mol.

Step 2 is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent that can be used in a normal Friedel-Crafts acylation reaction. Specific examples include dichloromethane, nitrobenzene, acetone, acetonitrile and the like.
The reaction temperature in step 2 is preferably −50 to 5 ° C. (preferably −10 to 5 ° C.) at the start of the reaction, and gradually returned to room temperature (about 15 to 25 ° C.) as the reaction proceeds. The reaction time varies depending on the type and amount of the carbonylalkyl group-introduced product (3a), acylating agents (4) and (5), and the reaction temperature, but it is usually preferably 1 to 30 hours. When both of the acylating agents (4) and (5) are acyl halides or acid anhydrides, the product is obtained after reacting the carbonylalkyl group-introduced product (3a) with the acylating agent (4). Can be subsequently reacted with the acylating agent (5) without isolation. In that case, the reaction time of the carbonylalkyl group-introduced product (3a) and the acylating agent (4) is about 30 minutes to 5 hours (preferably 30 minutes to 3 hours), while the carbonylalkyl group-introduced product (3a ) And the acylating agent (5) are preferably provided with a long reaction time of about 30 minutes to 24 hours (preferably 30 minutes to 18 hours) for sufficient reaction.

From the viewpoint of yield, two preferred embodiments of step 2 are described below.
[1] The carbonylalkyl group-introduced product (3a) and the acylating agent (4) are appropriately mixed in a solvent while cooling in an ice bath, and the Lewis acid is slowly added to the mixed solution (preferably 5 minutes to 1 hour, more (Preferably over 10 to 40 minutes), and after the addition is completed, the temperature is returned to room temperature and stirring is continued for a certain time (about 30 to 5 hours). Preferably, the product is once separated and obtained by performing usual organic compound separation means such as extraction and washing.
The product thus obtained is appropriately dissolved in a solvent, the acylating agent (5) is added while cooling in an ice bath, and the Lewis acid is slowly added thereto (preferably 5 minutes to 1 hour, more preferably 10 minutes to (Over 40 minutes), and after completion of the addition, the mixture is returned to room temperature and stirred for a certain time (about 30 minutes to 24 hours) to obtain the diketone body (6a).
[2] The carbonyl alkyl group-introduced product (3a) is appropriately mixed with a solvent while cooling in an ice bath, and then the Lewis acid is slowly added (preferably 5 minutes to 1 hour, more preferably 10 minutes to 40 minutes). The acylating agent (4) is added slowly (preferably over 5 minutes to 1 hour, more preferably over 10 minutes to 40 minutes) to the resulting mixed solution, and then returned to room temperature for a certain time (30 minutes). Continue stirring for ~ 5 hours. The Lewis acid is added slowly (preferably over 5 minutes to 1 hour, more preferably over 10 minutes to 40 minutes) while cooling in an ice bath again, and the acylating agent (5) is added slowly (preferably over 10 minutes to 40 minutes). Is added for 5 minutes to 1 hour, more preferably over 10 minutes to 40 minutes, and then returned to room temperature and continued to be stirred for a predetermined time or longer (preferably about 30 minutes to 24 hours) to thereby obtain a diketone product (6a). Can be obtained.
In addition, after completion | finish of reaction, diketone body (6a) can be obtained from the obtained reaction liquid mixture by the isolation | separation means of normal organic compounds, such as extraction. The purity of the diketone body (6a) can also be increased by appropriately purifying by a usual means for purifying organic compounds such as distillation, column chromatography, recrystallization and the like.

(Process 3)
Step 3 is a reaction of the diketone body (6a) obtained in Step 2 with hydroxylamine to give the following general formula (7a).
(Wherein R ^{2 to} R ¹¹ and Ar are as defined above, and preferred ones are also the same).
[Hereinafter referred to as the oxime body (7a). ] Is a step of obtaining.

In step 3, the hydroxylamine source is not particularly limited, but hydroxylamine chloride is preferred. The hydroxylamine chloride can be reacted with, for example, sodium acetate in water to obtain an aqueous solution of hydroxylamine.
The amount of hydroxylamine (hydroxylamine chloride) to be used is preferably 0.8 to 2 mol, more preferably 1 to 1.5 mol, and still more preferably 1 to 1.3 mol, per 1 mol of the diketone body (6a). From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially equal amounts.
Step 3 is preferably performed in the presence of a solvent. As the solvent, a water-soluble organic solvent is preferable, and as the water-soluble organic solvent, for example, alcohols such as methanol and ethanol, dimethylformamide (DMF) and the like are preferable.

Although there is no restriction | limiting in particular in the reaction temperature of the process 3, From a viewpoint of the yield of an oxime body (7a), Usually, Preferably it is 40-160 degreeC, More preferably, it is 50-140 degreeC, More preferably, it is 70-110 degreeC. is there. Although reaction time changes also with the kind and usage-amount of diketone body (6a), and reaction temperature, Usually, it is preferably 2 to 20 hours, More preferably, it is 4 to 12 hours.
There is no particular limitation on the embodiment of step 3. For example, hydroxylamine chloride and sodium acetate are mixed in water to obtain an aqueous solution of hydroxylamine, and a diketone (6a) and a solvent are added thereto, preferably An oxime body (7a) can be obtained by stirring in the said temperature range.
After completion of the reaction, the oxime body (7a) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the oxime body (7a) can also be increased by appropriately purifying by a usual means for purifying organic compounds such as distillation, column chromatography, recrystallization and the like.

(Process 4)
Step 4 includes the oxime (7a) obtained in Step 3 and the following general formula (8):
(In the formula, Y represents a halogen atom or —OC (═O) R ^1. R ¹ is as defined above, and preferred ones are also the same.)
The esterifying agent represented by the formula [hereinafter referred to as esterifying agent (8). And the following general formula (Ia):

(Wherein R ^{1 to} R ¹¹ and Ar are as defined above.)
[Hereinafter referred to as photopolymerization initiator (Ia). ] Is a step of obtaining.

In the above formula, examples of the halogen atom represented by Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
Although there is no restriction | limiting in particular in the usage-amount of the esterifying agent (8) used at the process 4, Preferably it is 0.5-2 mol with respect to 1 mol of oxime bodies (7a), More preferably, 0.8-1. From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially the same amount.
Step 4 may be performed in the presence of a base to promote the reaction. Examples of the base include organic bases and inorganic bases. Examples of the organic base include amines such as triethylamine and tributylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal hydroxides such as sodium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide Is mentioned. Among these, organic bases are preferable, amines and nitrogen-containing heterocyclic aromatic compounds are more preferable, and triethylamine and pyridine are more preferable from the viewpoint of reaction efficiency and production cost.
When a base is used, the amount used is preferably from 1 to 5 mol, more preferably from 1 mol of the oxime (7a), from the viewpoint of the yield of the photopolymerization initiator (Ia) and the production cost. Is 1.5-3 mol.

Step 4 is preferably performed in the presence of a solvent. Preferred examples of the solvent include ethers such as t-butyl methyl ether, ethyl methyl ether, cyclopentyl methyl ether, and tetrahydrofuran (THF).
The reaction temperature in step 4 is preferably −50 to 5 ° C. (preferably −10 to 5 ° C.) at the start of the reaction, and gradually returned to room temperature (about 15 to 25 ° C.) as the reaction proceeds. The reaction time varies depending on the type and amount of the oxime (7a) and esterifying agent (8), and the reaction temperature, but is usually preferably 0.5 to 10 hours, more preferably 1 to 5 hours. .
There is no restriction | limiting in particular in embodiment of process 4, For example, an oxime body (7a) and esterifying agent (8) are mixed in a solvent suitably, a base is dripped there, and the temperature of a reaction liquid is gradually made to drop after completion | finish of dripping. The photopolymerization initiator (Ia) can be obtained by returning to room temperature and continuing stirring.
After the completion of the reaction, the photopolymerization initiator (Ia) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the photopolymerization initiator (Ia) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

In the photopolymerization initiator (Ia) thus obtained, a special substituent containing an ester group is attached to the nitrogen atom in the carbazole skeleton. Therefore, compatibility with a compound having at least one polymerizable reactive group in the photosensitive resin composition (particularly a compound having a (meth) acryloyloxy group) or solubility in a compound having at least one polymerizable reactive group. I guess that is high. Therefore, it is thought that the sensitivity to light of the photosensitive resin composition, resolution, and deep part curability are increased. Furthermore, the composition has good adhesion to the substrate, but is excellent in peelability from the template after curing.
In addition, this photoinitiator (Ia) does not have the contamination of the polymer by the decomposition product generated with the light at the time of exposure, and contamination of an apparatus.

[2. Method for producing photopolymerization initiator (Ib)]
Although there is no restriction | limiting in particular in the manufacturing method of a photoinitiator (Ib), For example, it can manufacture easily by the following process 1-process 4.

(Process 1)
Since the manufacturing method of Step 1 is different depending on W and Z, each case will be described below.
<When W is a single bond and Z is> NR ³ '>
The following general formula (1)
(In the formula, R ^{6 to} R ¹¹ are as defined above, and preferred ones are also the same.)
[Hereinafter referred to as a carbazole derivative (1). And the following general formula (2b)

(In the formula, R ³ , R ³ ′, R ⁴ and R ⁵ are as defined above, and preferred ones are also the same.)
[Hereinafter referred to as acrylamide derivative (2b). And in the presence of a base, the following general formula (3b)

(In the formula, R ³ , R ³ ′ and R ^{4 to} R ¹¹ are as defined above, and preferred ones are also the same.)
[In the following, it is referred to as an amide group introduced product (3b). ] Is a step of obtaining.

Although there is no restriction | limiting in particular in the usage-amount of the acrylamide derivative (2b) used at the process 1, Preferably it is 0.5-2 mol with respect to 1 mol of carbazole derivatives (1), More preferably, it is 0.8-1.2. From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially equal amounts.
Step 1 is performed in the presence of a base. As the base, a base that can be used for the Michael addition reaction can be used, and there is no particular limitation, and either an organic base or an inorganic base can be used. Examples of the organic base include pyridine, diazabicycloundecene (DBU), diazabicyclononene (DBN), and the like. Bases with low nucleophilicity are preferable, and DBU and DBN are more preferable. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; Examples include alkali metal hydroxides such as sodium and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide. Among these, alkali metal carbonates and alkaline earth metal carbonates are preferable, alkali metal carbonates are more preferable, and potassium carbonate is more preferable.
Although there is no restriction | limiting in particular in the usage-amount of this base, From a viewpoint of reaction efficiency and manufacturing cost, Preferably it is 0.5-2 mol with respect to 1 mol of carbazole derivative (1), More preferably, it is 0.8-1. More preferably, it is 2 moles and is used in an approximately equal amount.
Step 1 is preferably performed in the presence of a solvent. What is necessary is just to select suitably the solvent which can melt | dissolve a carbazole derivative (1), an acrylamide derivative (2b), and a base as this solvent. Specific examples include dimethylformamide (DMF), dimethylsulfoxide (DMSO), methylene chloride and the like.

Although there is no restriction | limiting in particular in the reaction temperature of the process 1, Usually, it is preferably 10-50 degreeC, More preferably, it is 15-40 degreeC, More preferably, it implements at 15-30 degreeC. Although there is no restriction | limiting in particular in the reaction pressure, Implementing under 1 atmosphere, ie, a normal pressure, is preferable. The reaction time varies depending on the type and amount of the carbazole derivative (1), acrylamide derivative (2b) and base, reaction temperature, reaction pressure, etc., but it is usually preferably about 2 to 48 hours.
There is no restriction | limiting in particular in embodiment of process 1, For example, carbazole derivative (1), acrylamide derivative (2b), and a base are all added to a solvent, Preferably it is stirred at the said temperature, Amide group introduction body (3b) Can be manufactured.
After the completion of the reaction, the amide group-introduced product (3b) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the amide group-introduced product (3b) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

-Alternative method-
The following method can also be adopted for the production of the amide group-introduced product (3b).
The carbazole derivative (1) and the following general formula (2b ′)
(In the formula, R ⁴ and R ⁵ are as defined above. R ²⁴ represents an alkyl group having 1 to 5 carbon atoms.)
[Hereinafter referred to as a carboxylic acid group introducing agent (2b ′). ] In the presence of a base (first reaction)
(In the formula, R ^{4 to} R ¹¹ are as defined above, and preferred ones are also the same.)
In the presence of thionyl chloride, for example, HNR ³ R ³ ′ (R ³ and R ³ ′ are as defined above, and preferred ones are also the same). This is a method for obtaining an amide group-introduced product (3b) by reacting with the amine to be reacted (second reaction). A commercial item can also be used as this amide group introduction | transduction body (3b).
As the alkyl group having 1 to 5 carbon atoms represented by R ^24, a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, a t- butyl group and the like can be mentioned. Among these, a methyl group and an ethyl group are preferable.

There is no restriction | limiting in particular as a base used by said 1st reaction, Both an organic base and an inorganic base can be used. Examples of the organic base include pyridine, diazabicycloundecene (DBU), diazabicyclononene (DBN), and the like. Bases with low nucleophilicity are preferable, and DBU and DBN are more preferable. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; Examples include alkali metal hydroxides such as sodium and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide. Among these, as the base, an inorganic base is preferable, and an alkali metal hydroxide is more preferable.
Although there is no restriction | limiting in particular in the usage-amount of this base, From a viewpoint of reaction efficiency and manufacturing cost, Preferably it is 0.5-2 mol with respect to 1 mol of carbazole derivative (1), More preferably, it is 0.8-1. More preferably, it is 2 moles and is used in an approximately equal amount.
The first reaction is preferably carried out in the presence of a solvent. What is necessary is just to select suitably the solvent which can melt | dissolve a carbazole derivative (1), a carboxylic acid group introduction | transduction agent (2b '), and the said base as a solvent. Specific examples include dimethylformamide (DMF), dimethylsulfoxide (DMSO), methylene chloride and the like, and DMF is preferred.

Although there is no restriction | limiting in particular in the reaction temperature of 1st reaction, Preferably it is 10-50 degreeC, More preferably, it is 15-40 degreeC, More preferably, it implements at 15-30 degreeC. Although there is no restriction | limiting in particular in the reaction pressure of a 1st reaction, Implementing under 1 atmosphere, ie, a normal pressure, is preferable. The reaction time varies depending on the type and amount of the carbazole derivative (1) and base, the amount of the carboxylic acid group introducing agent (2b ′), the reaction temperature, the reaction pressure, and the like, but it is usually preferably 2 hours to 48 hours. It is about time.
There is no particular limitation on the embodiment of the first reaction. For example, the carbazole derivative (1), the carboxylic acid group introducing agent (2b ′) and the base are all added to the solvent, and preferably stirred at the above temperature to obtain the carboxylic acid. A group-containing carbazole derivative can be produced.
After completion of the first reaction, the carboxylic acid group-containing carbazole derivative can be obtained by an ordinary organic compound separation means such as extraction. The purity of the carboxylic acid group-containing carbazole derivative can be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

The amount of thionyl chloride used in the second reaction is preferably about 1 to 10 mol, more preferably about 2 to 5 mol, per 1 mol of the carbazole derivative (1) used in the first reaction. It is.
The amount of the amine represented by HNR ³ R ³ ′ used in the second reaction is preferably about 1 to 10 mol per 1 mol of the carbazole derivative (1) used in the first reaction, More preferably, it is about 2-7 mol.
The second reaction is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent capable of dissolving the carboxylic acid group-containing carbazole derivative and the amine. For example, dichloromethane, nitrobenzene, acetone, acetonitrile and the like can be mentioned, and acetonitrile is preferable.

Although there is no restriction | limiting in particular in the reaction temperature of 2nd reaction, Preferably it is 10-50 degreeC, More preferably, it is 15-40 degreeC, More preferably, it implements at 15-30 degreeC. Although there is no restriction | limiting in particular in the reaction pressure of a 2nd reaction, Implementing under 1 atmosphere, ie, a normal pressure, is preferable. The reaction time varies depending on the type and amount of the carboxylic acid group-containing carbazole derivative, amine and base, reaction temperature, reaction pressure, and the like, but is usually preferably about 1 hour to 10 hours.
The embodiment of the second reaction is not particularly limited. For example, the carboxylic acid group-containing carbazole derivative and the amine are added to a solvent, and thionyl chloride is added dropwise thereto. After completion of the addition, stirring is preferably performed at the temperature. By doing so, an amide group-introduced product (3b) can be produced.
After the completion of the reaction, the amide group-introduced product (3b) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the amide group-introduced product (3b) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

<When W is an oxygen atom and Z is a single bond>
The following general formula obtained by reacting the carbazole derivative (1) with ethylene carbonate in the presence of a base (first reaction).

(In the formula, R ^{6 to} R ¹¹ are as defined above, and preferred ones are also the same.)

In the presence of a base, the hydroxyl group-containing carbazole derivative is R ³ COY (where R ³ is as defined above, and the preferred one is also the same. Y represents a halogen atom). By reacting with the acyl halide represented (second reaction), the following general formula (3b ′)
(In the formula, R ^{3 to} R ¹¹ are as defined above, and preferred ones are also the same.)
An ester group-introduced body represented by the formula [hereinafter referred to as an ester group-introduced body (3b ′). ] Is preferable.

The amount of ethylene carbonate used in the first reaction is preferably 0.7 to 15 mol, more preferably 1 to 10 mol, relative to 1 mol of the carbazole derivative (1).
The base used in the first reaction is preferably an organic base, and examples thereof include amines such as triethylamine and tributylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine. Among these, amines are preferable, and triethylamine is more preferable. Although there is no restriction | limiting in particular in the usage-amount of this base, From a viewpoint of reaction efficiency and manufacturing cost, Preferably it is 0.5-2 mol with respect to 1 mol of carbazole derivative (1), More preferably, it is 0.8-1. More preferably, it is 2 moles and is used in an approximately equal amount.
The first reaction is preferably carried out in the presence of a solvent. What is necessary is just to select suitably the solvent which can melt | dissolve a carbazole derivative (1), ethylene carbonate, and the said base as a solvent. Specific examples include dimethylformamide (DMF), dimethylsulfoxide (DMSO), methylene chloride and the like, and DMF is preferred.

Although there is no restriction | limiting in particular in the reaction temperature of 1st reaction, Usually, it is preferably 60-130 degreeC, More preferably, it is 80-120 degreeC, More preferably, it implements at 90-110 degreeC. Although there is no restriction | limiting in particular in the reaction pressure of a 1st reaction, Implementing under 1 atmosphere, ie, a normal pressure, is preferable. The reaction time varies depending on the type and amount of the carbazole derivative (1) and base, the amount of ethylene carbonate used, the reaction temperature, the reaction pressure, and the like, but is usually preferably about 1 hour to 10 hours.
The embodiment of the first reaction is not particularly limited, and for example, the carbazole derivative (1), ethylene carbonate and base are all added to a solvent, and preferably stirred at the temperature to produce the hydroxyl group-containing carbazole derivative. be able to.
After the completion of the first reaction, the hydroxyl group-containing carbazole derivative can be obtained from the obtained reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the hydroxyl group-containing carbazole derivative can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

Examples of the acyl halide represented by R ³ COY used in the second reaction include acyl chloride and acyl iodide, and acyl chloride is preferred.
The amount of the acyl halide used is preferably about 0.7 to 3 moles, more preferably 1 to 2 moles per mole of the carbazole derivative (1) used in the first reaction. More preferably.
As the base used in the second reaction, for example, amines such as triethylamine, tributylamine and diisopropylethylamine are preferable. The amount of the base used is preferably about 0.7 to 3 mol, more preferably 1 to 2 mol, more preferably about 1 to 2 mol, relative to 1 mol of the acyl halide.
The second reaction is preferably carried out in the presence of a solvent. As the solvent, a solvent that can be used in a usual acylation reaction can be used, and there is no particular limitation as long as the reaction is not inhibited. Specific examples include dichloromethane, nitrobenzene, acetone, acetonitrile and the like, and acetonitrile is preferred.

Although there is no restriction | limiting in particular in the reaction temperature of 2nd reaction, Preferably it is 10-50 degreeC, More preferably, it is 15-40 degreeC, More preferably, it implements at 15-30 degreeC. Although there is no restriction | limiting in particular in the reaction pressure of a 2nd reaction, Implementing under 1 atmosphere, ie, a normal pressure, is preferable. The reaction time varies depending on the types and amounts of the hydroxyl group-containing carbazole derivative, acyl halide and base, reaction temperature, reaction pressure, and the like, but is usually preferably about 1 hour to 10 hours.
The embodiment of the second reaction is not particularly limited. For example, the hydroxyl group-containing carbazole derivative, the acyl halide, and the base are all added to a solvent, and preferably stirred at the temperature, thereby introducing an ester group-introduced product ( 3b ′) can be produced.
After completion of the reaction, an ester group-introduced product (3b ′) can be obtained from the resulting reaction mixture by a usual organic compound separation means such as extraction. The purity of the ester group-introduced product (3b ′) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

(Process 2)
In step 2, the amide group introduced product (3b) or ester group introduced product (3b ′) obtained in step 1 [hereinafter, these are collectively referred to as a functional group introduced product (3b) for convenience. ] And the following general formulas (4) and (5)
(In the formula, X represents a halogen atom or —OC (═O) Ar, and X ′ represents a halogen atom or —OC (═O) R ^2. Ar and R ² are as defined above. The preferred one is also the same.)
These are referred to as acylating agent (4) and acylating agent (5), respectively. In the presence of a Lewis acid, the following general formula (6b)

(In the formula, R ^{2 to} R ¹¹ , Ar, W and Z are as defined above, and preferred ones are also the same.)
[Hereinafter referred to as a diketone body (6b). ] Is a step of obtaining.

In the above formula, examples of the halogen atom independently represented by X and X ′ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferred.
In step 2, the reaction between the functional group-introduced product (3b) and the acylating agents (4) and (5) is performed in terms of the yield of the desired diketone product (6b). It is preferable to react the acylating agent (5) with the acylating agent (4).
The amount of the acylating agent (4) and (5) used is from the viewpoint of introducing each acyl group into the functional group-introduced body (3b) one by one with respect to 1 mol of the functional group-introduced body (3b). Preferably it is 0.8-1.3 mol, More preferably, it is 1-1.3 mol, and it is still more preferable to make it react in a substantially equal amount from a viewpoint of reducing an unreacted substance. In particular, when the functional group-introduced product (3b) and the acylating agent (4) are reacted, and then the acylating agent (5) is reacted, the amount of the acylating agent (5) used is within the above range. There is no problem if the amount exceeds the limit, but even if the amount is excessively large, the yield corresponding to that is not obtained, and the production cost may be unnecessarily high.
Step 2 is performed in the presence of a Lewis acid. As the Lewis acid, aluminum chloride and boron trifluoride diethyl ether complex are preferable. The amount of Lewis acid used is usually preferably from 0.8 to 2.5 mol, more preferably from 1 mol of the acylating agent (4) or (5) from the viewpoint of the yield of the diketone body (6b). Is 1-2 mol.

Step 2 is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent that can be used in a normal Friedel-Crafts acylation reaction. Specific examples include dichloromethane, nitrobenzene, acetone, acetonitrile and the like.
The reaction temperature in step 2 is preferably −50 to 5 ° C. (preferably −10 to 5 ° C.) at the start of the reaction, and gradually returned to room temperature (about 15 to 25 ° C.) as the reaction proceeds. The reaction time varies depending on the type and amount of the functional group-introduced product (3b), acylating agents (4) and (5), and the reaction temperature, but is usually preferably 1 to 30 hours. When both of the acylating agents (4) and (5) are acyl halides or acid anhydrides, after reacting the functional group-introducing body (3b) with the acylating agent (4), the product is It can also be reacted with the acylating agent (5) without isolation. In that case, the reaction time of the functional group-introduced body (3b) and the acylating agent (4) is about 30 minutes to 5 hours (preferably 30 minutes to 3 hours), while the functional group-introduced body (3b) and It is preferable that the reaction time with the acylating agent (5) is sufficiently long to be about 30 minutes to 24 hours (preferably 30 minutes to 18 hours) for sufficient reaction.

From the viewpoint of yield, one preferred embodiment of step 2 will be described. For example, the functional group-introducing body (3b) is appropriately mixed with a solvent while cooling in an ice bath, and the Lewis acid is slowly added to the mixed solution (preferably 5 minutes to 1 hour, more preferably 10 minutes to 40 minutes). After the addition, the acylating agent (4) is added slowly (preferably over 5 minutes to 1 hour, more preferably over 10 minutes to 40 minutes), and returned to room temperature for a certain time (30 minutes to 5 hours) Degree) Continue stirring. Again, the acylating agent (5) is added while cooling in an ice bath, and the Lewis acid is slowly added thereto (preferably over 5 minutes to 1 hour, more preferably over 10 minutes to 40 minutes). The diketone body (6b) can be obtained by returning to room temperature and continuing stirring for a certain period of time (about 30 minutes to 24 hours).
After completion of the reaction, the diketone body (6b) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the diketone body (6b) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

(Process 3)
Step 3 is a reaction of the diketone body (6b) obtained in Step 2 with hydroxylamine to give the following general formula (7b):
(In the formula, R ^{2 to} R ¹¹ , Ar, W and Z are as defined above, and preferred ones are also the same.)
[Hereinafter referred to as the oxime body (7b). ] Is a step of obtaining.

In step 3, the hydroxylamine source is not particularly limited, but hydroxylamine chloride is preferred. The hydroxylamine chloride can be reacted with, for example, sodium acetate in water to obtain an aqueous solution of hydroxylamine.
The amount of hydroxylamine (hydroxylamine chloride) to be used is preferably 0.8 to 2 mol, more preferably 1 to 1.5 mol, and still more preferably 1 to 1.3 mol, per 1 mol of the diketone body (6b). From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially equal amounts.
Step 3 is preferably performed in the presence of a solvent. As the solvent, a water-soluble organic solvent is preferable, and as the water-soluble organic solvent, for example, alcohols such as methanol and ethanol, dimethylformamide (DMF) and the like are preferable.

Although there is no restriction | limiting in particular in the reaction temperature of the process 3, From a viewpoint of the yield of an oxime body (7b), Usually, Preferably it is 40-160 degreeC, More preferably, it is 50-140 degreeC, More preferably, it is 70-110 degreeC. is there. Although reaction time changes also with the kind and usage-amount of diketone body (6b), and reaction temperature, Usually, it is preferably 0.5 to 20 hours, More preferably, it is 1 to 12 hours.
There is no particular limitation on the embodiment of Step 3. For example, hydroxylamine chloride and sodium acetate are mixed in water to obtain an aqueous solution of hydroxylamine, and a diketone (6b) and a solvent are added thereto, preferably An oxime body (7b) can be obtained by stirring in the said temperature range.
After completion of the reaction, the oxime body (7b) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the oxime body (7b) can also be increased by appropriately purifying by a usual means for purifying organic compounds such as distillation, column chromatography, recrystallization and the like.

(Process 4)
Step 4 includes the oxime body (7b) obtained in Step 3 and the following general formula (8):
(In the formula, Y represents a halogen atom or —OC (═O) R ^1. R ¹ is as defined above, and preferred ones are also the same.)
The esterifying agent represented by the formula [hereinafter referred to as esterifying agent (8). And the following general formula (Ib):

(Wherein R ^{1 to} R ¹¹ , Ar, W and Z are as defined above.)
Photopolymerization initiator represented by the formula [hereinafter referred to as photopolymerization initiator (Ib). ] Is a step of obtaining.

In the above formula, examples of the halogen atom represented by Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
Although there is no restriction | limiting in particular in the usage-amount of the esterifying agent (8) used at the process 4, Preferably it is 0.5-2 mol with respect to 1 mol of oxime bodies (7b), More preferably, it is 0.8-1. From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially the same amount.
Step 4 may be performed in the presence of a base to promote the reaction. Examples of the base include organic bases and inorganic bases. Examples of the organic base include amines such as triethylamine and tributylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal hydroxides such as sodium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide Is mentioned. Among these, organic bases are preferable, amines and nitrogen-containing heterocyclic aromatic compounds are more preferable, and triethylamine and pyridine are more preferable from the viewpoint of reaction efficiency and production cost.
When using a base in Step 4, the amount used is preferably 1 to 5 with respect to 1 mol of the oxime (7b) from the viewpoint of the yield of the photopolymerization initiator (Ib) and the production cost. Mol, more preferably 1.5 to 3 mol.

Step 4 is preferably performed in the presence of a solvent. Preferred examples of the solvent include ethers such as t-butyl methyl ether, ethyl methyl ether, cyclopentyl methyl ether, and tetrahydrofuran (THF).
The reaction temperature in step 4 is preferably −50 to 5 ° C. (preferably −10 to 5 ° C.) at the start of the reaction, and gradually returned to room temperature (about 15 to 25 ° C.) as the reaction proceeds. The reaction time varies depending on the type and amount of the oxime (7b) and esterifying agent (8), and the reaction temperature, but is usually preferably 0.5 to 10 hours, more preferably 1 to 5 hours. .
There is no restriction | limiting in particular in embodiment of process 4, For example, an oxime body (7b) and an esterifying agent (8) are mixed in a solvent suitably, a base is dripped there, and the temperature of a reaction liquid is gradually made to drop after completion | finish of dripping. By returning to room temperature and continuing stirring, the photopolymerization initiator (Ib) can be obtained.
After the completion of the reaction, the photopolymerization initiator (Ib) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the photopolymerization initiator (Ib) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

The photopolymerization initiator (Ib) thus obtained has a special substituent containing an ester group or an amide bond (or an amide bond forming a ring) on the nitrogen atom in the carbazole skeleton. Therefore, compatibility with a compound having at least one polymerizable reactive group in the photosensitive resin composition (particularly a compound having a (meth) acryloyloxy group) or solubility in a compound having at least one polymerizable reactive group. I guess that is high. Therefore, it is thought that the sensitivity to light of the photosensitive resin composition, resolution, and deep part curability are increased. Furthermore, the composition has good adhesion to the substrate, but is excellent in peelability from the template after curing.
In addition, this photoinitiator (Ib) does not have the contamination of the polymer by the decomposition product generated with the light at the time of exposure, and contamination of an apparatus.

[(B) Compound having one or more polymerizable reactive groups]
The photosensitive resin composition for optical imprinting of the present invention contains a compound having one or more polymerizable reactive groups as the component (B) together with the component (A). The compound having one or more polymerizable reactive groups is preferably a compound having one or more ethylenically unsaturated bond groups, an epoxy compound, a vinyl ether compound, or a styrene compound, and a compound having one or more ethylenically unsaturated bond groups. Is more preferable. As the ethylenically unsaturated bond group, a (meth) acryloyl group is preferable, and a (meth) acryloyloxy group is more preferable. In the compound having one or more ethylenically unsaturated bond groups, the number of ethylenically unsaturated bond groups is preferably 6 or less, and more preferably 5 or less.
The photosensitive resin composition for optical imprinting of the present invention contains at least one or more types as the component (B), and when two or more types of the component (B) are used, can function as a crosslinking agent or a reactive diluent. Things may be included. Needless to say, all are compounds having one or more polymerizable reactive groups.

Examples of the compound having one polymerizable reactive group include cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and adamantyl (meth). Acrylate, 3-hydroxyadamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, 2-acryloyloxyethyl phthalate, 2- Acryloyloxy 2-hydroxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl phthalate, 2-ethyl-2-butylpropanediol Relate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, acrylic acid dimer, aliphatic epoxy (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 3-phenylpropyl (meth) acrylate, phenoxyethyl (meth) acrylate, 9 -Anthrylmethyl (meth) acrylate, butanediol mono (meth) acrylate, butoxyethyl (meth) acrylate, butyl (meth) acrylate, caprolactone (meth) acrylate, cetyl (meth) acrylate Relate, ethylene oxide (hereinafter referred to as “EO”) modified cresol (meth) acrylate, dipropylene glycol (meth) acrylate, ethoxylated phenyl (meth) acrylate, ethyl (meth) acrylate, isoamyl (meth) acrylate, isobornyl ( (Meth) acrylate, isobutyl (meth) acrylate, isooctyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methyl (meth) acrylate, neopentyl glycol benzo Ate (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, octyl (meth) acrylate, paracumylphenoxyethylene glycol (meth) acrylate, epichlorohydrin modified phenoxy acrylate, phenoxyethyl (Meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polypropylene glycol ( (Meth) acrylate, stearyl (meth) Acrylate, EO-modified succinic acid (meth) acrylate, t-butyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, tribromophenyl ( (Meth) acrylate, EO-modified tribromophenyl (meth) acrylate, tridodecyl (meth) acrylate, trifluoroethyl (meth) acrylate, urethane mono (meth) acrylate, p-isopropenylphenol, 4-vinylpyridine, N-methylacrylamide N, N-dimethylacrylamide, N-acryloylmorpholine, N, N-diethylacrylamide, N-hydroxyethylacrylamide, N, N-dimethylaminoethyl ( Acrylate), diethylaminoethyl (meth) acrylate, N-cyclohexylmaleimide, styrene, α-methylstyrene, acrylonitrile, vinylcaprolactam, vinylcarbazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, imidoacrylate, vinyloxazoline , (Meth) acryloylmorpholine and the like, but are not particularly limited thereto.
As a compound having one polymerizable reactive group, a (meth) acrylic acid ester (preferably phenoxyethyl acrylate, 9-anthrylmethyl (meth) having at least an aromatic ring or an alicyclic skeleton is used from the viewpoint of dry etching resistance. ) Acrylate, isobornyl acrylate, dicyclopentenyloxy acrylate, dicyclopentenyloxyethyl acrylate).
Of the compounds having one polymerizable reactive group, a compound having a low viscosity (for example, a viscosity (25 ° C.) of 5 mPs or less) can function as a reactive diluent. As the reactive diluent, benzyl acrylate is preferred. When the viscosity of the photosensitive resin composition is high, the viscosity can be adjusted low by including a reactive diluent.

Examples of the compound having two polymerizable reactive groups include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and tricyclodecane dimethanol di (meth). Acrylate, diethylene glycol monoethyl ether (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, di (meth) acrylated isocyanurate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, 1,3-adamantyl diacrylate, 1,3-adamantane dimethanol diacrylate, EO modified 1 6-hexanediol di (meth) acrylate, epichlorohydrin modified 1,6-hexanediol di (meth) acrylate, allyloxy polyethylene glycol acrylate, 1,9-nonanediol di (meth) acrylate, EO modified bisphenol A di (Meth) acrylate, PO modified bisphenol A di (meth) acrylate, modified bisphenol A di (meth) acrylate, EO modified bisphenol F di (meth) acrylate, epichlorohydrin modified hexahydrophthalic acid diacrylate, hydroxypivalic acid neo Pentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, EO-modified neopentyl glycol diacrylate, propylene oxide (hereinafter referred to as “PO”) modified neo Nylglycol diacrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol, stearic acid-modified pentaerythritol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (Meth) acrylate, poly (propylene glycol-tetramethylene glycol) di (meth) acrylate, polyester diacrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, epichlorohydrin modified propylene glycol di (meth) ) Acrylate, silicone di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, Ripropylene glycol di (meth) acrylate, EO-modified tripropylene glycol di (meth) acrylate, triglycerol di (meth) acrylate, dipropylene glycol di (meth) acrylate, divinylethyleneurea, divinylpropyleneurea, N, N-methylene Although bisacrylamide is mentioned, it is not restricted to these in particular.
A compound having two or more polymerizable reactive groups can function as a crosslinking agent, and contributes to improvement in dry etching resistance. As the crosslinking agent, ethylene glycol diacrylate is preferred.

  Furthermore, examples of the compound having three or more polymerizable reactive groups include propane-1,2,3-triol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, epi Chlorohydrin modified glycerol tri (meth) acrylate, EO modified glycerol tri (meth) acrylate, PO modified glycerol tri (meth) acrylate, pentaerythritol triacrylate, EO modified phosphate triacrylate, caprolactone modified trimethylolpropane tri (meth) Acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, dipentaene Thritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, dipentaerythritol poly (meth) acrylate, alkyl Modified dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. are mentioned, but not particularly limited thereto. .

The molecular weight of component (B) (viscosity average molecular weight in the case of a polymer) is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1 from the viewpoint of the viscosity of the photosensitive resin composition. 1,000 or less, particularly preferably 500 or less.
As the component (B), the vapor pressure at 25 ° C. is preferably 5 Torr (about 666 Pa) or less, more preferably 1 Torr (about 133 Pa) or less, more preferably from the viewpoint of using the photosensitive resin composition for photoimprinting. Is 0.1 Torr (about 13.3 Pa) or less, particularly preferably 0.01 Torr (about 1.3 Pa) or less.
There is no restriction | limiting in particular in the measuring method of vapor pressure, What is necessary is just to employ | adopt a well-known method. Examples thereof include a static method, a boiling point method, an isoteniscope method, a gas flow method, a differential calorimetry (DSC) method, and an absolute method. In addition, the vapor pressure is described in the physical property database.

  In the photosensitive resin composition for optical imprints of the present invention, it is preferable to contain two or more types as the component (B), and to have a component that can function as a crosslinking agent or a reactive diluent. As a preferable use ratio, the crosslinking agent is 0 to 80% by mass (more preferably 1 to 50% by mass, more preferably 5 to 30% by mass), and the reactive diluent is 0 to 80% by mass (more preferably 1 to 50% by mass). 50 mass%, more preferably 5 to 45 mass%). The remainder may be referred to as a resist main monomer. By containing a crosslinking agent and a reactive diluent in the above range, the dry etching resistance of the photosensitive resin composition for photoimprinting is further improved.

[(C) Surfactant]
In the photosensitive resin composition of the present invention, the wettability of the photosensitive resin composition to the substrate or the adhesion layer laminated on the substrate, the filling property to the unevenness of the template, the photocured resin composition laminated on the substrate or substrate. In order to further improve the adhesion to the adhesion layer, the peeling force (release property) between the photocured resin composition and the template, a surfactant may be further contained as the component (C).
A known surfactant can be used as the surfactant, but a nonionic surfactant is preferable from the viewpoint of becoming a salt in the photocured resin composition and preventing it from becoming a foreign substance.
Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol Polyoxyethylene alkylaryl ethers such as ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene Polyoxyethylene sorbitan fatty acid esters such as sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, methyl perfluorooctanoate, methyl trifluoroacetate , Ethyl pentafluoropropionate, ethyl perfluorobutyrate, methyl pentafluorobenzoate, methyl 2,3,4,5,6-pentafluorophenyl acetate, methyl nonadecafluorodecanoate, trade name Florard FC-430, FC-431 (manufactured by Sumitomo 3M Limited), trade name Surflon "S-382" (manufactured by Asahi Glass Co., Ltd.), EFTOP "EF-122A, 122B, 122C, EF-121, EF-" 26, EF-127, MF-100 "(manufactured by Tochem Products Co., Ltd.), trade names PF-636, PF-6320, PF-656, PF-6520 (all of which are OMNOVA), trade names FT250, FT251 , DFX18 (all manufactured by Neos Co., Ltd.), trade names Unidyne DS-401, DS-403, DS-451 (all manufactured by Daikin Industries, Ltd.), trade names Megafuak 171, 172, 173, 178K, 178A, (any DIC Co., Ltd.), trade name SI-10 series (Takemoto Yushi Co., Ltd.), Megafuck Paintad 31 (DIC Co., Ltd.), KP-341 (Shin-Etsu Chemical Co., Ltd.), FZ-2191 (Toray Industries, Inc.) -Dow Corning Co., Ltd.), trade names X-70-090, X-70-091, X-70 -092, X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.), trade name Megafuk R-08, XRB-4 (all manufactured by DIC Corporation), 3, 3, 4, 4, 5, 5 , 6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heneicosafluorodecyl (meth) acrylate, 3,3,4,4,5 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12, 12-heneicosafluorododecyl (meth) acrylate, 2, 2, 3, 3 , 3-pentafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, 1H, 1H, 2H, 2H-perfluorodecyl (meth) acrylate, 2,2 , 2-Trifluoroethyl (meth) a Relate, 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro Heptyl (meth) acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7, 8,8,8-tridecafluorooctyl (meth) acrylate, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-hepta Examples include decafluorodecyl (meth) acrylate and (meth) acryl-modified silicone surfactants.
Of these, fluorine-based and / or silicone-based surfactants are preferable from the viewpoint of improving the peeling force (release property) between the cured resin and the template. In addition, in order to avoid remaining as an unreacted substance in the resin composition after photocuring, it is preferable to use those containing a polymerizable reactive group similar to the component (B) to be used.

If necessary, the photosensitive resin composition for photoimprinting of the present invention may further contain a photopolymerization initiator other than the photopolymerization initiator (I) and other components described later. The photosensitive resin composition thus obtained is useful for optical imprint applications.
In the photosensitive resin composition for photoimprinting of the present invention, the content of the photopolymerization initiator (I) as the component (A) is selected from the viewpoints of sensitivity and resolution, and the photosensitive resin composition for photoimprinting. Preferably it is 0.1-50 mass% with respect to the whole quantity, More preferably, it is 1-20 mass%, More preferably, it is 2-15 mass%, Most preferably, it is 2.5-10 mass%.
Moreover, when the photosensitive resin composition for photoimprints of this invention contains photoinitiators other than the said photoinitiator (I), photoinitiators other than the said photoinitiator (I) The content is not particularly limited as long as the effect of the present invention is not significantly inhibited, but is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, more preferably 100 parts by mass with respect to the photopolymerization initiator (I). Is 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less.

(Other ingredients)
If necessary, the photosensitive resin composition for photoimprinting of the present invention further includes a sensitizer; a mold release agent; an inorganic filler; a conductive compound; an adhesion promoter; an antioxidant; Stopper; chain transfer agent; leveling agent; plasticizer; antifoaming agent; silane coupling agent and the like may be contained. Any known one can be used.

(Physical properties and characteristics of photosensitive resin composition for photoimprint)
The photosensitive resin composition for photoimprinting of the present invention has a viscosity at 25 ° C. of 25 cPs or less, preferably 3 to 20 cPs, more preferably 3 to 15 cPs. Application in picoliter order is possible. In the present invention, the viscosity of the photosensitive resin composition is determined by using a rheometer “AR-G2” (manufactured by TA Instruments Inc.) to apply the photosensitive resin composition for photoimprinting on a disk plate. It is a value at 25 ° C. and 1000 (1 / s) when dripping and changing a standard steel cone having a diameter of 40 mm to a shear rate of 10 to 1000 (1 / s).
In addition, the photosensitive resin composition for optical imprinting of the present invention was dropped as a droplet of 40 ± 5 pl (picoliter) onto a 1.5 μl substrate having a pure water contact angle of 112 ° ± 5 °, and 1 atm. And the change in the diameter of the droplet (the diameter of the circle on the surface in contact with the substrate) when left at 25 ° C. for 1 minute is preferably within 15%, more preferably within 10%, and even more preferably 7%. %, Particularly preferably 5% or less. That is, it can be said that the volatile matter from the composition is extremely small or substantially absent, and substantially does not contain a general solvent (an organic solvent that does not cause a polymerization reaction). Therefore, even if droplets in the picoliter order are applied by the ink jet method, the composition change is extremely small or substantially absent, and the ink is applied as a photosensitive resin composition for photoimprinting, particularly using the ink jet method. It is suitable as a photosensitive resin composition for photoimprinting.
As will be described later, the photosensitive resin composition for optical imprinting of the present invention has a high filling property in the recesses of a template used when producing a resist substrate. That is, the details of the concave portion of the template are filled cleanly and quickly. Furthermore, the cured product after exposure has high releasability from commonly used templates (such as quartz templates) and has excellent substrate adhesion. At the same time, it has high strength and has very few curves and chips. The later cured product reproduces the concave portion of the template with extremely high accuracy and is excellent in resolution. When the photosensitive resin composition for optical imprinting of the present invention is used, a concave-convex shape (sometimes referred to as a pattern) in which the width of the concave portion or convex portion is 50 nm or less (about 20 to 40 nm) is clearly formed. Can do.
Further, since the photosensitive resin composition for optical imprinting and the cured product thereof according to the present invention have high dry etching resistance, even if the aspect ratio of the resist uneven shape (the ratio of the height of the convex portion to the lateral width of the convex portion) is small. There is a merit that it is good.

[Resist Substrate and Semiconductor Device Manufacturing Method]
In the present invention, “resist” means a photo-cured photosensitive resin composition, and “resist substrate” means irregularities formed by photo-curing the photosensitive resin composition on a substrate or an adhesion layer laminated on the substrate. This means that the shape (resist uneven shape) is formed.
There is no restriction | limiting in particular in the manufacturing method of a resist substrate and a semiconductor device, A well-known method is employable. For example, a method for manufacturing a resist substrate having the following steps (1) to (4) in this order, and a method for manufacturing a semiconductor device having the following steps (5) to (7), and further, step (8) in this order. Preferably mentioned.
(1) A step of adhering the photosensitive resin composition for optical imprinting of the present invention on the substrate or the adhesion layer laminated on the substrate by an ink jet method.
(2) From above the photosensitive resin composition attached in the step (1), a template having a concavo-convex shape is brought into contact with the substrate or an adhesion layer laminated on the substrate, and the concavo-convex shape is brought into contact with the substrate. A step of filling a photosensitive resin composition.
(3) The process which hardens the said photosensitive resin composition by exposure, and forms a resist uneven | corrugated shape on the contact | adherence layer laminated | stacked on the board | substrate or the board | substrate.
(4) The process of peeling a template from the board | substrate with which the resist uneven | corrugated shape was formed.
(5) In the resist substrate obtained by the manufacturing method described in the above steps (1) to (4), a step of performing dry etching processing on the concave portions of the resist uneven shape until the substrate is exposed.
(6) A step of further subjecting the exposed portion of the substrate appearing in the step (5) to dry etching to form a recess in the substrate itself.
(7) A step of removing the resist on the substrate, or a step of removing both the adhesion layer and the resist when the adhesion layer is laminated on the substrate.
(8) A step of removing a part of the layer when the substrate is composed of multiple layers.
Hereinafter, each process is demonstrated in order.

-Step (1)-
The substrate used in the step (1) may be appropriately selected from known materials depending on the application, and examples of the material include quartz (SiO ₂ ); metals such as nickel, copper, chromium, iron, molybdenum, and the like. Optical films; glasses such as soda glass, borosilicate glass, and blue glass; semiconductors such as silicon, silicon nitride, silicon oxide, amorphous silicon, gallium arsenide, and gallium nitride; Resin (film) such as polycarbonate, polypropylene, polyethylene, polyester, polyimide, etc .; conductive substrate such as indium tin oxide (ITO); insulating base material; composite materials composed of these combinations, etc. Is not to be done. Moreover, as a board | substrate used at a process (1), you may use what laminated | stacked these in multiple layers.
An adhesion layer may be laminated on the substrate. The adhesion layer is not particularly limited as long as it can improve the adhesion between the substrate and the photosensitive resin composition. For example, disilazan such as hexamethyldisilazane; silane coupling agent; acid anhydride; Treated with an adhesive such as phosphate ester, quartz (SiO ₂ ); silicon, silicon oxide; metals such as copper, chromium, iron, molybdenum, or oxides, nitrides, oxynitrides, silicon The thing which consists of a chemical compound etc. is mentioned. In particular, the resin composition preferably has one or more functional groups capable of reacting with the polymerizable reactive group. The compound having a functional group capable of reacting with the polymerizable reactive group is preferably an epoxy compound, a vinyl ether compound, or a styrene compound, and more preferably a compound having one or more ethylenically unsaturated bond groups. Those having a (meth) acryloyl group are more preferred, and those having a (meth) acryloyloxy group are particularly preferred. Examples of the compound having a functional group capable of reacting with a polymerizable reactive group include 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, acryloxymethyltrimethoxysilane, β-CEA (UCB Chemical), Ebecryl 3605 (UCB Chemical), Isorad501 (Scientady International, Inc), light ester P-disclosed in JP-A-2009-503139 At least one selected from the group consisting of 2M (manufactured by Kyoeisha Chemical Co., Ltd.) is preferred. These may be used individually by 1 type, may mix and use 2 or more types, and may use what superposed | polymerized. The adhesion layer may be laminated in multiple layers. The film thickness of the adhesion layer is preferably 20 nm or less, more preferably 10 nm or less, and further preferably 5 nm or less, from the viewpoint of adhesion performance and ease of dry etching in the step (5).
In the step (1), the photosensitive resin composition for optical imprinting of the present invention is adhered to the substrate or the adhesion layer laminated on the substrate by an inkjet method. In addition, it can be applied by a method such as spin coating, dip coating, ener knife coating, curtain coating, wire bar coating, gravure coating, etc., but from the viewpoint of filling into the recesses of the template, etc. An ink jet method is preferred. The ink jet method is not particularly limited, and deflection control type, divergence type, thermal ink jet method, piezo ink jet method, electrostatic suction method, electrostatic displacement method, acoustic energy method, thermal displacement method, bulb type, ERF ink jet, discharge method. Among them, the piezo ink jet method is particularly preferable in that it can deal with various inks and can discharge minute ink droplets.

-Step (2)-
In the step (2), the template having a concavo-convex shape is brought into contact with the photosensitive resin composition on the surface side having the concavo-convex shape, and the concave portion of the template is filled with the photosensitive resin composition.
As a template material, for example, silicon, quartz glass, silicate glass, calcium fluoride, blue plate glass, soda glass, BK-7, or the like can be used. Further, a resin film or porous alumina formed by an anodic oxidation method can be used. Etc. may be used.
The template may be a template subjected to a release treatment (provided with a release layer) in order to improve the peelability between the template and the photosensitive resin composition. For example, the template etc. which were processed with the disilazane, the silicone type, and the silane coupling agent are mentioned. Specifically, hexamethyldisilazane, Optool DSX (Daikin Industries), Novec EGC-1720 (Sumitomo 3M), Durasurf HD-1100 (harves), Durasurf HD-2100 (harves), (3, 3, 3 -Trifluoropropyl) trimethoxysilane (Gelest) and the like.
-Step (3)-
In the step (3), the photosensitive resin composition is cured by exposing from the template side.
The light used for the exposure is not particularly limited, and examples thereof include light or radiation having a wavelength in a region such as high energy ionizing radiation, vacuum ultraviolet light, near ultraviolet light, far ultraviolet light, visible light, and infrared light. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a cockcroft accelerator, a handagraaf accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, other radiations such as γ rays, X rays, α rays, neutron rays, proton rays emitted from radioisotopes and nuclear reactors can be used.
The radiation includes, for example, microwaves and EUV. In addition, semiconductor laser light, or laser light used in semiconductor microfabrication, such as 248 nm KrF excimer laser light or 193 nm ArF excimer laser, can also be suitably used in the present invention. These lights may be monochromatic lights, or may be lights having different wavelengths (mixed lights).
Among these, near ultraviolet rays and far ultraviolet rays are particularly preferable as light used for exposure, and examples of light sources include light emitting diodes (LEDs), low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps. A solar lamp or the like is preferable.
In the exposure, the illuminance is preferably 1 to 140 mW / cm ² from the viewpoint of shortening the exposure time, suppressing side reactions, and suppressing residual unreacted compounds. Further, the integrated light quantity is preferably 5 to 1,000 mJ / cm ² , more preferably 10 to 600 mJ / cm ² , and still more preferably 15 to 300 mJ / cm ² .
In addition, you may provide the process (process (3 ')) further hardened by applying heat after exposure. The heating temperature is preferably 80 to 280 ° C, more preferably 100 to 250 ° C, and still more preferably 130 to 250 ° C. The heating time is preferably 1 to 60 minutes, more preferably 10 to 40 minutes.
Since the photosensitive resin composition for optical imprinting of the present invention has a low curing shrinkage rate and high sensitivity, the unevenness of the template is clearly reproduced by this step.

-Step (4)-
Step (4) is a mold release step, and the template is pulled up and peeled off. The cured product of the photosensitive resin composition for optical imprinting of the present invention in which a resist concavo-convex shape is formed is excellent in peelability from the template, has excellent adhesion to the substrate, and has high strength, so that it adheres to the template. Thus, the resist uneven shape is prevented from being curved or chipped.

-Process (5), (6)-
Step (5) is a step of performing dry etching processing on the resist concave-convex recess until the substrate is exposed in the resist substrate obtained by the manufacturing method according to steps (1) to (4). Is a step of further subjecting the exposed portion of the substrate appearing in the step (5) to dry etching to form a recess in the substrate itself.
The dry etching process is usually performed using a dry etching apparatus. Any of an ion etching (IE) mode, an ICP etching mode, a reactive ion etching (RIE) mode, and a plasma etching (PE) mode may be used.
As the etchant gas, a gas suitable for the film to be etched may be used. Examples of the etchant gas include oxygen, chlorine + oxygen, carbon tetrafluoride + trifluoride methane for resist and adhesion layer; carbon tetrafluoride (for a-Si / n ⁺ and s-Si) ( Or chlorine) + oxygen, carbon tetrafluoride (or sulfur hexafluoride) + hydrogen chloride (or chlorine); for a-SiNx, carbon tetrafluoride + oxygen; for a-SiOx, carbon tetrafluoride + Oxygen, methane trifluoride + oxygen; for Ta, carbon tetrafluoride (sulfur hexafluoride) + oxygen; for MoTa / MoW, carbon tetrafluoride + oxygen; for Cr, chlorine + oxygen , Carbon tetrafluoride + methane trifluoride; for Al, boron trichloride + chlorine, hydrogen bromide, hydrogen bromide + chlorine, hydrogen iodide; for quartz, carbon tetrafluoride + trifluoromethane Is mentioned.

-Steps (7), (8)-
In the step (7), the resist on the substrate is removed, or when the adhesion layer is laminated on the substrate, the adhesion layer and the resist are removed together.
As a method of removing the resist and the adhesion layer, a wet stripping method using a stripping solution, a method of removing the gas by oxidizing with a plasma discharge of oxygen gas under reduced pressure, and a gas by oxidizing with ozone and ultraviolet rays. For example. Examples of stripping solutions include aqueous hydrogen peroxide solution, aqueous hydrogen peroxide solution, aqueous hydrogen peroxide solution, aqueous solution of hydrochloric acid and hydrogen peroxide, aqueous solution of sodium hydroxide and potassium hydroxide, amine such as monoethanolamine, dimethyl sulfoxide, An organic solvent-based stripping solution such as a mixture with N-methylpyrrolidone can be used.
In step (8), when the substrate is composed of multiple layers, a part of the layer is removed. “Part of the layer” refers to, for example, an upper layer in the case of two layers, and a layer other than the lowest layer in the case of three or more layers. As a method for removing a part of the layer when the substrate is composed of multiple layers, a wet stripping method using a stripping solution may be used. As the stripping solution, a sodium hydroxide aqueous solution, (hot) phosphoric acid, a hydrofluoric acid solution or an ammonium fluoride solution, “secondary ammonium nitrate + perchloric acid aqueous solution” or the like can be used.
As described above, a substrate useful for a semiconductor device to which the uneven shape of the template is transferred is manufactured.
The manufacturing of the semiconductor device is not limited to the above steps, and may further include other known semiconductor device manufacturing steps.

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.

<Synthesis Example 1>
(Process 1)
Carbazole (6.8 g, 40 mmol), ethyl acrylate (4.0 g, 40 mmol) and potassium carbonate (5.5 g, 40 mmol) were suspended in dimethylformamide (DMF) and stirred at room temperature for 24 hours. After completion of the reaction, water was added and the mixture was further stirred for 30 minutes, and then extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off and dried, whereby the above compound as a pale yellow liquid was obtained. (I) 9.6 g (93% yield) was obtained. The ¹ H-NMR measurement results of the compound (i) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.15 (t, 3H), 2.835 (t, 2H), 4.08 (q, 2H), 4.64 (t, 3H) ), 7.215-7.254 (m, 2H), 7.45-7.47 (m, 4H), 8.08 (d, 2H)

(Process 2)
2.7 g (10 mmol) of compound (i) was dissolved in 10 ml of dichloromethane, and 2.7 g (20 mmol) of aluminum chloride was added over 20 minutes while cooling with an ice bath. Benzoyl chloride 1.4g (11mmol) was dripped at the obtained mixed solution over 20 minutes. Thereafter, the mixture was gradually returned to room temperature and stirred for 1 hour. While cooling in an ice bath again, 2.7 g (20 mmol) of aluminum chloride was added over 20 minutes, and 1.2 g (15 mmol) of acetyl chloride was added dropwise thereto over 20 minutes. Thereafter, the mixture was gradually returned to room temperature and stirred overnight. After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off.
The product was isolated by silica gel column chromatography (eluent: dichloromethane → normal hexane: ethyl acetate = 2: 1) to obtain 2.8 g (yield 70%) of compound (ii) as a pale yellow solid. The ¹ H-NMR measurement result of the compound (ii) is shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.16 (t, 3H), 2.725 (s, 3H), 2.91 (t, 2H), 4.08 (q, 2H) ), 4.73 (t, 2H), 7.525-7.86 (m, 5H), 8.10 (dd, 2H), 8.18 (dd, 1H), 8.20 (dd, 1H) 8.625 (d, 1H), 8.725 (d, 1H)

(Process 3)
0.12 g (1.7 mmol) of hydroxylamine chloride and 0.17 g (2.0 mmol) of sodium acetate were dissolved in 1.4 ml of water, and 0.60 g (1.58 mmol) of compound (ii) and 11 ml of ethanol were added thereto. And refluxed for 7 hours.
After completion of the reaction, the solvent of the reaction solution was distilled off, and the resulting solid was washed with water, dissolved in THF, dried over magnesium sulfate, and the solvent was distilled off to give a pale yellow liquid compound (iii ) 0.60 g (89% yield) was obtained. The ¹ H-NMR measurement results of the compound (iii) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.16 (t, 3H), 2.41 (s, 3H), 2.89 (t, 2H), 4.09 (q, 2H) ), 4.69 (t, 2H), 7.475-7.63 (m, 5H), 7.85 (dd, 1H), 8.045 (dd, 2H), 8.07 (dd, 1H) 8.325 (d, 1H), 8.60 (d, 1H)

(Process 4)
0.60 g (1.4 mmol) of compound (iii) is dissolved in 7 ml of t-butyl methyl ether, 0.11 g (1.4 mmol) of acetyl chloride is added, and 0.28 ml (2.0 mmol) of triethylamine is added while cooling in an ice bath. ) Was added dropwise. The mixture was stirred for 3 hours while gradually returning to room temperature. After completion of the reaction, the reaction mixture was poured into ice water, extracted with ethyl acetate, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off. The product was isolated by silica gel column chromatography (eluent: dichloromethane → normal hexane: ethyl acetate = 2: 1) to obtain 0.30 g (yield 70%) of a light yellow solid compound (iv). The physical properties of the compound (iv) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.16 (t, 3H), 2.23 (s, 3H), 2.51 (s, 3H), 2.90 (t, 2H) ), 4.09 (q, 2H), 4.71 (t, 2H), 7.51-7.62 (m, 5H), 7.75 (dd, 2H), 7.99 (dd, 1H) 8.09 (dd, 1H), 8.46 (d, 1H), 8.59 (d, 1H)
UV spectrum (moving layer; acetonitrile): λmax = 260 nm, 292 nm, 333 nm
Thermal decomposition temperature (temperature at which a 1.5 mg sample is heated at a heating rate of 10 ° C./min under a nitrogen gas atmosphere and the mass is reduced by 5%): 224.5 ° C.
Molecular weight: 470.52

<Synthesis Example 2>
In Step 1 of Synthesis Example 1, isobutyl acrylate (40 mmol) was used instead of ethyl acrylate (40 mmol), and in Step 2, 2-methylbenzoyl chloride (11 mmol) was used instead of benzoyl chloride (11 mmol). The same operation as in Example 1 was performed to obtain the following pale yellow solid compound (v). The physical properties of the compound (v) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 0.81 (d, 6H), 1.805 (m, 1H), 2.29 (s, 3H), 2.35 (s, 3H) ), 2.50 (s, 3H), 2.90 (t, 2H), 3.81 (d, 2H), 4.70 (t, 2H), 7.28-7.53 (m, 6H) 7.97 (dd, 1H), 8.10 (dd, 1H), 8.42 (d, 1H), 8.51 (d, 1H)
UV spectrum (moving layer; acetonitrile): λmax = 260 nm, 295.5 nm, 334 nm
Thermal decomposition temperature (temperature at which a 1.5 mg sample was heated at a rate of temperature increase of 10 ° C./min and reduced by 5% in a nitrogen gas atmosphere): 236 ° C.
Molecular weight: 512.6

<Synthesis Example 3>
In Step 1 of Synthesis Example 1, 2-methoxyethyl acrylate (40 mmol) was used instead of ethyl acrylate (40 mmol), and in Step 2, 2-methylbenzoyl chloride (11 mmol) was used instead of benzoyl chloride (11 mmol). Except for this, the same operation as in Example 1 was carried out to obtain the following pale yellow solid compound (vi). The physical properties of the compound (vi) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 2.29 (s, 3H), 2.35 (s, 3H), 2.50 (s, 3H), 2.95 (t, 2H) ), 3.32 (s, 3H), 3.50 (t, 2H), 4.19 (t, 2H), 4.70 (t, 2H), 7.30-7.54 (m, 6H) 7.97 (dd, 1H), 8.10 (dd, 1H), 8.42 (d, 1H), 8.51 (d, 1H)
UV spectrum (moving layer; acetonitrile): λmax = 258.5 nm, 296 nm, 334.5 nm
Thermal decomposition temperature (temperature at which a 1.5 mg sample was heated at a heating rate of 10 ° C./min under a nitrogen gas atmosphere and the mass decreased by 5%): 243 ° C.
Molecular weight: 514.5

<Synthesis Example 4>
(Process 1)
Dissolve 5.0 g (30 mmol) of carbazole in 6 ml of dimethylformamide (DMF), add 13.2 g (150 mmol) of ethylene carbonate and 5.5 ml (037 mmol) of diazabicycloundecene (DBU) and add at 100 ° C. for 3 hours. Heated to reflux. After cooling, water was added, extracted with ethyl acetate, washed with water, and then the solvent was distilled off.
Next, the obtained concentrate was diluted with 15 ml of acetonitrile, 2 g (23 mmol) of acetyl chloride and 4 ml (29 mmol) of triethylamine were added thereto, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, water was added, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and the solvent was distilled off to obtain 6.0 g (yield) of the above compound (vii) as a pale yellow liquid. 80%).

(Process 2)
Compound (vii) (2.5 g, 9.9 mmol) was dissolved in dichloromethane (10 ml), and aluminum chloride (1.5 g) was added over 20 minutes while cooling in an ice bath. Thereafter, 1.4 g (10.0 mmol) of benzoyl chloride was added dropwise, and after gradually returning to room temperature, the mixture was stirred for 1 hour.
While cooling in an ice bath again, 1.5 g of aluminum chloride was added over 20 minutes, 0.93 g (11.8 mmol) of acetyl chloride was added thereto, and the mixture was gradually returned to room temperature and stirred for 1 hour.
After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off.
The compound was isolated by silica gel column chromatography (eluent: dichloromethane → normal hexane: ethyl acetate = 2: 1) to obtain 2.8 g (yield 70%) of a light yellow solid compound (viii).

(Process 3)
Hydroxylamine chloride (0.38 g, 5.4 mmol) and sodium acetate (0.54 g, 6.4 mmol) were dissolved in water (4.5 ml), and the compound (viii) (2.0 g, 5.0 mmol) and ethanol (35 ml) were added thereto. Added and refluxed for 2 hours.
After completion of the reaction, the solvent of the reaction solution was distilled off, and the resulting solid was washed with water, dissolved in THF, dried over magnesium sulfate, and the solvent was distilled off to obtain a compound (ix ) 1.8 g (yield 89%) was obtained.

(Process 4)
Compound (ix) 0.8 g (2.0 mmol) is dissolved in t-butyl methyl ether 10 ml, 0.16 g (2.0 mmol) of acetyl chloride is added, and triethylamine 0.4 ml (2. 9 mmol) was added dropwise. The mixture was stirred for 3 hours while gradually returning to room temperature.
After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off.
The compound was isolated by silica gel column chromatography (eluent: dichloromethane → normal hexane: ethyl acetate = 2: 1) to obtain 0.6 g (yield 70%) of a light yellow solid compound (x) having the following physical properties.

(Physical properties of compound (x))
¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.93 (s, 3H), 2.50 (s, 3H), 2.85 (s, 3H), 4.31 (t, 2H) ), 4.40 (t, 2H), 7.50-7.62 (m, 5H), 7.75 (dd, 2H), 7.99 (dd, 1H), 8.09 (dd, 1H) 8.46 (d, 1H), 8.59 (d, 1H)
UV spectrum (moving layer; acetonitrile): λmax = 260 nm, 296 nm, 334 nm
Thermal decomposition temperature (temperature at which a 1.5 mg sample is heated at a heating rate of 10 ° C./min under a nitrogen gas atmosphere and the mass is reduced by 5%): 225 ° C.
Molecular weight: 456.49

<Synthesis Example 5>
(Process 1)
After dissolving 0.96 g (40 mmol) of 9-carbazole-9-propionic acid in 10 ml of acetonitrile, 18 g (210 mmol) of morpholine was added. To the obtained mixture, 14 g (120 mmol) of thionyl chloride was added dropwise and stirred at room temperature for 3 hours.
After completion of the reaction, water was added and stirred for 30 minutes. Thereafter, the mixture was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain 10 g (yield 81%) of a light yellow liquid compound (xi).

(Process 2-4)

  As in the above chemical reaction formula, the same operations are performed in Steps 2 to 4 of Synthesis Example 5 except that Compound (xi) was used in Step 2 instead of Compound (vii) in Steps 2 to 4 of Synthesis Example 4. Was employed to obtain a light yellow solid compound (xii) having the following physical properties.

(Physical properties of compound (xii))
¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 2.50 (s, 3H), 2.80 (t, 2H) 2.85 (s, 3H), 2.90 (br, 2H) 3.00 (br, 2H), 3.35 (br, 2H), 3.46 (br, 2H) 4.72 (t, 2H), 7.51-7.62 (m, 5H), 7 .75 (dd, 2H), 7.99 (dd, 1H), 8.09 (dd, 1H), 8.46 (d, 1H), 8.59 (d, 1H)
UV spectrum (moving layer; acetonitrile): λmax = 260 nm, 292 nm, 335 nm
Thermal decomposition temperature (temperature when a 1.5 mg sample is heated at a rate of temperature increase of 10 ° C./min under a nitrogen gas atmosphere and the mass is reduced by 5%): 234 ° C.
Molecular weight: 511.57

<Examples 1-5, Comparative Examples 1 and 2> Compatibility (Solubility) Test As a compound having one or more polymerizable reactive groups, dicyclopentenyloxyethyl acrylate ((B) having one or more polymerizable reactive groups) Compound), the photopolymerization initiator (compounds (iv) to (vi), (x) and (xii)) obtained in Synthesis Examples 1 to 5, and the following photopolymerization initiator “IRGACURE OXE02” (Ciba Specialty Chemicals) Co., Ltd., for Comparative Test Example 1. Hereinafter, it may be abbreviated as “OXE02”) or the following photopolymerization initiator “N-1919” (manufactured by ADEKA, for Comparative Test Example 2). Mix and stir for 2 minutes. The mixing ratio of the dicyclopentenyloxyethyl acrylate and the photopolymerization initiator is 5.6% by mass of the photopolymerization initiator with respect to 100% by mass of the dicyclopentenyloxyethyl acrylate.
Here, the presence or absence of a solid in the mixture obtained by visual inspection is confirmed, and an indicator of compatibility (solubility) with a compound having at least one polymerizable reactive group (particularly a compound having a (meth) acryloyloxy group). It was. The results are shown in Table 1.

  From Table 1, the photopolymerization initiator (I) used in the present invention is a solvent-free photosensitive resin composition having high compatibility with a compound having one or more polymerizable reactive groups, particularly (meth) acrylate. It is possible to prepare. On the other hand, it was found that the photopolymerization initiators used in Comparative Examples 1 and 2 have insufficient compatibility or solubility with respect to (meth) acrylate, and there are restrictions on the use conditions.

Moreover, the viscosity, sensitivity, volatility, cure shrinkage rate and etching resistance were evaluated by the following methods.
(viscosity)
With a rheometer “AR-G2” (manufactured by TA Instruments Inc.), a photosensitive resin composition for photoimprinting is dropped on a disk plate, and a standard steel cone having a diameter of 40 mm is sheared at a rate of 10 to 1000 ( The value at 25 ° C. and 1000 (1 / s) was taken as the measurement value.
(sensitivity)
0.3 μL of photosensitive resin for photoimprinting was dropped on the substrate, and 5 mm square KBr was covered from above, and UV exposure was performed from the KBr side with an illuminance of 20 mW / cm ² under a nitrogen atmosphere. The amount of peak decrease of 810 cm ⁻¹ was recorded over time with an infrared spectrometer, and it was confirmed how much the disappearance of the C═C bond of the acrylic monomer had progressed (reaction rate). When the reaction rate was 80% The exposure amount was defined as sensitivity.
(volatility)
The droplet when the photosensitive resin composition for photoimprinting is dropped as a 40 ± 5 pl (picoliter) droplet on a substrate using an inkjet apparatus and left at 1 atm and 25 ° C. for 1 minute. The change of the diameter of was investigated. The substrate used was a 1.5 μl pure water contact angle of 112 ° ± 5 °. The change in the diameter of the droplet was calculated based on the photographed image.
(Curing shrinkage)
Using an atomic force microscope (AFM), the height (h ₁ ) of the resist line pattern having a line width of 32 nm obtained by transfer and the space depth (h ₀ ) of the template used were measured, and {(h ₀ − The cure shrinkage was determined from the formula h ₁ ) / h ₀ } × 100 (%).
(Etching resistance)
After forming a resist film according to each example, etching was performed using an ICP type dry etching apparatus (etchant gas: mixed gas of oxygen and chlorine). The amount of reduction of the resist film per unit time (etching rate [nm / sec]) was calculated from the resist film thickness before and after etching, and the relative value when the etching rate of ZEP520A was set to 1 was obtained and used as an index of etching resistance. ZEP520A is a positive resist for EB (electron beam direct pathology), and is generally known as a positive resist having high etching resistance. When the relative value is smaller than 1, it can be said that the etching resistance is higher than ZEP520A.

<Example 6> Formation of a resist pattern having a line width of 50 nm or less One polymerizable reactive group consisting of three types of dicyclopentenyloxyethyl acrylate, ethylene glycol diacrylate (crosslinking agent) and benzyl acrylate (reactive diluent) Two or more compounds and the photopolymerization initiator (compound (iv)) obtained in Synthesis Example 1 were mixed to obtain a photosensitive resin composition for photoimprinting. The mixing ratio of the compound having one or more of three kinds of polymerizable reactive groups and the photopolymerization initiator is as follows: dicyclopentenyloxyethyl acrylate, ethylene glycol diacrylate, benzyl acrylate, photopolymerization initiator (compound (iv)) In order, they are 41.4 mass%, 18.3 mass%, 34.7 mass%, and 5.6 mass%.
Each of the obtained photosensitive resin compositions was applied onto a chromium oxynitride / quartz substrate on which an adhesion layer (3-acryloxypropyltrimethoxysilane, trade name: KBM-5103) manufactured by Shin-Etsu Chemical Co., Ltd. was laminated. . Next, the uneven surface of the template which has an unevenness | corrugation of a line and space line width of 24 nm or 32 nm was made to contact. From the template side, an ultraviolet ray was irradiated (exposed) at an illuminance of 20 mW / cm ² and an integrated light amount of 100 mJ / cm ² to form a resist pattern, and the template was peeled off.
Next, by using an ICP type dry etching apparatus (etchant gas: mixed gas of oxygen and chlorine), the concave portion was dry etched until the substrate was exposed, and further dry etched to the substrate portion as it was. Next, the resist and the adhesion layer were peeled off with a sulfuric acid hydrogen peroxide aqueous stripping solution), and then the chromium oxynitride on the quartz substrate was peeled and washed with ceric ammonium nitrate + perchloric acid aqueous solution, and the uneven shape was transferred. A substrate (semiconductor device) was obtained. Table 2 shows the evaluation results of viscosity, sensitivity, volatility, cure shrinkage, and etching resistance.
SEM photographs of the resist pattern obtained by the above method are shown in FIGS. It can be seen that fine resist patterns with line widths of 24 nm and 32 nm are clearly formed. This is because the photosensitive resin composition is highly compatible with a compound having one or more polymerizable reactive groups in the photosensitive resin composition or highly soluble in a compound having one or more polymerizable reactive groups, A photosensitive resin composition containing a photopolymerization initiator with high sensitivity to light and excellent in resolution and deep part curability, and has high filling properties in the recesses of the template, while the cured product after exposure is peeled off from the template It shows that the photosensitive resin composition is excellent in adhesiveness and adhesion to the substrate, has very little unevenness or curvature of the cured product, has a low curing shrinkage, and is excellent in dry etching resistance.

<Examples 7 to 10, Comparative Examples 3 and 4>
In Example 6, the same operation was performed except that the photopolymerization initiator shown in Table 2 was used instead of the photopolymerization initiator (compound (iv)) obtained in Synthesis Example 1. Table 2 shows the evaluation results of viscosity, sensitivity, volatility, cure shrinkage, and etching resistance.

From Table 2, the photosensitive resin composition containing the photopolymerization initiator represented by the general formula (I) has low viscosity, high sensitivity, low volatility and curing shrinkage, and high etching resistance. It was.
On the other hand, the photosensitive resin composition containing the conventional photopolymerization initiator was poor in sensitivity as compared with the photosensitive resin composition of the present invention.

  The photosensitive resin composition of the present invention is a photopolymerization initiator that is highly compatible with a compound having one or more polymerizable reactive groups or highly soluble in a compound having one or more polymerizable reactive groups and has high sensitivity to light. Is a photosensitive resin composition excellent in resolution and deep part curability, and has a high filling property in the recesses of the template, while the cured product after exposure has excellent peelability from the template and adhesion to the substrate. It is a photosensitive resin composition that is excellent in resistance, has very little unevenness or curvature of the cured product, has a low cure shrinkage, and is excellent in dry etching resistance. Therefore, it can be effectively used as a photosensitive resin composition for photoimprinting.

Claims (8)

(A) A photopolymerization initiator represented by the following general formula (I) and (B) a photoimprinting photosensitivity containing a compound having one or more polymerizable reactive groups and having a viscosity at 25 ° C. of 25 cPs or less. Resin composition.
Wherein R ^{1 to} R ¹¹ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, Or an unsubstituted cycloalkyl group having 3 to 10 ring atoms, a substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or Unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted ring forming carbon number .R ³ showing a 6-14 aryl group, or a substituted or unsubstituted heterocyclic group ring atoms 3-14, to form a ring together with R ⁴ or R ⁵ Good .R ⁴ may form a ring together with R ^5.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
W represents a single bond or an oxygen atom. Z represents a single bond, an oxygen atom, or> NR ³ ′ (R ³ ′ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ³ ′ is connected to R ³ together with a nitrogen atom. Forming a ring).
n represents an integer of 1 to 10. When n is an integer of 2 to 10, a plurality of R ⁴ and R ⁵ may be the same or different. )   The photosensitive resin composition for optical imprinting according to claim 1, wherein the photosensitive resin composition is 40 ± 5 pl (picoliter) on a substrate having a pure water contact angle of 112 ° ± 5 ° of 1.5 μl. The photosensitive resin composition for photoimprinting, wherein the change in the diameter of the droplets is within 15% when dropped at 1 atm and 25 ° C. for 1 minute. ^{3. The} general formula (I) according to claim 1, wherein Z is an oxygen atom, and R ³ is an alkyl group having 1 to 20 carbon atoms substituted with an alkoxy group having 1 to 18 carbon atoms. Photosensitive resin composition for optical imprint.   Furthermore, the photosensitive resin composition for optical imprints in any one of Claims 1-3 which contains surfactant as (C) component.   The photosensitive resin composition for optical imprints in any one of Claims 1-4 whose said (B) component is a compound which has a (meth) acryloyl group.   Hardened | cured material obtained by exposing the photosensitive resin composition for optical imprints in any one of Claims 1-5. The manufacturing method of a resist substrate which has the following process (1)-(4) in this order.
(1) The process which adheres the photosensitive resin composition in any one of Claims 1-5 on the board | substrate or the adhesion layer laminated | stacked on the board | substrate by the inkjet system.
(2) From above the photosensitive resin composition attached in the step (1), a template having a concavo-convex shape is brought into contact with the substrate or an adhesion layer laminated on the substrate, and the concavo-convex shape is brought into contact with the substrate. A step of filling a photosensitive resin composition.
(3) The process which hardens the said photosensitive resin composition by exposure, and forms a resist uneven | corrugated shape on the contact | adherence layer laminated | stacked on the board | substrate or the board | substrate.
(4) The process of peeling a template from the board | substrate with which the resist uneven | corrugated shape was formed. The manufacturing method of a semiconductor device which has the following process (5)-(7) in this order.
(5) In the resist substrate obtained by the manufacturing method according to claim 7, the step of dry etching the concave portions of the concave and convex shapes of the resist until the substrate is exposed.
(6) A step of further subjecting the exposed portion of the substrate appearing in the step (5) to dry etching to form a recess in the substrate itself.
(7) A step of removing the resist on the substrate, or a step of removing both the adhesion layer and the resist when the adhesion layer is laminated on the substrate.