KR101965095B1 - A composition for forming an adhesion layer, a method for producing a cured product, a method for producing an optical component, a method for producing a circuit board, a method for manufacturing an imprint mold, and a device part - Google Patents

Abstract

The adhesive layer-forming composition contains either or both of an alkoxyalkyl group and an alkylol group, and the number of alkoxyalkyl groups and alkylol groups per molecule or the number of alkoxyalkyl groups and alkylol groups per molecule is at least 5 A specific compound (A), and a compound (B) containing at least two thiol groups per molecule.

Description

A composition for forming an adhesion layer, a method for producing a cured product, a method for producing an optical component, a method for producing a circuit board, a method for manufacturing an imprint mold, and a device part

The present invention relates to a composition for forming an adhesion layer, a method for producing a cured product, a method for producing an optical component, a method for producing a circuit board, a method for manufacturing an imprint mold, and a device component.

BACKGROUND ART [0002] In semiconductor devices, microelectromechanical systems (MEMS) and the like, there is an increasing demand for microfabrication. In particular, optical nanoimprint technology is attracting attention.

In the photo-nanoimprint technique, a mold having a fine concavo-convex pattern on its surface is pressed against a substrate such as a substrate (wafer) coated with a photo-curable composition (resist), and the photo-curable composition is cured. Thereby, the concavo-convex pattern of the mold is transferred to the cured film of the photo-curable composition to form the concavo-convex pattern on the substrate. The optical nanoimprint technique can form a fine structure of several nanometers order on a substrate.

In the photo-nanoimprint technique, the photo-curable composition is applied to the pattern formation region of the substrate (batch step). The photocurable composition is then molded using a patterned mold (mold contacting step). The photo-curable composition is cured (photoirradiation step) by irradiating light to the photo-curable composition, followed by release (release step). Through these steps, a pattern of resin (photopolymerization) having a predetermined shape is formed on the substrate.

In the release step of the photo-nanoimprint technique, the adhesion between the photocurable composition and the substrate is important. When the adhesion between the photo-curable composition and the substrate is low, in the operation of separating the mold in the mold-releasing step, a part of the photo-cured product obtained by curing the photo-curable composition is peeled off while adhering to the mold, In some cases.

Conventionally, as a technique for improving the adhesion between the photocurable composition and a substrate, there has been proposed a technique for forming an adhesion layer between the photocurable composition and the substrate to adhere the photocurable composition to the substrate (Patent Document 1).

Japanese Patent Application Laid-Open No. 2013-202982

In the technique disclosed in Patent Document 1, an adhesive layer is formed using a composition containing a curable base resin and a urea crosslinking agent. However, since the composition contains a urea crosslinking agent, the curability of the composition is insufficient to form the adhesive layer. Therefore, there is a problem that the adhesion between the photocurable composition and the substrate can not be sufficiently improved, and a pattern peeling defect occurs.

In view of the above circumstances, the present invention provides an adhesive layer-forming composition capable of suppressing the occurrence of pattern peeling defects.

The present invention relates to a compound having at least one of an alkoxyalkyl group and an alkylol group per molecule and a total number of alkoxyalkyl groups and alkylol groups per molecule of at least 5, (A), and a compound (B) containing at least two thiol groups per molecule.

Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the accompanying drawings.

1 (a) is a schematic cross-sectional view showing a method of manufacturing a cured product pattern according to an embodiment of the present invention.
Fig. 1 (b) is a schematic cross-sectional view showing a method for producing a cured product pattern.
Fig. 1 (c) is a schematic cross-sectional view showing a method for producing a cured product pattern.
1 (d) is a schematic cross-sectional view showing a method for producing a cured product pattern.
1 (e) is a schematic cross-sectional view showing a method for producing a cured product pattern.
1 (f) is a schematic cross-sectional view showing a method for producing a cured product pattern.
FIG. 1 (g) is a schematic cross-sectional view showing a method for producing a cured product pattern.
1 (h) is a schematic cross-sectional view showing a method for producing a cured product pattern.

Now, embodiments of the present invention will be described in detail. The present invention is not limited to the embodiments. Modifications and improvements made to the embodiments based on the knowledge of those skilled in the art without departing from the spirit of the present invention are also included within the scope of the present invention.

The adhesive layer forming composition 100 according to one embodiment of the present invention is a composition for forming the adhesive layer 101 between the base material 102 and the photocurable composition 103. [ The adhesive layer-forming composition (100) contains one or both of an alkoxyalkyl group and an alkylol group, and the number of the alkoxyalkyl groups and alkylol groups per molecule or the number of alkoxyalkyl groups and alkylol groups per molecule A compound (A) having at least 5 in total, and a compound (B) containing at least two thiol groups per molecule.

The adhesive layer forming composition 100 is preferably used in such a manner that the adhesive layer forming composition 100 is disposed on the substrate 102 and cured to form a photo-cured product. The laminate including the adhesive layer 101 and the base material 102 obtained by curing the adhesive layer forming composition 100 is a laminate comprising the photo-cured product 109 obtained by arranging the photo-curing composition 103 on the laminate, Can be preferably used as a base material for obtaining a base material. The adhesion layer forming composition (100) can be used as a composition for forming an adhesion layer for imprinting, and is particularly useful as a composition for forming a contact layer for a light nanoimprint.

Hereinafter, the components contained in the adhesive layer-forming composition (100) will be described in detail.

The compound (A)

The compound (A) contains one or both of an alkoxyalkyl group and an alkylol group (hereinafter referred to as " functional group a "), and the number of alkoxyalkyl groups and alkylol groups per molecule or alkoxyalkyl And the number of the alkylol groups is at least 5 in total.

The functional group a contained in the compound (A) is a functional group that reacts with the thiol group contained in the compound (B) in the following step of forming the adhesion layer. Thus, a bond is formed between the compound (A) and the compound (B). Since the compound (A) contains the functional group a, each molecule of the compound (A) can be bonded to a plurality of molecules of the compound (B). Since each molecule of the compound (A) can be bonded to a plurality of molecules of the compound (B), a structure (crosslinked structure) in which the compounds forming the adhesive layer 101 are crosslinked with each other can be formed.

The reaction between the functional group a contained in the compound (A) and the thiol group contained in the compound (B) is preferably generated by a heating process in the adhesion layer formation step.

The amount of the free unreacted compound (A) or (B) that is not bonded to the base material 102 can be reduced by forming the adhesion layer 101 to have a crosslinked structure as described above. This enables the strength of the adhesion layer 101 to be improved.

When the unreacted compounds (A) and (B) are present in the adhesive layer 101 in a free state, the unreacted compounds (A) and (B) 103). ≪ / RTI > As a result, the composition of the photo-curing composition 103 is changed, and therefore, the characteristics of the photo-curing composition 103 are changed. For example, the photo-curing composition 103 obtained by curing the photo- Lt; / RTI >

However, the use of the adhesion layer forming composition 100 makes it possible to significantly reduce the amount of the free glass compound (A) or (B) that is not bonded to the base material 102, as compared with the prior art. This makes it possible to significantly inhibit the elution of the compound (A) or (B) in the photo-curable composition 103 in the step of arranging the photo-curing composition 103. As a result, it is possible to suppress the occurrence of pattern peeling defects and the like in the photocatalyst 109.

The functional group a contained in the compound (A) may form an interaction or a chemical bond such as a covalent bond, an ionic bond, a hydrogen bond, or an intermolecular force with a functional group present on the base material 102. For example, when the substrate 102 has a hydroxyl group such as a silanol group on the surface, a dealcoholation reaction occurs between the alkoxyalkyl group and the silanol group. Therefore, a covalent bond can be formed between the compound (A) and the substrate 102. This makes it possible to improve the adhesion between the adhesive layer 101 and the substrate 102. [

The compound (A) is preferably a compound represented by the following formula (1).

≪ Formula 1 >

In formula (1), R ₁ to R ₆ independently represent a hydrogen atom, an alkyl group, an alkoxyalkyl group or an alkylol group, and at least five of R ₁ to R ₆ are an alkoxyalkyl group or an alkylol group.

The compound represented by Formula 1 is a derivative of melamine containing a triazine ring at the center of its structure. That is, the compound represented by Chemical Formula 1 has a structure in which each nitrogen atom is bonded to one of the 2-, 4-, and 6-positions of 1,3,5-triazine. The compound represented by the general formula (1) contains 5 or 6 functional groups a. That is, the compound represented by Formula 1 contains a larger number of functional groups a than urea compounds such as glycoluril derivatives.

The urea compound contains an electron-withdrawing oxygen atom in the molecule. Therefore, the reactivity of the functional group a contained in the functional group a-containing urea compound with the thiol group or the like tends to be lower than that in the case of not containing the electron-withdrawing oxygen atom in the molecule. However, the triazine ring is the nucleus of the compound represented by the formula (1) and contains no electron-withdrawing oxygen atom in the structure. Therefore, the functional group a contained in the compound represented by the formula (1) will probably have a higher reactivity than the functional group a in such a urea compound.

From the above, it can be seen that the use of the compound (A) represented by the general formula (1) enables the adhesive layer-forming composition (100) to have improved curability, Thereby enabling the strength of the layer 101 to be improved.

The kind of the alkoxyalkyl group or alkylol group contained in the compound (A) is not particularly limited. The alkoxyalkyl group is preferably a methoxymethyl group, and the alkylol group is preferably a methylol group. Use of a functional group having a low chemical formula as an alkoxyalkyl group or an alkylol group makes it possible to improve the crosslinking density per unit mass of the adhesive layer 101 and thus to improve the strength of the adhesive layer 101 do.

Examples of the compound (A) include pentamethoxymethylmelamine, hexamethoxymethylmelamine, (hydroxymethyl) pentakis (methoxymethyl) melamine, hexaethoxymethylmelamine, hexabutoxymethylmelamine, pentamethylolmelamine, And hexamethylol melamine, but are not limited thereto.

The compound (A) may be composed of a single kind of compound, or may be composed of many kinds of compounds.

The compound (B)

The compound (B) of the present invention is a compound containing at least two thiol groups in the molecule.

The thiol group contained in the compound (B) is a functional group which reacts with the functional group a contained in the compound (A) as described above. Thus, a bond is formed between the compound (A) and the compound (B). Since the compound (B) contains a thiol group, each molecule of the compound (B) can be bonded to a plurality of molecules of the compound (A). Since each molecule of the compound (B) can be bonded to a plurality of molecules of the compound (A), a structure (crosslinked structure) in which the compounds forming the adhesive layer 101 are crosslinked with each other can be formed.

The amount of the free unreacted compound (A) or (B) that is not bonded to the base material 102 can be reduced by forming the adhesion layer 101 to have a crosslinked structure as described above. This enables the substrate 102 to have an enhanced strength and is capable of significantly inhibiting the elution of the compound (A) or (B) in the photo-curable composition 103 in the placement step of the photo- do. As a result, it is possible to suppress the occurrence of pattern peeling defects and the like in the photocatalyst 109.

The thiol group contained in the compound (B) may form an interaction or a chemical bond such as a covalent bond, a hydrogen bond, or an intermolecular force with the functional group present on the substrate (102). This makes it possible to improve the adhesion between the adhesive layer 101 and the substrate 102. [

The thiol group contained in the compound (B) is contained in the photocurable composition (103) through a chain transfer reaction between the thiol group contained in the compound (B) and the radical generated in the photocurable composition (103) Bonded to the polymerizable compound. This makes it possible to improve the adhesion between the adhesive layer 101 and the photo-curing composition 103 or the photo-cured product 109. [ The adhesion layer 101 may form a chemical bond or interaction with the substrate 102 as described above and thus improve the adhesion between the substrate 102 and the photocurable composition 103 or the photocurable 109 .

In order to exhibit the above effect, the number of thiol groups contained in the compound (B) is preferably large, more preferably at least three, and still more preferably at least four. When the number of thiol groups contained in the compound (B) is at least 3, the crosslinked structure formed by the compound (B) is three-dimensional, and the adhesive layer 101 has an improved strength. Further, the compound (B), the compound (A) and the substrate 102 are easily bonded to each other. The larger the number of thiol groups contained in the compound (B), the more remarkable the above effect is. Therefore, the number of thiol groups contained in the compound (B) is preferably at least 4.

The compound (B) is preferably a primary thiol. When the compound (B) is a primary thiol, steric hindrance around the thiol group contained in the compound (B) can be reduced. As a result, the reactivity of the thiol group contained in the compound (B) can be enhanced, and the curability of the adhesive layer-forming composition 100 can be improved.

Examples of the compound (B) include 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 1,4-butanediol bis (thioglycolate) Bifunctional thiol compounds such as 3-mercaptobutyryloxy) butane; 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, trimethylolpropane tris (3- Mercapto propionate), and trifunctional thiol compounds such as pentaerythritol tris (3-mercaptobutyrate); (3-mercaptobutyrate), pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetrakis (mercaptoacetate), and pentaerythritol tetrakis (3-mercaptopropionate) But is not limited thereto.

The compound (B) may be composed of a single kind of compound, or may be composed of many kinds of compounds.

The compounding ratio of the compound (A) and the compound (B)

When the blending ratio of the compound (A) or (B) in the adhesive layer-forming composition (100) is extremely small, the adhesive layer (101) has reduced crosslink density, insufficient strength and insufficient curing ability. Therefore, when the weight percentage of the compound (A) is? (%) And the weight fraction of the compound (B) is? (%) When the entirety of the adhesion layer forming composition 100 is 100% Is preferably 1: 9 to 9: 1, more preferably 1: 4 to 4: 1. That is, the ratio? /? Is preferably 0.11 or more and 9 or less, more preferably 0.25 or more and 4 or less. The optimum mixing ratio of the compound (A) and the compound (B) varies depending on the number of the functional groups of the compounds (A) and (B) and the molecular weight and reactivity, Making it possible to improve the curability of the forming composition (100).

The mixing ratios (sum of? And?) Of the compounds (A) and (B) in the adhesive layer forming composition 100 can be appropriately adjusted according to the viscosity of the adhesive layer forming composition 100, the target thickness of the adhesive layer 101, have. The sum of? and? is preferably 0.01 or more and 10 or less, more preferably 0.1 or more and 10 or less, still more preferably 0.1 or more and 7 or less. Adjustment of the compounding ratio of the compounds (A) and (B) in the adhesive layer-forming composition (100) within the above range makes it possible to lower the viscosity of the adhesive layer- It is possible to reduce the thickness of the film.

The volatile solvent (C)

The adhesion layer-forming composition (100) further contains a volatile solvent (C) (hereinafter simply referred to as "solvent (C)"). Since the adhesive layer-forming composition 100 contains the solvent (C), the viscosity of the adhesive layer-forming composition 100 can be lowered. As a result, the applicability of the adhesive layer-forming composition 100 to the substrate 102 can be improved.

The solvent (C) is not particularly limited, but the compound (A) and the compound (B) can be dissolved. The solvent (C) preferably has a boiling point at atmospheric pressure of from 80 캜 to 200 캜. The solvent (C) is preferably an organic solvent having at least one of a hydroxy group, an ether structure, an ester structure and a ketone structure. Such a solvent (C) is excellent in dissolving the compound (A) and the compound (B), and has excellent wettability with respect to the base material (102).

Examples of the solvent (C) include alcohol solvents such as propyl alcohol, isopropyl alcohol, and butyl alcohol; Ether solvents such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether; Ester solvents such as butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate; And ketone solvents such as methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone,? -Butyrolactone, and ethyl lactate. These solvents may be used singly or in combination. Particularly, a mixture containing propylene glycol monomethyl ether acetate or propylene glycol monomethyl ether acetate is preferable from the viewpoint of coatability.

The compounding ratio of the solvent (C) in the adhesive layer forming composition (100) is appropriately adjusted according to the viscosity of the compounds (A) and (B), the coating properties of the compounds (A) and (B) . The mixing ratio of the solvent (C) in the adhesive layer-forming composition (100) is preferably 70% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more with respect to the amount of the adhesive layer- %. The greater the proportion of the solvent (C) in the adhesive layer-forming composition 100, the lower the thickness of the adhesive layer 101, which is preferable for the composition for forming an adhesion layer for imprints. When the compounding ratio of the solvent (C) in the adhesive layer-forming composition (100) is less than 70% by mass, sufficient coating properties may not be obtained. The upper limit of the mixing ratio of the solvent (C) is not particularly limited. The upper limit of the mixing ratio of the solvent (C) is preferably 99.9% by mass or less, more preferably 99% by mass or less.

Another component (D)

The adhesive layer forming composition 100 may further contain, in addition to the compound (A), the compound (B) and the solvent (C), the component (D) . Examples of the component (D) include a surfactant, a crosslinking agent, a polymer component, an oxidation inhibitor, and a polymerization inhibitor. The adhesive layer forming composition 100 is placed on the base material 102 and then cured while evaporating the solvent C by heating so that the thickness of the adhesive layer 101 can be reduced. Therefore, it is preferable that the adhesion layer-forming composition 100 does not contain any photopolymerization initiation system used for the purpose of curing the adhesion layer-forming composition 100 by light irradiation. When the adhesive layer-forming composition 100 contains a photopolymerization initiator, the adhesive layer-forming composition 100 is cured before photopolymerization occurs and the solvent (C) completely volatilizes during the formation of the adhesive layer 101; Therefore, there is a possibility that the thickness of the adhesive layer 101 is increased.

Viscosity of the adhesive layer-forming composition

The viscosity of the adhesive layer-forming composition 100 varies depending on the kinds and blending ratios of the components such as the compound (A), the compound (B) and the solvent (C). The viscosity of the adhesive layer forming composition 100 is preferably from 0.5 to 20 milli-pascals-sec, more preferably from 1 to 10 mPas-sec at 23 ° C, 1 milli-pascal-second and more than 5 milli-pascal-second.

When the viscosity of the adhesive layer-forming composition 100 is 20 milli-pascals-second or less, the applicability of the adhesive layer-forming composition 100 to the substrate 102 is excellent. Therefore, the thickness of the layer of the adhesion layer forming composition 100 disposed on the base material 102 can be easily adjusted.

Impurities incorporated into the adhesive layer-forming composition

The adhesive layer-forming composition (100) is preferably substantially free of impurities. As used herein, the term " impurity " refers to compounds other than compounds (A), (B), (C) and (D). When the adhesive layer-forming composition 100 is used in a nanoimprint process, the adhesive layer-forming composition 100 particularly preferably does not contain any of particles and solid components. The term " particle " as used herein refers to a gel or solid particulate material typically having a size (diameter) of from several nanometers to several micrometers. Therefore, the content of particles having a size larger than 0.2 占 퐉 in the adhesive layer-forming composition 100 is preferably 0% by mass or more and less than 3% by mass based on 100% by mass of the entire adhesive layer forming composition 100.

Thus, the adhesion layer-forming composition 100 is preferably obtained through a purification step. In such a purification step, filtration using a filter or the like is preferably performed.

Specifically, the mixture obtained by mixing the compound (A), the compound (B), the solvent (C) and the component (D) to be added as required is preferably used, for example, with a pore size of 0.001 filtration through a filter of not less than μm but not more than 5.0 μm. More preferably, the mixture is filtered through a filter having a pore size of 0.001 μm or more and 0.2 μm or less. It is more preferable to perform the filtration using the filter in a plurality of stages or by repeating the use of the filter many times. The filtrate can be filtered again. A plurality of filters having different hole sizes may be used for filtration. The filter used for the filtration is not particularly limited, but it may be made of a polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin or the like.

Through such a purification step, impurities such as particles incorporated in the adhesive layer-forming composition 100 can be removed. This makes it possible to prevent inadvertent occurrence of defects in the adhesive layer 101 obtained by applying the adhesive layer forming composition 100. [

When the adhesive layer-forming composition 100 is used for producing a circuit board for use in a semiconductor device such as a semiconductor integrated circuit, an impurity (metal impurity) containing a metal atom is mixed in the adhesive layer- Preferably as much as possible. This is because impurities such as metals prevent the operation of the circuit board from being hindered. In such a case, the concentration of the metal impurity in the adhesion layer-forming composition 100 is preferably 10 ppm or less, more preferably 100 ppb or less.

Thus, the adhesion layer forming composition 100 is preferably manufactured without contacting the metal in the manufacturing step. That is, when the raw materials of the compound (A), the compound (B), the solvent (C) and optionally the component (D) to be added are weighed, compounded and mixed together, preferably a metal weighing device or container Do not use. In the purification step, filtration is preferably performed using a metal impurity removal filter. The metal impurity removal filter is not particularly limited, but may be a filter made of cellulose and diatomaceous earth, an ion exchange resin, or the like. The metal impurity removal filter is preferably used after cleaning. The cleaning method is preferably as follows: washing with ultrapure water, washing with alcohol, and washing with the adhesive layer forming composition 100 are performed in this order.

Photo-curing composition

The photo-curable composition 103 used together with the adhesive layer 101 formed from the adhesive layer-forming composition 100 usually contains a component (E) which is a polymerizable compound and a component (F) which is a photopolymerization initiator.

Component (E): Polymerizable compound

Component (E) is a polymerizable compound. As used herein, the term " polymerizable compound " refers to a compound that reacts with polymerization initiators (such as radicals) generated from a photopolymerization initiator (component (F)) to form a film made of a polymer compound ≪ / RTI >

Component (E) may be composed of a single kind of polymerizable compound or may be composed of plural kinds of polymerizable compounds.

As such a polymerizable compound, for example, a radical polymerizable compound can be mentioned. The radical polymerizable compound is preferably a compound containing at least one acryloyl group or methacryloyl group, that is, a (meth) acrylic compound.

Therefore, the component (E) which is a polymerizable compound preferably contains a (meth) acrylic compound. The main component of the component (E) is more preferably a (meth) acrylic compound. Component (E) is most preferably a (meth) acrylic compound. As used herein, the expression " the main component of component (E) is a (meth) acrylic compound " means that at least 90% by weight of component (E) is a (meth) acrylic compound.

When the radically polymerizable compound is composed of a plurality of kinds of compounds containing at least one acryloyl group or methacryloyl group, the radical polymerizable compound is preferably a monofunctional (meth) acrylate monomer and a polyfunctional Meth) acrylate monomer. This is because a cured film having high strength can be obtained by using a combination of a monofunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer.

Examples of monofunctional (meth) acrylic compounds containing one acryloyl group or methacryloyl group include phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxyethoxy (Meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (Meth) acrylate of EO-modified p-cumylphenol, 2-bromophenoxyethyl (meth) acrylate, 2,4-dibromo Modified phenoxy (meth) acrylate, PO-modified phenoxy (meth) acrylate, polyoxyethylene (meth) acrylate, Nonylphenyl ether (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) Acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (Meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, Hexyl (meth) acrylate, heptyl (meth) acrylate, (Meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (Meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylate, 2-naphthylmethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (Meth) acrylate, methoxyethylene (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene (meth) acrylate, (Meth) acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, (Meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl Amide, and N, N-dimethylaminopropyl (meth) acrylamide.

Examples of the monofunctional (meth) acrylic compound include Aronix M101, Aronix M102, Aronix M110, Aronix M111, Aronix M101 commercially available from Toagosei Co., Ltd. Products such as Knicks M113, Aronix M117, Aronix M5700, TO1317, Aronix M120, Aronix M150, and Aronix M156; MEDOL 10, MIBDOL 10, CHDOL 10, MMDOL 30, MEDOL 30, MIBDOL 30, CHDOL 30, LA, IBXA, 2-MTA, HPA, and bis (2-hydroxyethyl) amine, which are commercially available from Osaka Organic Chemical Industry Ltd. Viscoat # 150, Viscoat # 150, Viscoat # 150, Viscoat # 150, Biscoat # 155, Biscoat # 158, Biscoat # 190, Biscoat # 192, Biscoat # 193, Biscoat # 220, Biscoat # # 2150; Light Acrylate BO-A, Light Acrylate EC-A, Light Acrylate DMP-A, Light Acrylate (commercially available from Kyoeisha Chemical Co., Ltd.) Light acrylate HOP-A, light acrylate HOA-MPE, light acrylate HOA-MPL, light acrylate PO-A, light acrylate P-200A, light acrylate NP-4EA, light acrylate NP -8EA, and EPOXY ESTER M-600A; Products such as KAYARAD TC110S, Kayalad R-564, and Kayalad R-128H, which are commercially available from Nippon Kayaku Co., Ltd.; Products such as NK ester AMP-10G and NK ester AMP-20G, which are commercially available from Shin-Nakamura Chemical Co., Ltd.; Products such as FA-511A, FA-512A, and FA-513A, which are commercially available from Hitachi Chemical Co., Ltd.; PHE-2, PHE-4, BR-31, BR-31M and BR-32 commercially available from Dai-ichi Kogyo Seiyaku Co., Products such as; VPs commercially available from BASF; And products such as ACMO, DMMA, and DMAPAA, which are commercially available from Kohjin Co., Ltd., but are not limited thereto.

Examples of the polyfunctional (meth) acrylate compound containing two or more acryloyl groups or methacryloyl groups include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane (Meth) acrylate, trimethylolpropane trimethacrylate, tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-PO modified trimethylolpropane tri (meth) acrylate, dimethylol tricyclodecane diacrylate, (Meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, p-xylylene di (meth) acrylate, p-xylylene di (meth) acrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (acryloyloxy) isocyanurate (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified 2,2-bis (4- ( (Meth) acryloxy) phenyl) propane, PO modified 2,2-bis (4 - ((meth) acryloxy) phenyl) propane, and EO- ) Phenyl) propane, but are not limited thereto.

Examples of the polyfunctional (meth) acrylic compound include products such as YUPIMER UV, Yupimer SA1002, and Yupimer SA2007 commercially available from Mitsubishi Chemical Corporation; Biscot # 230, Viscot # 215, Viscot # 260, Viscot # 335HP, Viscot # 295, Viscot # 300 and Viscot # 360, commercially available from Osaka Organic Chemical Industries, Products such as Viscot # 700, Viscot GPT, and Viscot 3PA; A, light acrylate NP-A, light acrylate DCP-A, light acrylate BP-4EA, and light acrylate commercially available from Kyoeisha Chemical Co., Ltd. Products such as Late BP-4PA, light acrylate TMP-A, light acrylate PE-3A, light acrylate PE-4A, and light acrylate DPE-6A; Products such as A-DCP, A-HD-N, A-NOD-N, and A-DOD-N commercially available from Shin-Nakamura Chemical Co., Ltd.; GAYARADD DPCA-30, GAYARAD DPCA-60, GAYARADD R-604, GAYARAD DPHA, GAYARAD DPCA-20, GAYARAD DPCA-60, Products such as Kayalad DPCA-120, Kayalad HX-620, Kayalad D-310, and Kayalad 330; Aronix M205, Aronix M215, Aronix M220, Aronix M240, Aronix M305, Aronix M309, Aronix M310, Aronix M315, Aronix M325 commercially available from Toagosei Co., Ltd. , And Aronix M400; And products such as Ripoxy VR-77, Lipoxy VR-60, and Lipoxy VR-90 commercially available from Showa Denko KK. Do not.

In such compounds, the term " (meth) acrylate " refers to acrylate or methacrylate containing alcohol residues equivalent to acrylate; The term " (meth) acryloyl group " refers to an acryloyl group, or a methacryloyl group containing an alcohol moiety equivalent to an acryloyl group, wherein EO represents ethylene oxide; The term " EO modified compound A " refers to a compound wherein the (meth) acrylic acid moiety and the alcohol moiety of Compound A are linked together through a block structure of an ethylene oxide group; PO represents propylene oxide; The term " PO modifying compound B " refers to a compound in which the (meth) acrylic acid moiety and the alcohol moiety of compound B are linked to each other through a block structure of a propylene oxide group.

Component (F): A photopolymerization initiator

Component (F) is a photopolymerization initiator. The term " photopolymerization initiator " as used herein refers to a compound that absorbs light of a predetermined wavelength to generate polymerization factors (radicals). In particular, the photopolymerization initiator is a polymerization initiator (radical generator) that absorbs light (a charged particle beam such as an infrared ray, a visible ray, an ultraviolet ray, a deep ultraviolet ray, an X ray, an electron beam, or a radiation) to generate a radical. More particularly, the photopolymerization initiator is a polymerization initiator that generates radicals by absorbing light having a wavelength of 150 nm or more and 400 nm or less, for example.

Component (F) may be composed of a single type of photopolymerization initiator, or may be composed of plural kinds of photopolymerization initiators.

Examples of the radical generator include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer , 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- 2,4,5-triarylimidazole dimer such as methoxyphenyl) -4,5-diphenylimidazole dimer; Benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, Benzophenone derivatives such as? -Dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, and 4,4'-diaminobenzophenone; Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-l- - < / RTI > aminoaromatic ketone derivatives such as < RTI ID = Dianthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-di (tert-butylanthraquinone) 2-methyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethyl Quinones such as anthraquinone; Benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether; Benzoin derivatives such as benzoin, methylbenzoin, ethylbenzoin, and propylbenzoin; Benzyl derivatives such as benzyl dimethyl ketal; Acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane; N-phenylglycine derivatives such as N-phenylglycine; Acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzylketal, 1-hydroxycyclohexyl phenyl ketone, and 2,2-dimethoxy-2-phenylacetophenone; Thioxanthone derivatives such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; Acylphosphine oxide derivatives such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide; (2-methylbenzoyl) -9H-carbaldehyde, 1- [4- (phenylthio) -, 2- Oxazol-3-yl] -, 1- (O-acetyloxime); Xanthone; Fluorenone; Benzaldehyde; Fluorene; Anthraquinone; Triphenylamine; Carbazole; 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one; And 2-hydroxy-2-methyl-1-phenylpropan-1-one. The 2,4,5-triarylimidazole dimer may contain a substituent.

Examples of the radical generators include Irgacure 184, Irgacure 369, Irgacure 651, Irgacure 500, Irgacure 819, Irgacure 907, Irgacure 784 commercially available from BASF , Irgacure 2959, Irgacure CGI-1700, Irgacure CGI-1750, Irgacure CGI-1850, Irgacure CG24-61, Darocure 1116, But are not limited to, products such as TPO, lucylline LR 8893, and lucylline LR 8970, and Uvecryl P36 commercially available from UCB.

The proportion of the component (F) in the photocurable composition (103) is preferably 0.01 wt% or more and 10 wt% or less, more preferably 0.1 wt% or more and 7 wt% or less based on the amount of the component (E).

When the proportion of the component (F) in the photocurable composition (103) is 0.01% by weight or more based on the amount of the component (E), the curing rate of the photocurable composition (103) is high and the reaction efficiency can be improved It becomes. When the compounding ratio of the component (F) in the photo-curing composition (103) is 10.0% by weight or less based on the amount of the component (E), the mechanical strength of the obtained cured film (109,110) is often prevented from being lowered.

Another additive component (G)

In addition to the component (E) and the component (F), the photo-curing composition (103) may further contain an additive component (G), depending on various purposes, so long as the effect of the present invention is not impaired. Examples of the additive component (G) include a sensitizer, a hydrogen donor, an internal release agent, a surfactant, an oxidation inhibitor, a volatile solvent, a polymer component, and a polymerization initiator other than the component (F).

The sensitizer is a compound used for the purpose of promoting the polymerization reaction or improving the conversion rate of the reaction. As the sensitizer, for example, a sensitizer may be mentioned.

The sensitizing dye is a compound which is excited by absorbing light of a specific wavelength and interacts with the component (F). The term " interaction " as used herein refers to the transfer of energy or electrons from the excited enhancement dye to the component (F).

Examples of the sensitizing dyes include anthracene derivatives, anthraquinone derivatives, pyrene derivatives, pentalcene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, A thioxanthone derivative, a phenothiazine derivative, a camphorquinone derivative, an acridine dye, a thiopyrilium dye, a merocyanine dye, a quinoline dye, a styrylquinoline dye, a ketokmarine dye, , Cyanine dyes, rhodamine dyes, and pyrilium dyes.

The sensitizers may be used alone or in combination.

The hydrogen donor is a starting radical generated from component (F) or a compound which reacts with a growing end radical generated during polymerization to generate a more active radical. When component (F) is a photo-radical generator, a hydrogen donor is preferably added.

Examples of such a hydrogen donor include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiouronium-p- toluenesulfinate, triethylamine, diethyl Aminoethyl acrylate, triethylenetetramine, 4,4'-bis (dialkylamino) benzophenone, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl- Aminobenzoate, triethanolamine and N-phenylglycine, and mercapto compounds such as 2-mercapto-N-phenylbenzoimidazole and mercaptopropionic acid esters, but the present invention is not limited thereto.

The hydrogen donors may be used alone or in combination.

The hydrogen donor may function as a sensitizer.

When the photocurable composition 103 contains a sensitizer or a hydrogen donor as the additive component G, the amount of sensitizer or hydrogen donor contained in the photocurable composition 103 is preferably in the range of Is not less than 0.1% by weight and not more than 20% by weight, more preferably not less than 0.1% by weight nor more than 5.0% by weight, further preferably not less than 0.2% by weight nor more than 2.0% by weight. When the amount of the sensitizer contained therein is 0.1% by weight or more of the component (E), the polymerization accelerating effect can be effectively exhibited. When the amount of the sensitizer or the hydrogen donor contained therein is 5.0% by weight or less based on the amount of the component (E), the molecular weight of the polymer compound forming the cured film can be made sufficiently high. In addition, incomplete dissolution of the sensitizer or hydrogen donor in the photocurable composition (103) or deterioration of the storage stability of the photocurable composition (103) can be suppressed.

The internal mold release agent is used for the purpose of reducing the interfacial bond strength between the photo-cured product 109 and the mold 104 obtained by curing the photo-curing composition 103, that is, for the purpose of reducing the release force in the following mold- May be added to the photo-curable composition 103. [ As used herein, the term " internal form " means that the agent is added to the photo-curable composition 103 prior to the placement step of the photo-curable composition 103. The internal release agent may be used alone or in combination with another internal release agent.

Examples of the internal mold release agent include a surfactant such as a silicone surfactant, a fluorine surfactant, and a hydrocarbon surfactant. In the present embodiment, the internal release agent is not polymerizable.

Examples of the fluorine surfactant include polyalkylene oxide adducts of an alcohol containing a perfluoroalkyl group (a polyethylene oxide adduct and a polypropylene oxide adduct), and polyalkylene oxide adducts of a perfluoropolyether Water (polyethylene oxide adduct and polypropylene oxide adduct). The fluorine surfactant may contain a hydroxy group, an alkoxy group, an alkyl group, an amino group, a thiol group and the like in a part (for example, an end group) of the molecular structure.

The fluorine surfactant may be a commercially available product. Examples of such commercially available products include products such as MEGAFACE F-444, Megaface TF-2066, Megaface TF-2067, and Megaface TF-2068 available from DIC Corporation; Products such as FLUORAD FC-430 and Fluorad FC-431 available from Sumitomo 3M Limited; SURFLON S-382, available from AGC Seimi Chemical Co., Ltd.; Products such as EFTOP EF-122A, EFTOP EF-122B, EFTOP EF-122C, EFTOP EF-121, EFTOP EF-126, EFTOP EF-127 and EFTOP MF-100 available from Tohkem Products Corporation; Products such as PF-636, PF-6320, PF-656, and PF-6520, available from OMNOVA Solutions Inc.; Products such as UNIDYNE DS-401, Unidyne DS-403, and Unidyne DS-451 available from Daikin Industries, Ltd.; And products such as Ftergent 250, Pratet 251, Pratent 222F, and Pratent 208G available from NEOS Company Limited, but are not limited thereto.

The internal release agent may be a hydrocarbon surfactant.

Examples of the hydrocarbon surfactant include an alkyl alcohol-alkylene oxide adduct obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an alkyl alcohol having 1 to 50 carbon atoms.

Examples of alkyl alcohol-alkylene oxide adducts include methyl alcohol-ethylene oxide adduct, decyl alcohol-ethylene oxide adduct, lauryl alcohol-ethylene oxide adduct, cetyl alcohol-ethylene oxide adduct, Alcohol-ethylene oxide adducts, and stearyl alcohol-ethylene oxide / propylene oxide adducts. The terminal group of each alkyl alcohol-alkylene oxide adduct is not limited to a hydroxy group which can be prepared simply by adding a polyalkylene oxide to an alkyl alcohol. Such a hydroxy group can be converted into a hydrophobic functional group such as a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a thiol group or a silanol group, or an alkyl group or an alkoxy group.

The alkyl alcohol-alkylene oxide adduct may be a commercially available product. Examples of commercially available products include BLAUNON MP-400, BLAUNON MP-550 and BLAUNON MP-1000 available from Aoki Oil Industrial Co., Ltd. Of polyoxyethylene methyl ether (methyl alcohol-ethylene oxide adduct); Polyoxyethylene decyl ether (decyl alcohol-ethylene oxide) such as FINESURF D-1303, Pine Surf D-1305, Pine Surf D-1307 and Pine Surf D-1310 available from Aoki Oil Industrial Corp., Seed adducts); Polyoxyethylene lauryl ether (lauryl alcohol-ethylene oxide adduct) such as Blaunone EL-1505 available from Aoki Oil Industrial Co., Ltd.; Polyoxyethylene cetyl ether (cetyl alcohol-ethylene oxide adduct) such as BLAUNON CH-305 and BLAUNON CH-310 available from Aoki Oil Industrial Company, Limited; Polyoxides such as Blaunon SR-705, Blaunon SR-707, Blaunon SR-715, Blaunon SR-720, Blaunon SR-730 and Blaunon SR-750 available from Aoki Oil Industrial Company, Ethylene stearyl ether (stearyl alcohol-ethylene oxide adduct); Random polymer type polyoxyethylene polyoxypropylene stearyl ether such as BLAUNON SA-50/50 1000R and BLAUNON SA-30/70 2000R available from Aoki Oil Industrial Company, Limited; Polyoxyethylene methyl ethers such as Pluriol A760E available from BASF; And polyoxyethylene alkyl ethers, such as the Emulgen series surfactants available from Kao Corporation, but are not limited thereto.

Among these hydrocarbon surfactants, the internal release agent is preferably an alkyl alcohol-alkylene oxide adduct, more preferably a long-chain alkyl alcohol-alkylene oxide adduct.

When the photo-curable composition 103 contains an annular release agent as the additive component G, the amount of the internal release agent contained therein is preferably from 0.001% by weight to 10% by weight based on the amount of the component (E) %, More preferably not less than 0.01 wt% and not more than 7 wt%, and still more preferably not less than 0.05 wt% and not more than 5 wt%. When the amount of the internal mold release agent contained therein is 0.001% by weight or more and 10% by weight or less based on the amount of the component (E), the releasing force reduction effect and the filling property are excellent.

The photocurable composition 103 may contain a volatile solvent as the additive component (G), but preferably contains substantially no volatile solvent. As used herein, the expression " substantially free of solvent " means that it does not contain any volatile solvents other than volatile solvents that are unintentionally contained, such as impurities. That is, for example, the amount of the volatile solvent contained in the photo-curable composition 103 is preferably 3% by weight or less, more preferably 1% by weight or less based on the amount of the photo-curing composition 103. The term " volatile solvent " as used herein refers to a photo-curable composition 103 or a volatile solvent commonly used in photoresists. The type of the volatile solvent is not particularly limited, but the volatile solvent can dissolve and uniformly disperse the different compound forming the photo-curable composition 103, and may be non-reactive with the compound.

The temperature at which the photocurable composition is blended

In the process of producing the photo-curing composition (103), the component (E) and the component (F) are mixed and dissolved under predetermined temperature conditions, particularly in the range of 0 ° C to 100 ° C. This is also true when the photocurable composition 103 contains the additive component (G).

Viscosity of photocurable composition

The mixture of the components of the photo-curing composition (103), which is a component excluding the volatile solvent, has a viscosity at 23 캜 of preferably 1 mPa · s to 100 mPa · s, more preferably 1 mPa · s to 50 Milli-pascal-second or less, more preferably 1 milli-pascal-second and 20 milli-pascal-second or less.

The photocurable composition 103 is filled in the concave portion of the fine pattern on the mold 104 in the process of bringing the photocurable composition 103 into contact with the mold 104 when the viscosity of the mixture is 100 milli-pascals-second or less It does not take long time. In addition, pattern defects due to poor charging are unlikely to occur.

When the viscosity of the mixture is not less than 1 milli-pascal-second, non-uniform application hardly occurs during the application of the photo-curing composition 103 to the base material 102, It is difficult for the photocurable composition 103 to leak out from the end of the mold 104 during the contact.

The surface tension of the photocurable composition

The mixture of the components of the photocurable composition 103 excluding the volatile solvent preferably has a surface tension at 23 DEG C of preferably 5 mN / m or more and 70 mN / m or less, more preferably 7 mN / m or more and 35 mN / m or less, and more preferably 10 mN / m or more and 32 mN / m or less. When the surface tension of the mixture is 5 mN / m or more, the photocurable composition 103 is filled in the concave portion of the fine pattern on the mold 104 in the process of bringing the photocurable composition 103 into contact with the mold 104 It does not take long time.

When the surface tension of the mixture is 70 mN / m or less, the cured films 109 and 110 obtained by photo-curing the photo-curable composition 103 have surface smoothness.

Impurities incorporated into the photo-curable composition

Like the adhesive layer-forming composition 100, the photo-curable composition 103 preferably also contains substantially no impurities.

Like the adhesive layer-forming composition 100, the photocurable composition 103 is also preferably obtained through a purification step. In such a purification step, filtration using a filter or the like is preferably performed.

The mixture obtained by mixing the component (E), the component (F) and the additive component (G) added as required in the case of performing the filtration using the filter is preferably, for example, from 0.001 μm to 5.0 μm Filter through the following filters. It is more preferable to perform the filtration using the filter in a plurality of stages or by repeating the use of the filter many times. The filtrate can be filtered again. A plurality of filters having different hole sizes may be used for filtration. The filter used for the filtration is not particularly limited, but it may be made of a polyethylene resin, a polypropylene resin, a fluororesin, a nylon resin or the like.

Through such a purification step, impurities such as particles incorporated in the photo-curable composition 103 can be removed. This makes it possible to prevent pattern defects caused by unevenness inadvertently from occurring in the photo-cured product 109 obtained by photo-curing the photo-curing composition 103.

In the case where the photo-curing composition 103 is used for producing a circuit board for use in a semiconductor device such as a semiconductor integrated circuit, it is preferable that impurities (metal impurities) containing metal atoms are incorporated in the photo- Preferably, avoid as much as possible. This is because impurities as well as the impurities incorporated into the adhesion layer forming composition 100 prevent the operation of the circuit board from being hindered. In this case, the concentration of the metal impurity in the photo-curable composition 103 is preferably 10 ppm or less, more preferably 100 ppb or less.

Thus, the photo-curable composition 103 is preferably manufactured without contacting the metal in the manufacturing step. That is, when the raw materials of the component (E), the component (F) and the additive component (G) are weighed, compounded and mixed together, preferably a metal weighing device or container is not used. In the purification step, filtration is preferably performed using a metal impurity removal filter. The metal impurity removal filter is not particularly limited, but may be a filter made of cellulose and diatomaceous earth, an ion exchange resin, or the like. The metal impurity removal filter is preferably used after cleaning. The cleaning method is preferably as follows: washing with ultrapure water, washing with alcohol, and washing with photo-curable composition 103 in this order.

Method of manufacturing cured pattern

A method of producing a cured product pattern 111 (a cured film having a pattern shape) according to an embodiment of the present invention will be described below. 1 (a) to 1 (h) are schematic cross-sectional views showing an example of a manufacturing method of the cured product pattern 111. Fig.

The manufacturing method of the cured product pattern 111

(1) a first step (adhesion layer formation step) of forming the adhesion layer 101 on the base material 102 by using the adhesion layer-forming composition 100,

(2) a second step (placement step) of placing the photo-curing composition 103 on the adhesion layer 101,

(3) a third step (mold contacting step) of bringing the photocurable composition 103 on the adhesion layer 101 and the mold 104 into contact with each other,

(5) a fourth step (light irradiation step) of irradiating light to the photo-curable composition 103 in a state in which the photo-curable composition 103 and the mold 104 are in contact with each other, and

(6) a fifth step (release step) of separating the mold 104 from the cured product obtained in the fourth step,

.

The manufacturing method of the cured product pattern 111 may further include (4) positioning the substrate 102 and the mold 104 (alignment step) between the third step and the fourth step.

The manufacturing method of the cured product pattern 111 is a method using a photo-nanoimprint technique.

The cured product pattern 111 obtained by this method is preferably a film having a pattern with a size of 1 nm or more and 10 mm or less, and more preferably 10 nm or more and 100 占 퐉 or less. In addition, a pattern formation technique for producing a film having a nano-sized (1 nm or more and 100 nm or less) pattern (concavo-convex structure) is generally referred to as a photo-nanoimprint technique.

Each step will be described below.

(1) Step of forming adhesion layer

In this step (adhesion layer formation step), the adhesion layer 101 is formed on the base material 102 by using the adhesion layer-forming composition 100 as shown in Fig. 1 (a). The adhesive layer 101 mainly contains a polymer compound (polymer).

The substrate 102 to which the photocurable composition 103 is to be disposed is a substrate or a support, and may be selected from any substrate according to various purposes. The substrate 102 may be, for example, a silicon wafer; A semiconductor device substrate made of aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, silicon nitride or the like; Quartz substrate; A glass substrate; Optical film; Ceramic membranes; Vapor deposition; Magnetic film; Reflective film; Ni, Cu, Cr, Fe, or the like; Paper sheet; A polymer substrate made of a polyester film, a polycarbonate film, or a polyimide film; TFT array substrate; An electrode plate for a PDP; Plastic substrates; A conductive substrate made of ITO or metal; Insulating substrate or the like. When the substrate 102 is processed by etching or the like in the following substrate processing step, the substrate 102 is preferably a silicon wafer or a semiconductor device substrate. The substrate 102 may be a substrate obtained by depositing a single kind or a plurality of kinds of films using a spin-on-glass, an organic material, a metal, an oxide, a nitride or the like on a semiconductor device substrate.

In the present embodiment, the substrate 102 preferably has a hydroxyl group (OH group) such as a silanol group (SiOH group) on the surface. Examples of such a substrate include silicon wafers, quartz wafers, glass wafers, and the like. In the case where the base material 102 has a hydroxy group on the surface, the hydroxy group present on the surface of the base material 102 by the heat treatment in the basic step may easily facilitate the chemical bonding with the thiol group of the compound (B) Will form. When the compound (A) contains an alkoxyalkyl group, the hydroxy group will possibly form a chemical bond with the alkoxyalkyl group of the compound (A).

For example, the following process can be used to apply the adhesion layer forming composition 100 to the substrate 102: an inkjet process, a dip coating process, an air knife coating process, a curtain coating process, a wire bar coating process, a gravure coating Process, an extrusion coating process, a spin coating process, a slit scanning process and the like are particularly preferable. Of these processes, a spin coating process is particularly preferable from the viewpoint of coating property, particularly thickness uniformity.

After the adhesive layer-forming composition 100 is applied to the substrate 102, the solvent (C) contained in the adhesive layer-forming composition 100 is evaporated by drying. In this operation, it is preferable that the substrate 102 is reacted with the compound (A) or (B) and the compounds (A) and (B) are reacted with each other, together with the evaporation of the solvent (C). This forms a bond between the substrate 102 and the adhesive layer 101 and a bond between the compound (A) and the adhesive (B) in the adhesive layer 101. The bond between the compound (A) and the compound (B) can be carried out by the following reaction: a dealcoholization reaction between the alkoxyalkyl group contained in the compound (A) and the thiol group contained in the compound (B) Is a sulfide bond formed by a dehydration reaction between thiol groups contained in the terephthalate compound (B).

In these reactions, heating is preferably carried out. The temperature at which these reactions take place depends on the reactivity between the substrate 102 and the compound (A) or (B); The reactivity between compounds (A) and (B); The boiling point of the compound (A), the compound (B) or the solvent (C). The temperature at the time of these reactions is preferably 70 占 폚 to 250 占 폚, more preferably 100 占 폚 to 220 占 폚, and still more preferably 140 占 폚 to 220 占 폚. The drying of the solvent (C), the reaction between the substrate (102) and the compound (A) or (B), and the crosslinking reaction between the compounds (A) and (B) can be carried out at the same temperature or different temperatures. That is, these reactions can be carried out simultaneously or in a sequential manner.

The thickness of the adhesive layer 101 formed by disposing the adhesive layer forming composition 100 on the substrate 102 varies depending on the application. The thickness of the adhesive layer 101 is preferably, for example, 0.1 nm or more and 100 nm or less, more preferably 0.5 nm or more and 60 nm or less, and further preferably 1 nm or more and 10 nm or less.

When the adhesive layer 101 is formed by applying the adhesive layer-forming composition 100 to the substrate 102, another adhesive layer is formed on the adhesive layer 101 by using the adhesive layer- May be formed by coating. The surface of the formed adhesion layer 101 is preferably as flat as possible. The surface roughness of the adhesive layer 101 is preferably 1 nm or less.

Through the above steps, a laminate including the substrate 102 and the polymer layer deposited on the substrate 102 (the adhesion layer 101) can be formed. The adhesion layer 101 contains a sulfide bond formed by a reaction between an alkoxyalkyl group or an alkylol group contained in the compound (A) and a thiol group contained in the compound (B) as described above.

(2) Placement step

In this step (placement step), as shown in Fig. 1 (b), the photocurable composition 103 is disposed (applied) on the adhesion layer 101 formed on the base material 102 to form a wet coating.

In the present embodiment, for example, the following processes can be used: a process such as an ink jet process, a dip coating process, an air knife coating process, a curtain coating process, a wire bar coating process, a gravure coating process, an extrusion coating process, Can be used to dispose the Mars composition (103) on the adhesion layer (101). Among these processes, an inkjet process is particularly preferable in the optical nanoimprint technique. The thickness of the wet coating (gravure transfer layer) varies depending on the application, and is, for example, not less than 0.01 μm and not more than 100.0 μm.

(3) Mold contact step

Then, as shown in Fig. 1 (c), the mold 104 having a circular pattern used for transferring the pattern shape is formed by a wet coating formed in the previous step (batch step) and made of the photocurable composition 103 (Fig. 1 (c-1)). This forms the coating film 105 so that the wet coating (part thereof) made of the photo-curable composition 103 is filled in the concave portion of the fine pattern on the surface of the mold 104 to fill the fine pattern (Fig. 1 -2)).

The mold 104 is preferably made of a light-transmitting material in consideration of the subsequent step (light irradiation step). As a material for forming the mold 104, a transparent resin such as glass, quartz, PMMA or polycarbonate, a transparent metal vapor deposition film, a flexible film made of polydimethylsiloxane, a photopolymerization film, a metal film and the like are preferable . In the case where a transparent resin is used to form the mold 104, such a transparent resin needs to be insoluble in the components contained in the photo-curing composition 103. The quartz has a small coefficient of thermal expansion, has little pattern deformation, and is thus particularly preferably used to form the mold 104.

The fine pattern on the surface of the mold 104 preferably has a height of 4 nm or more and 200 nm or less and an aspect ratio of 1 or more and 10 or less.

The mold 104 may be heated before the present step as a mold contacting step in which the photocurable composition 103 and the mold 104 are brought into contact with each other for the purpose of improving the peelability of the mold 104 from the photocurable composition 103, Can be surface-treated. As an example of the method of surface-treating the mold 104, a method of forming a release agent layer by applying a release agent on the surface of the mold 104 can be mentioned.

Examples of the releasing agent applied to the surface of the mold 104 include a silicone releasing agent, a fluorine releasing agent, a hydrocarbon releasing agent, a polyethylene releasing agent, a polypropylene releasing agent, a paraffin releasing agent, a Montane releasing agent and a Carnauba releasing agent. For example, a coating release agent such as OPTOOL DSX commercially available from Daikin Industries, Ltd. may be preferably used. These release agents may be used alone or in combination. Of these release agents, fluorine and hydrocarbon release agents are particularly preferred.

In this step (mold contacting step), when the mold 104 and the photocurable composition 103 are brought into contact with each other as shown in Fig. 1 (c-1), the pressure applied to the photocurable composition 103 Pressure) is not particularly limited. The pressure applied to the photo-curable composition 103 is usually 0 MPa or more and 100 MPa or less. In particular, the pressure applied to the photo-curable composition 103 is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, further preferably 0 MPa or more and 20 MPa or less.

In this step, the contact time of the mold 104 and the photo-curing composition 103 is not particularly limited, but is usually 0.1 second or more and 600 seconds or less. The contact time of the mold 104 and the photocurable composition 103 is preferably 0.1 second or more and 300 seconds or less, more preferably 0.1 second or more and 180 seconds or less, and still more preferably 0.1 second or more and 120 seconds or less.

This step may be performed under any one of an atmospheric atmosphere, a reduced-pressure atmosphere, and an inert gas atmosphere. A reduced pressure atmosphere and an inert gas atmosphere are preferable because it is possible to prevent the influence of oxygen or water on the curing reaction. Examples of the inert gas which can be used in the case of carrying out this step under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, chlorofluorocarbon gas, and mixtures of these gases. In the case where this step is carried out under a specific gas atmosphere including an atmospheric atmosphere, the pressure is preferably 0.0001 to 10 atm.

The mold contacting step may be performed under an atmosphere containing a condensable gas (hereinafter referred to as a " condensable gas atmosphere "). As used herein, the term " condensable gas " refers to a gas that condenses and liquefies at capillary pressure produced by the pressure at the time of charging. Particularly, the condensable gas is condensed together with the concave portion of the fine pattern formed on the mold 104 and the coating film 105 (a part thereof) on the gap between the mold 104 and the substrate 102 or the adhesive layer 101 And condensed and liquefied when the gas is charged in the gas atmosphere. 1 (c-1)), the condensable gas exists in a gaseous form in the condensable gas atmosphere before contacting the photocurable composition 103 (the surface transfer layer) and the mold 104 with each other in the mold contact step .

The step of performing the mold contacting step in a condensable gas atmosphere liquefies the condensable gas in the concave portion of the fine pattern to thereby annihilate the bubbles and is therefore excellent in the filling property. The condensable gas can be dissolved in the photo-curing composition (103).

The boiling point of the condensable gas is not particularly limited, but may be lower than or equal to the temperature of the atmosphere used in the mold contacting step. The boiling point of the condensable gas is preferably -10 ° C to 23 ° C, more preferably 10 ° C to 23 ° C. When the boiling point of the condensable gas is within this range, the filling property is excellent.

The vapor pressure of the condensable gas at the ambient temperature used in the mold contacting step is not particularly limited, but may be lower than the mold pressure at the time of stamping in the mold contacting step. The vapor pressure of the condensable gas at the ambient temperature is preferably 0.1 MPa to 0.4 MPa. When the vapor pressure of the condensable gas at the ambient temperature is within this range, the packing property is excellent. If the vapor pressure of the condensable gas at the atmospheric temperature is larger than 0.4 MPa, the bubble decaying effect may not be sufficiently obtained. However, if the vapor pressure of the condensable gas at the atmospheric temperature is lower than 0.1 MPa, a reduced pressure is required. The manufacturing method according to the present embodiment tends to complicate the structure of the imprint device for producing a film having a pattern shape.

The atmospheric temperature in the mold contacting step is not particularly limited, but is preferably 20 to 25 占 폚.

Examples of condensable gases include chlorofluorocarbons (CFCs) such as trichlorofluoromethane, fluorocarbons (FC), hydrochlorofluorocarbons (HCFC), 1,1,1,3,3-pentafluoro (CF ₃ CF ₂ OCH ₃ , HFE-245mc) such as hydrofluorocarbons (HFC) such as rheophthalonitrile (RfCO 2) and rofurovan (CHF ₂ CH ₂ CF ₃ , HFC-245fa, PFP), and hydrofluorocarbons such as pentafluoroethyl methyl ether Ether (HFE), but are not limited thereto.

Among these compounds, 1,1,1,3,3-pentafluoropropane (having a vapor pressure of 0.14 MPa at 23 deg. C and a pressure of 0.14 MPa at 25 deg. C, Boiling point 15 ° C), trichlorofluoromethane (vapor pressure at 23 ° C 0.1056 MPa and boiling point 24 ° C), and pentafluoroethyl methyl ether are preferred. From the viewpoint of excellent safety, 1,1,1,3,3-pentafluoropropane is particularly preferable.

The condensable gas may be used alone or in combination with another condensable gas. Alternatively, a gas mixture prepared by mixing a condensable gas with a non-condensable gas such as air, nitrogen, carbon dioxide, helium or argon may be used. The non-condensable gas to be mixed with the condensable gas is preferably helium from the viewpoint of the filling property. Helium can permeate the mold 104. Therefore, when the gas (the condensable gas and the helium) in the atmosphere is filled with the coating film 105 (part thereof) on the concave portion of the fine pattern formed on the mold 104 in the mold contacting step, the condensable gas is liquefied , Helium is transmitted through the mold 104. Therefore, the use of helium as the non-condensable gas is excellent in the filling property.

(4) Position alignment step

Subsequently, as shown in Fig. 1 (d), the position of the mold 104 and / or the position of the mold 104 are aligned such that the mold side positioning mark 106 is aligned with the positioning mark 107 of the substrate 102 The position of the base material 102 is adjusted.

(5) Light irradiation step

Subsequently, as shown in Fig. 1 (e), with the mold side positioning mark 106 aligned with the positioning mark 107 by step (positioning), the photocurable composition 103 Is irradiated with light through the mold 104. In this case, In particular, the coating film 105 filled in the fine pattern of the mold 104 is irradiated with light through the mold 104 (Fig. 1 (e-1)). This enables the coating film 105 filled in the fine pattern of the mold 104 to be cured by the irradiation light 108 to form the photo-cured product 109 (Fig. 1 (e-2)).

Here, the light to be irradiated to the photo-curing composition 103 forming the coating film 105 filled in the fine pattern of the mold 104 is selected according to the sensitivity wavelength of the photo-curing composition 103. In particular, ultraviolet light having a wavelength of 150 nm or more and 400 nm or less, X-ray, electron beam, or the like is appropriately selected and preferably used.

The light (irradiation light 108) irradiated to the photo-curable composition 103 is preferably ultraviolet light. This is because most commercially available curing aids (photopolymerization initiators) have sensitivity to ultraviolet light. Examples of the light source that emits ultraviolet light include high pressure mercury lamps, ultra high pressure mercury lamps, low pressure mercury lamps, dip-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, ₂ < / RTI > excimer laser. An ultra-high pressure mercury lamp is preferably used. The number of light sources used may be one or more. The light can be irradiated to all or a part of the coating film 105 filled in the fine pattern of the mold 104.

Light can be intermittently irradiated to the entire area on the base material 102 multiple times or continuously irradiated to the entire area. Alternatively, the light can be irradiated onto the region A during the first irradiation process and irradiated onto the region B different from the region A during the second irradiation process.

In this embodiment, the exposure amount of the photo-curable composition 103 in this step is preferably 90 mJ / cm ² or less, more preferably 30 mJ / cm ² or less.

(6)

Then, the optical pencil 109 and the mold 104 are separated from each other. At this point, there is a cured film 110 having a predetermined pattern shape on the base material 102.

In this step (release step), the cured product 110 is obtained by separating the photo-cured product 109 from the mold 104, as shown in Fig. 1 (f). In step (5) (light irradiation step), the cured film 110 is obtained so as to have an inverted pattern shape of a fine pattern formed on the mold 104.

The pressure at the interface between the photo-cured product 109 and the mold 104 is lowered when the photo-cured product 109 and the mold 104 are separated from each other in the mold-releasing step in the case where the mold contacting step is performed in a condensable gas atmosphere Therefore, the condensable gas evaporates. This tends to have the effect of reducing the releasing force required for separating the light guide 109 and the mold 104 from each other.

The method of separating the optical fiber bundle 109 and the mold 104 from each other is not particularly limited but causes physical damage to a part of the optical bundle 109 when the optical bundle 109 and the mold 104 are separated from each other I can not. The conditions for separating the light guide body 109 and the mold 104 from each other are also not particularly limited. The mold 104 can be separated from the photocurable 109, for example, in a manner that secures the substrate 102 and moves the mold 104 away from the substrate 102. Alternatively, the photohardener 109 can be separated from the mold 104 in a manner that secures the mold 104 and moves the substrate 102 away from the mold 104. The optical pencil 109 and the mold 104 can be separated from each other in such a manner that the base material 102 and the mold 104 are pulled in opposite directions.

A cured film having desired concave-convex pattern shapes (pattern shapes conforming to the concavo-convex shapes of the mold 104) at desired positions can be obtained through a series of steps (manufacturing process) including steps (1) to (6). The obtained cured film can be used as an optical member (including a part used as an optical member) such as a Fresnel lens or a diffraction grating. In this case, an optical member including the substrate 102 and the cured film 110 disposed thereon can be obtained.

In the production method of the cured product pattern 111, it is possible to repeatedly repeat a plurality of repetitive units (shots) composed of the steps (1) to (6) on the substrate 102. Repeating the repetition units (shots) composed of the steps (1) to (6) a plurality of times may cause the cured film 110 to have a plurality of desired concavo-convex pattern shapes (the convexo-concave shape of the mold 104) Pattern shape that follows).

(7) a residual film removing step for partially removing the cured film

The cured film 110 obtained in step (6) (mold-releasing step) has a specific pattern shape. A part of the cured film 110 may possibly remain on a region other than the region of the cured film 110 having a pattern shape (hereinafter, a part of the cured film 110 is referred to as a & ). In this case, as shown in Fig. 1 (g), the residual film located in the region of the cured film 110 located in the region to be removed and the adhesion layer 101 under the residual film are removed. This makes it possible to obtain the cured product pattern 111. [ The cured product pattern 111 has a desired concavo-convex pattern shape (pattern shape conforming to the concavo-convex shape of the mold 104).

One example of a method for removing the residual film and the adhesion layer 101 under the residual film is to remove the residual film in the concave portion of the cured film 110 by a process such as etching. This makes it possible to expose the surface of the substrate 102 from the concave portion of the cured film 110.

The method of removing the residual film and the adhesion layer 101 when the residual film in the concave portion of the cured film 110 and the adhesion layer 101 under the residual film are removed by etching is not particularly limited. For example, dry etching may be used. For dry etching, a known dry etching system may be used. The source gas at the time of dry etching is appropriately selected according to the composition of the cured film 110 to be etched. Containing gases such as CF ₄ , C ₂ F ₆ , C ₃ F ₈ , CCl ₂ F ₂ , CCl ₄ , CBrF ₃ , BCl ₃ , PCl ₃ , SF ₆ , and Cl ₂ ; A gas containing oxygen atoms such as O ₂ , CO, and CO ₂ ; Inert gases such as He, N ₂ , and Ar; H ₂ ; And the NH ₃ can be used. These gases can be used in combination.

The cured product pattern 111 having the desired concavo-convex pattern shape (pattern shape conforming to the concavo-convex shape of the mold 104) at a desired position can be obtained by the manufacturing process including steps (1) to (7) An article comprising the cured article pattern 111 can also be obtained. A base material 102; An adhesion layer (101) disposed on the substrate (102); A device part including the photo-cured product (cured product pattern 111) disposed on the adhesive layer 101 and having a concave-convex pattern can be obtained.

In the device part obtained in the present embodiment, the adhesive layer 101 has a crosslinked structure formed from the compounds (A) and (B). When the compound (A) to be used is a compound represented by the general formula (1), the adhesion layer (101) has a sulfide bond and a 1,3,5-tri The azine ring is contained in the structure. That is, the device part includes a substrate, a photo-cured product on the substrate and having a concavo-convex pattern, and an organic layer disposed between the substrate and the photo-cured product. The organic layer contains a 1,3,5-triazine ring and a sulfide bond.

In the case of processing the base material 102 by using the cured material pattern 111, a base material processing step (step (8)) as described below is performed.

The optical component can be obtained by using the cured product pattern 111 as an optical member such as a diffraction grating or a polarizing plate (including those used as a part of an optical member). This enables the optical component to include a substrate 102 and a cured pattern 111 disposed on the substrate 102.

(8) Substrate processing step

The cured product pattern 111 having a concavo-convex pattern can be used as an interlayer insulating film for use in electronic parts such as semiconductor devices. Further, the cured resin pattern 111 can be used as a resist film in the production of a semiconductor device. The term "semiconductor device" as used herein includes, but is not limited to, for example, LSI, system LSI, DRAM, SDRAM, RDRAM, and D-RDRAM.

The area of the substrate 102 exposed in step 7 (residual film removing step) (the area indicated by reference numeral 112 in FIG. 1 (g)) when the cured product pattern 111 is used as a resist film, Etching, ion implantation, and the like are performed. In this operation, the cured product pattern 111 functions as an etching mask. In addition, a circuit structure 113 (Fig. 1 (h)) based on the pattern shape of the cured product pattern 111 can be formed on the base material 102 by forming electronic members. This makes it possible to manufacture a circuit board for use in a semiconductor device or the like. By connecting such a circuit board to a circuit control system or the like, an electronic device such as a display, a camera, or a medical device can be manufactured.

Similarly, device parts such as an optical part, a microfluidic flow path structure, or a structure for a patterned medium can be obtained by etching, ion implantation or the like using the cured resin pattern 111 as a resist film.

In addition, the optical component can be obtained by a method in which the cured product pattern 111 is used as a mask (resist film) and etching, ion implantation, or the like is performed.

Alternatively, the mold for imprinting can be manufactured in such a manner that the cured material pattern 111 is used to etch the quartz substrate corresponding to the substrate 102. [ In this case, the quartz substrate corresponding to the base material 102 can be directly etched by using the cured material pattern 111 as a mask. The quartz substrate can be etched in such a manner that the hard mask material layer is etched using the cured pattern 111 as a mask and the pattern made of the hard mask material transferred from the etched hard mask material layer is used as a mask . Alternatively, the quartz substrate can be etched in such a manner that a second hardened material is formed by using a second hardenable material in the concave portion of the hardened pattern 111, and the second hardened material is used as a mask.

In the case where the exposed surface portion of the substrate is etched using the cured pattern 111 as a mask, dry etching may be used. For dry etching, a known dry etching system may be used. The source gas at the time of dry etching is appropriately selected according to the composition of the cured film to be etched. A halogen-containing gas such as CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₈ , CCl ₂ F ₂ , CCl ₄ , CBrF ₃ , BCl ₃ , PCl ₃ , SF ₆ and Cl ₂ ; A gas containing oxygen atoms such as O ₂ , CO, and CO ₂ ; Inert gases such as He, N ₂ , and Ar; H ₂ ; And the NH ₃ can be used. Containing gas such as CF ₄ , CHF ₃ , C ₂ F ₆ , C ₃ F ₈ , C ₄ F ₈ , CCl ₂ F ₂ , CBrF ₃ , and SF ₆ is preferable. This is because the photo-curable composition 103 has high resistance to dry etching using a fluorine-containing gas. These gases can be used in combination.

Etching and ion implantation are described as a method of processing the base material 102 using the cured material pattern 111 as a mask. The method of processing the base material 102 using the cured material pattern 111 as a mask is not limited to etching or ion implantation. For example, the base material 102 can be plated with the cured material pattern 111 disposed on the base material 102. [

In the case of producing a circuit board or an electronic component, the cured product pattern 111 can be removed from the finally processed substrate 102. The cured product pattern 111 may remain in the form of a member forming the element.

Example

Hereinafter, the present invention will be described in detail with reference to Examples. The technical scope of the present invention is not limited to the embodiments. In addition, the following " parts " and "% " are by weight unless otherwise specified.

(1) Evaluation of hardenability

The adhesive layer-forming composition was evaluated for curability by the following method.

(1-1) Preparation of composition for forming adhesion layer

Compound (A) and compound (B) were compounded in the weight ratios shown in Table 1, and volatile solvents (C), which is propylene glycol monomethyl ether acetate available from Tokyo Chemical Industry Co., ) To obtain a mixed solution having a total concentration of the compounds (A) and (B) of 5%.

Then, the resulting mixed solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.2 m. In this manner, compositions 1 to 11, which are adhesion layer-forming compositions for evaluation of curability, were prepared.

(Compound (A))

(A-1) Compound containing 6 methoxymethyl groups: Hexa represented by formula a available under the trade name NIKALAC MW-390 from Sanwa Chemical Co., Ltd. Methoxymethylmelamine.

<Formula a>

(A-2) Compounds containing four methoxymethyl groups (for comparative examples): 1,3,4,6-tetra (4-methoxyphenyl) propane represented by formula b available from Sanwa Chemical Company, Kiss (methoxymethyl) glycoluril.

<Formula b>

(Compound (B))

(B-1) 1,3,5-tris (3-mercaptobutyryloxyethyl) - 1 (represented by the formula c) available under the trade name Karenz MT NR-1 from Showa Denko K.K. , 3,5-triazine-2,4,6 (1H, 3H, 5H) -triene.

<Formula c>

(B-2) trimethylolpropane tris (3-mercaptopropionate) represented by the formula d available from Tokyo Chemical Industry Co., Ltd.

<Formula d>

(B-3) pentaerythritol tetrakis (3-mercaptobutyrate) represented by the chemical formula (e) available under the trade name Karenz MT PE-1 from Showa Denko K.K.

<Formula e>

(B-4) pentaerythritol tetrakis (3-mercaptopropionate) represented by the formula (f) available from Tokyo Chemical Industry Co., Ltd.

<Formula f>

[Table 1]

(1-2) Formation of adhesion layer

Each of the prepared compositions 1 to 11 was applied to a silicon wafer by spin coating at 3,000 rpm for 30 seconds. Thereafter, the prepared compositions 1 to 11 were heated on a hot plate to form an adhesive layer. The heating conditions are shown in Table 2.

(1-3) Evaluation of hardenability

The surface of the adhesion layer formed in (1-2) was wiped with acetone-impregnated BEMCOT, and the adhesion layer was evaluated for curability in such a manner that dissolution and peeling of the adhesion layer were visually confirmed. In the evaluation, evaluation was made with respect to A in which the adhesion layer was not dissolved or peeled, and B in which the adhesion layer was partially dissolved or peeled. The evaluation results are summarized in Table 2.

[Table 2]

Compositions 1 to 7 are compositions in which the compound (A) used is A-1. Compositions 1 to 7 had excellent curability (Examples 1 to 7).

Compositions 8 to 11 are compositions in which the compound (A) used is A-2. Compositions 8 to 11 had insufficient curability (Comparative Examples 1 to 4).

A-1 contains 6 methoxymethyl groups which are functional groups capable of binding to the thiol group contained in the compound (B). Thus, A-1 will probably be highly reactive with compound (B), and the network structure formed by crosslinking A-1 and compound (B) in the adhesion layer formed after reaction will probably be dense. As a result, Compositions 1 to 7 had excellent curability.

On the other hand, A-2 contains four methoxymethyl groups which are functional groups capable of binding to the thiol group contained in the compound (B). That is, the number of methoxymethyl groups contained in A-2 is smaller than the number of methoxymethyl groups contained in A-1. Therefore, A-2 probably will be insufficient in reactivity with compound (B). Also, the network structure formed by crosslinking A-2 and compound (B) in the adhesive layer formed after the reaction will probably be less scarce than the network structure formed by crosslinking A-1 and compound (B).

As a result, Compositions 8 to 11 had insufficient curability.

A-2 contains a carbonyl group in the molecular structure. The methoxymethyl group contained in A-2 is more reactive with the thiol group contained in compound (B) than the methoxymethyl group contained in A-1, since the oxygen atom in the carbonyl group exhibits electron withdrawing property low. This would probably be part of a factor that compositions 8-11 have insufficient curing properties. On the other hand, A-1 does not contain a carbonyl group in the molecular structure. Therefore, unlike the above, the methoxymethyl group contained in A-1 does not lower the reactivity. Therefore, it is considered that the compositions 1 to 7 have excellent curing properties.

As described above, Compositions 1 to 7 have sufficient curability. Therefore, by forming the adhesion layer using each of the compositions 1 to 7, it is possible to suppress the occurrence of the pattern peeling defect.

(2) Evaluation of adhesion

Then, the adhesion between the substrate and the cured film obtained by curing the photo-curable composition was evaluated by the following method.

(2-1) Preparation of composition for forming adhesion layer

Compositions 1 to 7, which exhibited sufficient curability in the evaluation of the curability as described above, were diluted 10 times with volatile solvent (C), which is propylene glycol monomethyl ether acetate available from Tokyo Chemical Industry Co., Ltd., , The compound (B) and the additive component (D) was 0.5%.

Subsequently, the resulting mixed solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.2 μm to prepare compositions 1 'to 7' for evaluation of adhesion.

(2-2) Preparation of photo-curable composition

The following components (E) (polymerizable compound), component (F) (photopolymerization initiator) and the additive component (G) were blended together at a weight ratio shown in Table 3 to obtain a mixed solution. The values in Table 3 are by weight.

The resulting mixed solution was filtered through an ultra-high molecular weight polyethylene filter having a pore size of 0.2 μm to prepare a photocurable composition a and a photocurable composition b.

Compound (E): The polymerizable compound

Isobornyl acrylate available under the trade designation IB-XA from Ishikawa Chemical Co., Ltd. (E-1).

(E-2) benzyl acrylate available under the trade designation V # 160 from Osaka Organic Chemical Industries Limited.

(E-3) Neopentyl glycol diacrylate available from Ishikawa Chemical Co., Ltd. under the trade name NP-A.

Dimethylol tricyclodecane diacrylate available under the trade name DCP-A from Ishikawa Chemical Co., Ltd. (E-4).

Compound (F): A photopolymerization initiator

(F-1) Luciferin TPO represented by formula g available from BASF.

<Formula g>

Another compound (G)

(G-1) available from Tokyo Chemical Industry Co., Ltd.,

(G-2) polyoxyethylene stearyl ether represented by formula h, available under the tradename Mulgene 320P from Kao Corporation.

<Formula h>

[Table 3]

(2-3) Formation of adhesion layer

Each of the prepared compositions 1 'to 7' was applied to a silicon wafer by spin coating at 3,000 rpm for 30 seconds. Thereafter, each of the prepared compositions 1 'to 7' was heated on a hot plate to form an adhesion layer. The heating conditions were for 30 minutes at 220 ° C for compositions 1 'to 3' and for 3 minutes at 220 ° C for compositions 4 'to 7'. The thickness of the formed adhesion layer was 10 nm or less.

(2-4) Curing of photocurable composition

2 μL of the photo-curable composition a prepared in item (2-2) was dropped and placed on the adhesive layer formed on the silicon wafer as described in item (2-3). A 1 mm-thick quartz glass plate was placed on the resulting photo-curable composition a, and a 35 mm x 25 mm area was filled with the photo-curable composition a.

Subsequently, the light emitted from the UV light source equipped with the ultra-high pressure mercury lamp was filtered through the following interference filter, and then irradiated to the photo-curing composition a through the quartz glass plate for 200 seconds to cure the photo-curable composition a to obtain a cured film. The interference filter used in light irradiation was VPF-25C-10-15-31300, available from SIGMAKOKI Co., Ltd. The light used was a single wavelength UV light of 313 ± 5 nm and the illumination was 1 mW / cm ² .

Similarly to the photo-curable composition a, the photo-curable composition b was photo-cured to obtain a cured film.

(2-5) Evaluation of adhesion

After the photo-curing, the quartz glass plate was peeled off and visually confirmed whether or not the cured film was peeled off from the silicon wafer. In the present embodiment, the cured film was evaluated as A from the area of 35 mm x 25 mm on the whole surface, and rated B when the cured film was peeled off from a part of the area of 35 mm x 25 mm.

The evaluation results are summarized in Table 4.

[Table 4]

Examples 1a to 7a are examples in which the adhesive layer is formed using the compositions 1 'to 7' and a cured film is formed using the photo-curable composition a. Examples 1b to 7b are examples in which the adhesive layer is formed using the compositions 1 'to 7' and a cured film is formed using the photo-curable composition b. In Comparative Examples 5a and 5b, a direct-cured film was formed by using the photo-curable composition a and the photo-curable composition b, respectively, on a silicon wafer without forming an adhesion layer.

In Examples 1a to 7a and 1b to 7b, peeling defect did not occur. However, in Comparative Examples 5a and 5b in which no adhesion layer was formed, a peeling defect occurred.

That is, the use of the adhesive layer-forming composition makes it possible to form an adhesive layer capable of improving the adhesion between the substrate and the cured film, and to suppress the occurrence of pattern peeling defects.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.

This application claims the benefit of Japanese Patent Application No. 2015-017714, filed on January 30, 2015, and Japanese Patent Application No. 2015-221384, filed on November 11, 2015, which are incorporated herein by reference in their entirety. .

Claims (20)

A compound (A) containing either or both of an alkoxyalkyl group and an alkylol group, wherein the number of alkoxyalkyl groups and alkylol groups per molecule or the total number of alkoxyalkyl groups and alkylol groups per molecule is 5 or more; And
The compound (B) containing two or more thiol groups bonded to the hydrocarbon per molecule,
By weight based on the total weight of the composition. The adhesion layer-forming composition according to claim 1, further comprising a volatile solvent, wherein the content of the volatile solvent is 70% by mass or more and 99.9% by mass or less when the total amount of the adhesive layer-forming composition is 100% by mass. The composition for forming an adhesion layer according to claim 1, which does not contain a photopolymerization initiator. The adhesion layer-forming composition according to claim 1, wherein the content of the particles having a size larger than 0.2 μm is less than 3% by mass based on 100% by mass of the total content of the adhesive layer-forming composition. The adhesion layer-forming composition according to claim 1, wherein the compound (A) is a compound represented by the following formula.
&Lt; Formula 1 >

In the above formula, R ₁ to R ₆ independently represent a hydrogen atom, an alkyl group, an alkoxyalkyl group or an alkylol group, and at least five of R ₁ to R ₆ are an alkoxyalkyl group or an alkylol group. The composition of claim 1, wherein the compound (A) is selected from the group consisting of pentamethoxymethyl melamine, hexamethoxymethyl melamine, (hydroxymethyl) pentakis (methoxymethyl) melamine, hexaethoxymethyl melamine, hexabutoxymethyl melamine, Wherein the adhesive layer comprises at least one selected from the group consisting of polyamides, pentamethylol melamine, and hexamethylol melamine. The positive resist composition according to claim 1, wherein the compound (A) contains one or both of an alkoxyalkyl group and an alkylol group, and the number of alkoxyalkyl groups and alkylol groups per molecule or alkoxyalkyl groups and alkylol groups Is 6 or more in total. The adhesion layer-forming composition according to claim 1, wherein the compound (B) contains three or more thiol groups per molecule. The composition according to claim 1, wherein the compound (B) is a primary thiol. The method according to claim 1, wherein assuming that the weight fraction of the compound (A) is? (%) And the weight fraction of the compound (B) is? (%) When the entirety of the adhesion layer- , And the ratio? /? Is 0.25 or more and 4 or less. The method according to claim 1, wherein assuming that the weight fraction of the compound (A) is? (%) And the weight fraction of the compound (B) is? (%) When the entirety of the adhesion layer- , and the sum of? and? is 0.1 or more and 10 or less. The composition for forming an adhesion layer according to claim 1, which is used for a photo-nanoimprint. A first step of forming an adhesion layer by disposing the adhesion layer forming composition according to any one of claims 1 to 12 on a substrate;
A second step of disposing a photocurable composition on the adhesion layer;
A third step of bringing the photocurable composition and a mold having a circular pattern used for transferring a pattern shape into contact with each other;
A fourth step of irradiating the photocurable composition with light to produce a cured product; And
A fifth step of separating the cured product from the mold,
&Lt; / RTI &gt; 14. The method of claim 13, wherein the photocurable composition contains a compound containing an acryloyl group or a methacryloyl group. 14. The method of claim 13, wherein the substrate has a hydroxy group on the surface. A process for producing an optical component, comprising the step of obtaining a cured product pattern by the process for producing a cured product according to claim 13. Obtaining a cured product pattern by the method for producing a cured product according to claim 13; And
Performing etching or ion implantation on the substrate using the obtained cured product pattern as a mask
Wherein the method further comprises the steps of: 18. The method of claim 17, wherein the circuit board is a circuit board for use in a semiconductor device. A method for producing a cured product, comprising: obtaining a cured product pattern on a substrate by the method for producing a cured product according to claim 13; And
And etching the substrate using the obtained cured product pattern as a mask
Wherein the imprint mold is formed by a method comprising the steps of: delete

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