JP6632340B2 - Adhesive layer forming composition, method for producing cured product pattern, method for producing optical component, method for producing circuit board, method for producing imprint mold, and device component - Google Patents

Description

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

  In semiconductor devices, MEMS, and the like, demands for miniaturization are increasing, and among them, optical nanoimprint technology is receiving attention.

  In the photo-nanoimprint technology, a photo-curable composition is formed by pressing a mold (a mold) having a fine concavo-convex pattern on its surface against a substrate such as a substrate (wafer) coated with a photo-curable composition (resist). To cure. Thereby, the concave and convex pattern of the mold is transferred to the cured film of the photocurable composition, and the pattern is formed on the substrate. According to the optical nanoimprint technology, a fine structure of the order of several nanometers can be formed on a substrate.

  In the photo nanoimprint technique, first, a photocurable composition is applied to a pattern formation region on a substrate (arrangement step). Next, this photocurable composition is molded using a mold on which a pattern is formed (mold contact step). Then, the photocurable composition is cured by light irradiation (light irradiation step) and then separated (mold release step). By performing these steps, a resin pattern (photocured product) having a predetermined shape is formed on the base material.

  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 photocurable composition and the substrate is low, a part of the photocured product obtained by curing the photocurable composition adheres to the mold when the mold is separated in the mold release process. This is because there is a case where the pattern is peeled off as it is or a pattern peeling defect occurs.

  Conventionally, as a technique for improving the adhesion between the photocurable composition and the substrate, between the photocurable composition and the substrate, a layer for adhering the photocurable composition and the substrate (Patent Literature 1).

JP 2013-202982 A

  In the technique described in Patent Literature 1, the adhesive layer is formed using a composition containing a curable main agent and a urea-based crosslinking agent. However, when a composition containing a urea-based cross-linking agent is used, the curability of the composition at the time of forming the adhesion layer may be insufficient. As a result, there has been a problem that the adhesion between the photocurable composition and the substrate cannot be sufficiently improved, and a pattern peeling defect occurs.

  In view of the above-mentioned problems, an object of the present invention is to provide an adhesive layer forming composition that can suppress the occurrence of pattern peeling defects.

  The composition for forming an adhesion layer according to the present invention comprises a compound (A) having at least five of one or both of an alkoxyalkyl group and an alkylol group in one molecule, and at least a thiol group in one molecule. And compound (B) having two.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesion layer formation composition which can suppress generation | occurrence | production of a pattern peeling defect can be provided.

It is sectional drawing which shows typically the manufacturing method of the hardened | cured material pattern which concerns on this embodiment.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments, and may be appropriately modified based on ordinary knowledge of a person skilled in the art without departing from the spirit of the present invention. Modifications and the like are also included in the scope of the present invention.

  The adhesive layer forming composition 100 according to the present embodiment is a composition for forming an adhesive layer 101 between a substrate 102 and a photocurable composition 103. The adhesion layer forming composition 100 has a compound (A) having at least five of either or both of an alkoxyalkyl group and an alkylol group in one molecule and at least two thiol groups in one molecule. And compound (B).

  The adhesion layer forming composition 100 according to the present embodiment is particularly preferably used when it is arranged and cured on a substrate 102 to form a cured product. Further, the laminate having the adhesion layer 101 obtained by curing the adhesion layer forming composition 100 according to the present embodiment and the substrate 102 is obtained by disposing the photocurable composition 103 on the laminate and performing photocuring. It can be preferably used as a substrate for obtaining the product 109. Further, the composition 100 for forming an adhesion layer according to the present embodiment can be used as a composition for forming an adhesion layer for imprint, and is particularly useful as a composition for forming an adhesion layer for optical nanoimprint.

  Hereinafter, each component of the adhesive layer forming composition 100 according to the present embodiment will be described in detail.

<Compound (A)>
The compound (A) according to this embodiment is a compound having at least one of an alkoxyalkyl group and an alkylol group or both (hereinafter, referred to as “functional group a”) in one molecule. .

  The functional group a of the compound (A) according to the present embodiment is a functional group that reacts with the thiol group of the compound (B) in the adhesion layer forming step described later. As a result, a bond is formed between the compound (A) and the compound (B). Since the compound (A) has a plurality of functional groups a in one molecule, the compound (A) can form a bond with each of the plurality of compounds (B). By generating a bond between the compound (A) and the plurality of compounds (B), a structure in which the compounds constituting the adhesion layer 101 are cross-linked (cross-linked structure) can be formed.

  The reaction between the functional group a of the compound (A) according to the present embodiment and the thiol group of the compound (B) is preferably caused by a heating process in a later-described adhesion layer forming step.

  By forming the adhesion layer 101 having a crosslinked structure as described above, the amount of the free unreacted compound (A) or compound (B) that is not connected to the base material 102 can be reduced. Thereby, the film strength of the adhesion layer 101 can be improved.

  If the unreacted compound (A) or compound (B) is present in the adhesive layer 101 in a free state, these compounds may be used in the photocurable composition 103 in the step of arranging the photocurable composition 103 described below. May elute into 103. As a result, when the composition of the photocurable composition 103 changes, the characteristics of the photocurable composition 103 change. For example, a pattern peeling defect of the photocurable product 109 obtained by curing the photocurable composition 103. And so on.

  On the other hand, when the adhesive layer forming composition 100 according to the present embodiment is used, the amount of the free compound (A) or the compound (B) that is not connected to the base material 102 in the adhesive layer 101 can be significantly increased. Can be reduced. Thereby, the dissolution of the compound (A) or the compound (B) into the photocurable composition 103 in the step of disposing the photocurable composition 103 can be significantly suppressed. As a result, it is possible to suppress the occurrence of the peeling defect or the like of the pattern of the photocured product 109 described above.

  Further, the functional group a of the compound (A) is any one of a chemical bond such as a covalent bond, an ionic bond, a hydrogen bond, an intermolecular force or an interaction with a functional group present on the surface of the substrate 102. May occur. For example, when a substrate having a hydroxyl group such as a silanol group on the surface is used as the substrate 102, a dealcoholization reaction occurs between the alkoxyalkyl group and the silanol group. As a result, a covalent bond can be formed between the compound (A) and the substrate 102. Thereby, the adhesion between the adhesion layer 101 and the substrate 102 can be improved.

  Further, the compound (A) is preferably a compound represented by the following general formula (1).

In the formula (1), R _{1 to} R ₆ each independently represent any one of a hydrogen atom, an alkyl group, an alkoxyalkyl group, and an alkylol group. However, at least five of R _{1 to} R ₆ are an alkoxyalkyl group or an alkylol group.

  The compound represented by the general formula (1) is a melamine derivative having a triazine ring at the center of the structure. That is, the compound represented by the general formula (1) has a structure in which a nitrogen atom is bonded to each of the 2-, 4- and 6-positions of 1,3,5-triazine. Further, the compound represented by the general formula (1) has five or six functional groups a. That is, the compound represented by the general formula (1) has more functional groups a than urea-based compounds such as glycoluril derivatives.

  Further, since the urea-based compound has an electron-withdrawing oxygen atom in the molecule, the reactivity of the functional group a in the urea-based compound having the functional group a with the thiol group is such that the electron-withdrawing oxygen atom is present in the molecule. There is a tendency for it to decrease as compared to the case without atoms. On the other hand, the triazine ring which is the parent of the compound represented by the general formula (1) does not have an electron-withdrawing oxygen atom in the structure. Therefore, it is considered that the functional group a of the compound represented by the general formula (1) has higher reactivity than the functional group a in the urea-based compound.

  From the above, the curability of the adhesive layer forming composition 100 according to the present embodiment can be improved by using the compound represented by the general formula (1) as the compound (A). Further, the film strength of the adhesion layer 101 formed using the adhesion layer forming composition 100 can be improved.

  The type of the alkoxyalkyl group or the alkylol group of the compound (A) is not particularly limited, but the alkoxyalkyl group is preferably a methoxymethyl group, and the alkylol group is preferably a methylol group. By using a functional group having a small formula weight as the alkoxyalkyl group or the alkylol group in this manner, the crosslink density per unit mass in the adhesion layer 101 can be improved. As a result, the film strength of the adhesion layer 101 can be improved.

  Specific examples of the compound (A) include pentamethoxymethylmelamine, hexamethoxymethylmelamine, (hydroxymethyl) pentakis (methoxymethyl) melamine, hexaethoxymethylmelamine, hexabutoxymethylmelamine, pentamethylolmelamine, and hexamethylolmelamine. But not limited thereto.

  In addition, the compound (A) may be composed of one kind of compound, or may be composed of plural kinds of compounds.

<Compound (B)>
The compound (B) of the present invention is a compound having at least two thiol groups in one molecule.

  The thiol group of the compound (B) is a functional group that reacts with the functional group a of the compound (A) as described above. As a result, a bond is formed between the compound (A) and the compound (B). Since the compound (B) has a plurality of thiol groups in one molecule, the compound (B) can form a bond with each of the plurality of compounds (A). When the compound (B) forms a bond with each of the plurality of compounds (A), a structure in which the compounds constituting the adhesion layer 101 are cross-linked (cross-linked structure) can be formed.

  By forming the adhesion layer 101 having a crosslinked structure as described above, the amount of the free unreacted compound (A) or compound (B) that is not connected to the base material 102 can be reduced. Thereby, the film strength of the adhesion layer 101 can be improved. In addition, elution of the compound (A) or the compound (B) into the photocurable composition 103 in the step of disposing the photocurable composition 103 described later can be significantly suppressed. As a result, it is possible to suppress the occurrence of the peeling defect or the like of the pattern of the photocured product 109 described above.

  The thiol group of the compound (B) may cause any chemical bond or interaction such as a covalent bond, a hydrogen bond, or an intermolecular force with a functional group present on the surface of the base material 102. it can. Thereby, the adhesion between the adhesion layer 101 and the substrate 102 can be improved.

  Further, the thiol group of the compound (B) is converted into a polymerizable compound in the photocurable composition 103 by a chain transfer reaction with a radical generated in the photocurable composition 103 in a light irradiation step described below. Form a covalent bond between Thereby, the adhesiveness between the adhesive layer 101 and the photocurable composition 103 or the cured film 109 can be improved. As described above, since the adhesion layer 101 also has a chemical bond or interaction with the base material 102, as a result, the adhesion layer 101 causes the base material 102 and the photocurable composition 103 or the cured film 109 to be in contact with each other. Adhesion between them can be improved.

  In order to further exert the above effects, the compound (B) according to the present embodiment preferably has a large number of thiol groups, more preferably at least three, and preferably at least four. More preferred. By setting the number of thiol groups in the compound (B) to at least three, a crosslinked structure formed by the compound (B) becomes three-dimensional, and the strength of the film of the adhesion layer 101 is further improved. Further, the bond between the compound (B), the compound (A), and the base material 102 is easily generated. Since the effect described above increases as the number of thiol groups in the compound (B) increases, the number of thiol groups in the compound (B) is more preferably at least four.

  Further, the compound (B) is preferably a primary thiol. By making the compound (B) a primary thiol, steric hindrance around the thiol group of the compound (B) can be reduced. As a result, the reactivity of the thiol group of the compound (B) can be increased, and the curability of the adhesive layer forming composition 100 can be improved.

  Specific examples of the compound having at least two thiol groups that can be used as the compound (B) according to the present embodiment include 1,6-hexanedithiol, 1,8-octanedithiol, and 1,10-decanedithiol. Bifunctional thiol compounds such as 1,4-butanediol bis (thioglycolate) and 1,4-bis (3-mercaptobutyryloxy) butane; 1,3,5-tris (3-mercaptobutyryloxyethyl) ) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tris (3-mercaptobutyrate), etc. Trifunctional thiol compounds; pentaerythritol tetrakis (mercaptoacetate), pentaerythritol tetra Scan (3-mercapto butyrate), but tetrafunctional thiols such as pentaerythritol tetrakis (3-mercaptopropionate) and the like, but are not limited to.

  In addition, the compound (B) may be composed of one kind of compound, or may be composed of plural kinds of compounds.

<Compounding ratio of compound (A) and compound (B)>
When the compounding ratio of either the compound (A) or the compound (B) in the adhesive layer forming composition 100 is extremely small, the crosslinking density of the adhesive layer 101 becomes small, and the film strength and the curability are insufficient. Become. Therefore, assuming that the weight fractions of the compound (A) and the compound (B) with respect to the whole adhesive layer forming composition 100 are α and β, respectively, α: β is preferably 1: 9 to 9: 1, and 1: 9 to 9: 1. More preferably, the ratio is 4 to 4: 1. That is, α / β is preferably 0.11 or more and 9 or less, and more preferably 0.25 or more and 4 or less. The optimum mixing ratio varies depending on the number, molecular weight, and reactivity of the functional groups of the compound (A) and the compound (B). However, by setting the mixing ratio within the above range, the adhesion layer forming composition 100 Curability can be increased.

  The compounding ratio (the sum of α and β) of the compound (A) and the compound (B) in the adhesion layer forming composition 100 is appropriately determined according to the viscosity of the adhesion layer forming composition 100, the intended thickness of the adhesion layer 101, and the like. Can be adjusted. The sum of α and β is preferably 0.01 or more and 10 or less, more preferably 0.1 or more and 10 or less, and 0.1 or more 7 with respect to the total weight of the adhesion layer forming composition 100. It is more preferred that: By setting the compounding ratio of the compound (A) and the compound (B) in the adhesion layer forming composition 100 within the above range, the viscosity of the adhesion layer forming composition 100 can be reduced, and the formed film of the adhesion layer 101 is formed. The thickness can be reduced.

<Volatile solvent (C)>
The adhesive layer forming composition 100 according to the present embodiment contains a volatile solvent (C) (hereinafter, simply referred to as “solvent (C)”). When the adhesive layer forming composition 100 contains the solvent (C), the viscosity of the adhesive layer forming composition 100 can be reduced. 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 as long as it dissolves the compound (A) and the compound (B), but is preferably a solvent having a boiling point at normal pressure of 80 to 200 ° C. The solvent (C) is preferably an organic solvent having at least one of a hydroxyl group, an ether structure, an ester structure, and a ketone structure. These solvents are excellent in the solubility of the compound (A) and the compound (B), the wettability to the substrate 102, and the like.

  Specific examples of solvents that can be used as the solvent (C) according to the present embodiment include alcohol solvents such as propyl alcohol, isopropyl alcohol, and butyl alcohol; ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, and ethylene glycol monoethyl ether. , Ether solvents such as ethylene glycol diethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether; ester solvents such as butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate; methyl isobutyl Ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, γ Butyrolactone, alone is selected from a ketone solvent, such as ethyl lactate, or mixtures of these solvents. Among them, propylene glycol monomethyl ether acetate or a mixed solution thereof is particularly preferable from the viewpoint of applicability.

  The mixing ratio of the solvent (C) according to the present embodiment in the adhesion layer forming composition 100 is appropriately adjusted depending on the viscosity and the applicability of the compound (A) and the compound (B), the thickness of the adhesion layer 101 to be formed, and the like. be able to. The mixing ratio of the solvent (C) in the adhesion layer forming composition 100 is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more based on the total weight of the adhesion layer forming composition 100. . The larger the mixing ratio of the solvent (C) in the composition 100 for forming an adhesion layer, the smaller the thickness of the adhesion layer 101 to be formed. When the blending ratio of the solvent (C) in the adhesion 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, but is preferably 99.9% by mass or less, and more preferably 99% by mass or less.

<Other components (D)>
The adhesive layer forming composition 100 according to the present embodiment may be, in addition to the compound (A), the compound (B), and the solvent (C) described above, according to various purposes, within a range that does not impair the effects of the present invention. Further additional components (D) may be contained. Examples of such additional components include a surfactant, a crosslinking agent, a polymer component, an antioxidant, and a polymerization inhibitor. After the adhesion layer forming composition 100 is disposed on the substrate 102, the composition is cured while the solvent (C) is volatilized by heating, whereby the thickness of the adhesion layer 101 to be formed can be reduced. Therefore, the adhesive layer forming composition 100 according to the present embodiment preferably does not include a photopolymerization initiator added for the purpose of curing the adhesive layer forming composition 100 by light irradiation. When the adhesive layer forming composition 100 contains a photopolymerization initiator, photopolymerization occurs in the process of forming the adhesive layer 101, and the adhesive layer forming composition 100 is cured before the solvent (C) is completely volatilized. In addition, there is a possibility that the thickness of the adhesion layer 101 is increased.

<Viscosity of adhesive layer forming composition>
The viscosity at 23 ° C. of the adhesive layer forming composition 100 according to the present embodiment varies depending on the type and the mixing ratio of each component such as the compound (A), the compound (B) and the solvent (C), but is 0.5 mPa · s. It is preferably at least 20 mPa · s. It is more preferably 1 mPa · s or more and 10 mPa · s or less, and still more preferably 1 mPa · s or more and 5 mPa · s or less.

  By setting the viscosity of the adhesive layer forming composition 100 to 20 mPa · s or less, the coatability of the adhesive layer forming composition 100 to the substrate 102 is excellent, and the thickness of the adhesive layer forming composition 100 on the substrate 102 is adjusted. Can be easily performed.

<Impurities mixed into the adhesion layer forming composition>
It is preferable that the adhesive layer forming composition 100 according to the present embodiment does not contain impurities as much as possible. The impurities described here mean those other than the above-mentioned compound (A), compound (B), solvent (C) and other components (D).

  When the adhesive layer forming composition 100 is used in a nanoimprint process, it is particularly preferable that the composition does not contain particles and solid components. Here, the particles typically refer to gel-like or solid granular substances having a particle diameter (diameter) of several nm to several μm. Therefore, the content of the particles having a particle size larger than 0.2 μm is 0% by mass or more and less than 3% by mass when the whole of the composition 100 is 100% by mass. Is preferred.

  Therefore, the adhesive layer forming composition 100 according to the present embodiment is preferably obtained through a purification step. As such a purification step, filtration using a filter or the like is preferable.

  When performing filtration using a filter, specifically, after mixing the aforementioned compound (A), compound (B), solvent (C) and other components (D) to be added as necessary, For example, it is preferable to filter with a filter having a pore size of 0.001 μm or more and 5.0 μm or less. Further, it is more preferable to perform filtration with a filter having a pore size of 0.001 μm or more and 0.2 μm or less. When performing filtration using a filter, it is more preferable to perform the filtration in multiple steps or to repeat the filtration many times. Further, the filtered liquid may be filtered again. The filtration may be performed using a plurality of filters having different pore sizes. As a filter used for filtration, a filter made of polyethylene resin, polypropylene resin, fluorine resin, nylon resin, or the like can be used, but is not particularly limited.

  Through such a purification step, impurities such as particles mixed into the adhesive layer forming composition 100 can be removed. Accordingly, it is possible to prevent the adhesion layer 101 obtained after applying the adhesion layer forming composition 100 from being inadvertently generating a defect due to impurities such as particles.

  When the adhesive layer forming composition 100 is used for manufacturing a circuit board used for a semiconductor device such as a semiconductor integrated circuit, an impurity containing a metal atom in the adhesive layer forming composition 100 (metal impurity) It is preferable to avoid mixing as much as possible. This is to prevent the operation of the circuit board from being hindered by impurities such as metal. In such a case, the concentration of metal impurities contained in the adhesion layer forming composition 100 is preferably set to 10 ppm or less, more preferably 100 ppb or less.

  Therefore, it is preferable that the adhesive layer forming composition 100 is prepared without contacting the metal in the manufacturing process. That is, when weighing each raw material of the compound (A), the compound (B), the solvent (C), and other components (D) to be added as necessary, or when mixing and stirring, the metal It is preferable not to use a weighing instrument, a container or the like. Further, in the above-mentioned purification step, it is preferable to further perform filtration using a metal impurity removal filter. As the metal impurity removing filter, a filter made of cellulose and diatomaceous earth, an ion exchange resin, or the like can be used, but is not particularly limited. It is preferable that these metal impurity removal filters are used after being cleaned. As the cleaning method, it is preferable to perform cleaning with ultrapure water, cleaning with alcohol, and co-cleaning with the adhesion layer forming composition 100 in this order.

<Photocurable composition>
The photocurable composition 103 used together with the adhesion layer 101 formed from the adhesion layer forming composition 100 according to the present embodiment is generally composed of a component (E) which is a polymerizable compound and a component which is a photopolymerization initiator. (F).

[Component (E): polymerizable compound]
Component (E) is a polymerizable compound. Here, in the present specification, the polymerizable compound reacts with a polymerization factor (radical or the like) generated from a photopolymerization initiator (component (F)), and undergoes a chain reaction (polymerization reaction) to produce a polymer compound (polymer). Is a compound that forms a film consisting of

  Component (E) may be composed of one type of polymerizable compound, or may be composed of a plurality of types of polymerizable compounds.

  Examples of such a polymerizable compound include a radical polymerizable compound. The radical polymerizable compound is preferably a compound having at least one acryloyl group or methacryloyl group, that is, a (meth) acryl compound.

  Therefore, the polymerizable compound as the component (E) preferably contains a (meth) acrylic compound. Further, the main component of the component (E) is more preferably a (meth) acrylic compound, and most preferably a (meth) acrylic compound. The fact that the main component of the component (E) described herein is a (meth) acrylic compound means that 90% by weight or more of the component (E) is a (meth) acrylic compound.

  When the radical polymerizable compound is composed of a plurality of types of compounds having one or more acryloyl groups or methacryloyl groups, it is preferable to include a monofunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer. This is because a cured film having high strength can be obtained by combining a monofunctional (meth) acrylate monomer and a polyfunctional (meth) acrylate monomer.

  Examples of the monofunctional (meth) acryl compound having one acryloyl group or methacryloyl group include, for example, phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, and 3-phenoxy -2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, EO-modified p-cumylphenol (meth) acrylate, 2-bromophenoxyethyl (meth) acrylate, 2,4-dibromophenoxyethyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acryl EO-modified phenoxy (meth) acrylate, PO-modified phenoxy (meth) acrylate, polyoxyethylene nonyl phenyl 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 (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 Hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) TA) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 2-naphthylmethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxy Ethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate, methoxy polypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) Examples include, but are not limited to, acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and the like.

  Commercially available monofunctional (meth) acrylic compounds include Aronix M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (all manufactured by Toagosei), MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, viscote # 150, # 155, # 158, # 190, # 192, # 193, # 220, # 2000, # 2100, # 2150 (Above, manufactured by Osaka Organic Chemical Industry), Light Acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP- 4EA, NP-8EA, Epoxy S M-600A (Kyoeisha Chemical), KAYARAD TC110S, R-564, R-128H (Nippon Kayaku), NK ester AMP-10G, AMP-20G (Shin Nakamura Chemical), FA-511A, 512A, 513A (manufactured by Hitachi Chemical), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (manufactured by Daiichi Kogyo Seiyaku), VP ( BASF), ACMO, DMAA, DMAPAA (all manufactured by Kojin) and the like, but are not limited thereto.

  Examples of the polyfunctional (meth) acrylic compound having two or more acryloyl groups or methacryloyl groups include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and EO-modified trimethylolpropane tri (meth) acrylate , PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, dimethylol tricyclodecane diacrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di ( T) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-adamantane dimethanol diacrylate, o- Xylylene di (meth) acrylate, m-xylylene di (meth) acrylate, p-xylylene di (meth) acrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, tris (2-hydroxyethyl) isocyanurate tri (Meth) acrylate, tris (acryloyloxy) isocyanurate, bis (hydroxymethyl) tricyclodecanedi (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meta) Acrylate, EO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane, PO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane, EO, PO-modified 2,2- Examples include, but are not limited to, bis (4-((meth) acryloxy) phenyl) propane.

  Commercially available polyfunctional (meth) acrylic compounds include Iupimer UV SA1002, SA2007 (all manufactured by Mitsubishi Chemical), Biscoat # 195, # 230, # 215, # 260, # 335HP, # 295, # 300, # 360, # 700, GPT, 3PA (all manufactured by Osaka Organic Chemical Industry), light acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE- 3A, PE-4A, DPE-6A (all made by Kyoeisha Chemical), A-DCP, A-HD-N, A-NOD-N, A-DOD-N (all made by Shin-Nakamura Chemical), KAYARAD PET -30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (all manufactured by Nippon Kayaku) ), Aronix M208, M210, M215, M220, M240, M305, M309, M310, M315, M325, M400 (all manufactured by Toagosei), Lipoxy VR-77, VR-60, VR-90 (all manufactured by Showa Denko) ), But are not limited to these.

  In the above-mentioned compound group, (meth) acrylate means acrylate or methacrylate having an alcohol residue equivalent thereto. The (meth) acryloyl group means an acryloyl group or a methacryloyl group having an alcohol residue equivalent thereto. EO indicates ethylene oxide, and EO-modified compound A indicates a compound in which a (meth) acrylic acid residue and an alcohol residue of compound A are bonded via a block structure of an ethylene oxide group. PO indicates propylene oxide, and PO-modified compound B indicates a compound in which a (meth) acrylic acid residue and an alcohol residue of compound B are bonded via a propylene oxide group block structure.

[Component (F): Photopolymerization initiator]
Component (F) is a photopolymerization initiator. Here, in the present specification, the photopolymerization initiator is a compound that senses light having a predetermined wavelength to generate a polymerization factor (radical). Specifically, the photopolymerization initiator is a polymerization initiator (radical generator) that generates radicals by light (infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, charged particle beams such as X-rays, electron beams, and radiation). It is. More specifically, for example, a polymerization initiator that generates a radical by light having a wavelength of 150 nm or more and 400 nm or less.

  Component (F) may be composed of one type of photopolymerization initiator or may be composed of a plurality of types 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, (O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o- or p-methoxyphenyl) -4,5-diphenylimidazole dimer, which may have a substituent, 4,5-triarylimidazole dimer; benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy -4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diamino Benzophenone derivatives such as benzophenone; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane- Α-amino aromatic ketone derivatives such as 1-one; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone , 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantaraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. Quinones; benzoin methyl e Benzoin ether derivatives such as ether, benzoin ethyl ether and benzoin phenyl ether; benzoin derivatives such as benzoin, methyl benzoin, ethyl benzoin and propyl benzoin; benzyl derivatives such as benzyl dimethyl ketal; 9-phenyl acridine, 1,7-bis (9 Acridine derivatives such as, 9'-acridinyl) heptane; N-phenylglycine derivatives such as N-phenylglycine; acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2- Acetophenone derivatives such as phenylacetophenone; thioxane such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethyl Acylphosphine oxide derivatives such as pentylphosphine oxide; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- Oxime ester derivatives such as (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1- ( 4-isopropylphenyl) -2-hydr Carboxymethyl-2-methylpropan-1-one, 2-hydroxy-2-methyl-1 but one, and the like, but are not limited to.

  Commercial products of the above radical generators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin TPO, LR8893, and LR8970. (Above, manufactured by BASF), Ubecryl P36 (manufactured by UCB) and the like, but are not limited thereto.

  The compounding ratio of the component (F) in the photocurable composition 103 is preferably from 0.01% by weight to 10% by weight, and more preferably from 0.1% by weight to 7% by weight, based on the total amount of the component (E). % Is more preferable.

  By setting the mixing ratio of the component (F) in the photocurable composition 103 to 0.01% by weight or more based on the total amount of the component (E), the curing speed of the photocurable composition 103 is increased, and the reaction efficiency is increased. Can be increased. By setting the blending ratio of the component (F) to 10.0% by weight or less based on the total amount of the component (E), deterioration of the mechanical strength of the obtained cured film (109, 110) can be prevented in many cases. Because.

[Other additive components (G)]
The photocurable composition 103 contains, in addition to the components (E) and (F) described above, other additional components (G) according to various purposes within a range that does not impair the effects of the present invention. It may be. Examples of such an additive component (G) include a sensitizer, a hydrogen donor, an internal release agent, a surfactant, an antioxidant, a volatile solvent, a polymer component, and a polymerization initiator other than the component (F). And the like.

  The sensitizer is a compound appropriately added for the purpose of accelerating the polymerization reaction and improving the reaction conversion. Examples of the sensitizer include a sensitizing dye.

  The sensitizing dye is a compound that is excited by absorbing light of a specific wavelength and interacts with the component (F). The interaction described here refers to energy transfer, electron transfer, or the like from the sensitizing dye in the excited state to the component (F).

  Specific examples of the sensitizing dye include anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, and thiopyrylium salt-based dyes. Dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, pyrylium salt dyes, and the like, It is not limited to these.

  One type of sensitizer may be used alone, or two or more types may be mixed and used.

  The hydrogen donor is a compound that reacts with a starting radical generated from the component (F) or a radical at the terminal of polymerization growth to generate a radical having higher reactivity. It is preferable to add when component (F) is a photoradical generator.

  Specific examples of such a hydrogen donor include n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiuronium-p-toluenesulfinate, triethylamine, diethylaminoethyl Methacrylate, triethylenetetramine, 4,4'-bis (dialkylamino) benzophenone, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethanol Examples thereof include, but are not limited to, amines, amine compounds such as N-phenylglycine, and mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionate.

  As the hydrogen donor, one kind may be used alone, or two or more kinds may be used in combination.

  The hydrogen donor may have a function as a sensitizer.

  When the photocurable composition 103 contains a sensitizer or a hydrogen donor as the other additive component (G), the content of each of them is preferably 0.1% by weight based on the total amount of the component (E). % To 20% by weight. Further, the content is more preferably 0.1% by weight or more and 5.0% by weight or less, and still more preferably 0.2% by weight or more and 2.0% by weight or less. If the sensitizer is contained in an amount of 0.1% by weight or more with respect to the total amount of the component (E), the polymerization promoting effect can be more effectively exhibited. Further, by setting the content of the sensitizer or the hydrogen donor to 5.0% by weight or less, the molecular weight of the polymer compound constituting the cured film to be produced can be sufficiently increased. Furthermore, poor dissolution of these components in the photocurable composition 103 and a decrease in storage stability of the photocurable composition 103 can be suppressed.

  In order to reduce the interfacial bonding force between the cured film 109 obtained by curing the photocurable composition 103 and the mold 104, that is, to reduce the releasing force in a releasing step described later, the photocurable composition 103 is used. Can be added with an internal release agent. In this specification, the internal addition type means that the photocurable composition 103 is added to the photocurable composition 103 before the step of disposing the photocurable composition 103. One type of the internal release agent may be used alone, or two or more types may be used as a mixture.

  As the internal release agent, a surfactant such as a silicone-based surfactant, a fluorine-based surfactant, and a hydrocarbon-based surfactant can be used. In the present embodiment, the internal release agent has no polymerizability.

  Examples of the fluorinated surfactant include a polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adduct of an alcohol having a perfluoroalkyl group and a polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adduct of a perfluoropolyether. included. Note that the fluorine-based surfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, or the like in a part (for example, a terminal group) of a molecular structure.

  Commercial products may be used as the fluorine-based surfactant. Commercially available products include, for example, Megafac F-444, TF-2066, TF-2067, TF-2068 (all made by DIC), Florard FC-430, FC-431 (all made by Sumitomo 3M), Surflon S- 382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (all manufactured by Tochem Products), PF-636, PF-6320, PF-656 , PF-6520 (above, manufactured by OMNOVA Solutions), Unidyne DS-401, DS-403, DS-451 (above, manufactured by Daikin Industries), Futergent 250, 251, 222F, 208G (above, manufactured by Neos) and the like. But not limited to these.

  Further, the internal release agent may be a hydrocarbon-based surfactant.

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

  Examples of the alkyl alcohol polyalkylene oxide adduct include methyl alcohol ethylene oxide adduct, decyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide / And propylene oxide adducts. The terminal group of the alkyl alcohol polyalkylene oxide adduct is not limited to a hydroxyl group that can be produced by simply adding a polyalkylene oxide to an alkyl alcohol. This hydroxyl group may be converted into another substituent, for example, a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a thiol group, a silanol group, or a hydrophobic functional group such as an alkyl group or an alkoxy group.

  As the alkyl alcohol polyalkylene oxide adduct, a commercially available product may be used. Commercially available products include, for example, polyoxyethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, MP-550, MP-1000) manufactured by Aoki Yushi Kogyo, and polyoxyethylene decyl ether manufactured by Aoki Yushi Kogyo (Decyl alcohol ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, D-1310), polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) manufactured by Aoki Yushi Kogyo Kogyo (BLAUNON EL-1505) ), Polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) manufactured by Aoki Yushi Kogyo (BLAUNON CH-305, CH-310), polyoxyethylene stearyl ether manufactured by Aoki Yushi Kogyo Ter (stearyl alcohol ethylene oxide adduct) (BLAUNON SR-705, SR-707, SR-715, SR-720, SR-730, SR-750), randomized polyoxyethylene polyoxypropylene manufactured by Aoki Yushi Kogyo Kogyo Examples include stearyl ether (BLAUNON SA-50 / 50 1000R, SA-30 / 70 2000R), polyoxyethylene methyl ether (Plurio A760E) manufactured by BASF, and polyoxyethylene alkyl ether (Emulgen series) manufactured by Kao. It is not limited to these.

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

  When the photocurable composition 103 contains an internal additive release agent as another additive component (G), the content of the internal additive release agent is, for example, 0 with respect to the total amount of the component (E). It is preferably from 0.001% by weight to 10% by weight. It is more preferably 0.01% by weight or more and 7% by weight or less, and further preferably 0.05% by weight or more and 5% by weight or less. When the content is at least 0.001% by weight or more and 10% by weight or less, the releasing force reducing effect and the filling property are excellent.

  Further, the photocurable composition 103 may contain a volatile solvent as another additive component (G), but it is preferable that the photocurable composition 103 contains substantially no volatile solvent. Here, substantially not containing a solvent means that a volatile solvent other than a volatile solvent that is unintentionally included such as an impurity is not contained. That is, for example, the content of the volatile solvent in the photocurable composition 103 is preferably 3% by weight or less, more preferably 1% by weight or less based on the entire photocurable composition 103. Here, the volatile solvent refers to a volatile solvent generally used in the photocurable composition 103 and the photoresist. That is, the type of the volatile solvent is not particularly limited as long as it dissolves and uniformly disperses each compound constituting the photocurable composition 103 and does not react with the compound.

[Temperature at the time of mixing the photocurable composition]
When preparing the photocurable composition 103 according to this embodiment, at least the component (E) and the component (F) are mixed and dissolved under a predetermined temperature condition. Specifically, the heat treatment is performed in a range of 0 ° C. or more and 100 ° C. or less. The same applies to the case where other additive components (G) are contained.

[Viscosity of photocurable composition]
In the photocurable composition 103 according to this embodiment, the viscosity at 23 ° C. of the mixture of each component excluding the volatile solvent is preferably from 1 mPa · s to 100 mPa · s. Further, it is more preferably 1 mPa · s or more and 50 mPa · s or less, and still more preferably 1 mPa · s or more and 20 mPa · s or less.

  By setting the viscosity of the photocurable composition 103 to 100 mPa · s or less, when the photocurable composition 103 comes into contact with the mold 104, the photocurable composition 103 fills the concave portions of the fine pattern on the mold. The time it takes to do so does not have to be long. In addition, pattern defects due to poor filling hardly occur.

  Further, by setting the viscosity to 1 mPa · s or more, coating unevenness is less likely to occur when the photocurable composition 103 is applied on the substrate 102, and when the photocurable composition 103 is brought into contact with the mold 104. This makes it difficult for the photocurable composition 103 to flow out of the end of the mold 104.

[Surface tension of photocurable composition]
As for the surface tension of the photocurable composition 103 according to the present embodiment, the surface tension at 23 ° C. of the mixture of each component excluding the solvent is preferably 5 mN / m or more and 70 mN / m or less. Further, it is more preferably 7 mN / m or more and 35 mN / m or less, and still more preferably 10 mN / m or more and 32 mN / m or less. Here, by setting the surface tension to 5 mN / m or more, when the photocurable composition 103 is brought into contact with the mold 104, the concave portion of the fine pattern on the mold 104 is filled with the photocurable composition 103. The time does not need to be long.

  Further, by setting the surface tension to 70 mN / m or less, the cured films (109, 110) obtained by photocuring the photocurable composition 103 become cured films having surface smoothness.

[Impurities mixed into the photocurable composition]
It is preferable that the photocurable composition 103 according to the present embodiment does not contain impurities as much as possible, similarly to the adhesive layer forming composition 100.

  Therefore, the photocurable composition 103 is preferably obtained through a purification step, similarly to the adhesive layer forming composition 100. As such a purification step, filtration using a filter or the like is preferable.

  When performing filtration using a filter, specifically, after mixing the above-mentioned component (E), component (F) and other additional components (G) to be added as needed, for example, It is preferable to filter with a filter of 0.001 μm or more and 5.0 μm or less. When performing filtration using a filter, it is more preferable to perform the filtration in multiple steps or to repeat the filtration many times. Further, the filtered liquid may be filtered again. The filtration may be performed using a plurality of filters having different pore sizes. As a filter used for filtration, a filter made of polyethylene resin, polypropylene resin, fluorine resin, nylon resin, or the like can be used, but is not particularly limited.

  Through such a purification step, impurities such as particles mixed into the photocurable composition 103 can be removed. Accordingly, it is possible to prevent the cured film 109 obtained after photocuring the photocurable composition 103 by impurities such as particles from inadvertently causing irregularities, thereby preventing pattern defects.

  When the photocurable composition 103 is used for manufacturing a circuit board used for a semiconductor device such as a semiconductor integrated circuit, an impurity containing a metal atom in the photocurable composition 103 (metal impurity) It is preferable to avoid mixing as much as possible. This is to prevent the operation of the circuit board from being hindered by impurities such as metals, as in the case of the impurities mixed in the adhesion layer forming composition 100. In such a case, the concentration of the metal impurities contained in the photocurable composition 103 is preferably set to 10 ppm or less, more preferably 100 ppb or less.

  Therefore, it is preferable that the photocurable composition 103 is prepared without being brought into contact with metal in the production process. That is, when weighing each raw material of the component (E), the component (F), and the additive component (G), or when mixing and stirring, it is preferable not to use a metal weighing instrument, a container, or the like. . Further, in the above-mentioned purification step, it is preferable to further perform filtration using a metal impurity removal filter. As the metal impurity removing filter, a filter made of cellulose and diatomaceous earth, an ion exchange resin, or the like can be used, but is not particularly limited. It is preferable that these metal impurity removal filters are used after being cleaned. As the cleaning method, it is preferable to perform the cleaning with ultrapure water, the cleaning with alcohol, and the co-washing with the photocurable composition 103 in this order.

<Method of manufacturing cured product pattern>
Next, a method for manufacturing a cured product pattern (a cured film having a pattern shape) according to the present embodiment will be described. FIG. 1 is a cross-sectional view schematically illustrating an example of a method for manufacturing a cured product pattern according to the present embodiment.

The method for producing a cured product pattern according to the present embodiment includes:
[1] a first step (adhesion layer forming step) of forming an adhesion layer on a substrate using the above-described adhesion layer forming composition according to the present embodiment;
[2] a second step (arranging step) of arranging the photocurable composition on a substrate,
[3] a third step of bringing the photocurable composition disposed on the substrate into contact with the mold (a mold contact step);
[5] a fourth step (light irradiation step) of irradiating the photocurable composition with light in a state where the photocurable composition and the mold are in contact with each other;
[6] a fifth step of releasing the cured product obtained in the fourth step and the mold (release step);
Having.

In addition, the method for manufacturing a cured product pattern according to the present embodiment includes the following steps between the third step and the fourth step.
[4] Step of aligning the position of the substrate and the mold (alignment step)
May be provided.

  The method for manufacturing a cured product pattern according to the present embodiment is a method for manufacturing a cured product pattern using a photo nanoimprint method.

  The cured product pattern obtained by the method for producing a cured product pattern according to the present embodiment is preferably a film having a pattern having a size of 1 nm or more and 10 mm or less. It is more preferable that the film has a pattern having a size of 10 nm or more and 100 μm or less. In general, a pattern forming technique for forming a film having a nano-sized (1 nm or more and 100 nm or less) pattern (irregular structure) using light is called an optical nanoimprint method.

  Hereinafter, each step will be described.

[[1] Adhesive layer forming step]
In this step (adhesion layer forming step), as shown in FIG. 1A, an adhesion layer containing a polymer compound (polymer) as a main component using the above-described adhesion layer forming composition 100 according to the present embodiment. 101 is formed on a substrate 102.

  The substrate 102 on which the photocurable composition 103 is to be disposed is a substrate or a support, and any substrate can be selected for various purposes. For example, substrates for semiconductor devices such as silicon wafers, aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, silicon nitride, quartz, glass, optical films, ceramic materials, vapor-deposited films, Magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, etc., polymer substrate such as paper, polyester film, polycarbonate film, polyimide film, TFT array substrate, PDP electrode plate, plastic substrate, ITO A conductive base such as metal or metal, an insulating base, or the like can be used. However, when the substrate is processed by etching or the like in the substrate processing step described later, it is preferable to use a semiconductor device substrate such as a silicon wafer. As the base material 102, one or more kinds of films such as spin-on-glass, organic substances, metals, oxides, and nitrides formed on the above-described substrate may be used.

  In the present embodiment, it is particularly preferable to use a substrate having a hydroxyl group (OH group) such as a silanol group (SiOH group) on the surface. Examples of these base materials include a silicon wafer, quartz, and glass. It is considered that by using a substrate having a hydroxyl group on the surface, the hydroxyl group on the surface of the substrate 102 and the thiol group of the compound (B) easily form a chemical bond by heat treatment in the basic step. Also, when the compound (A) has an alkoxyalkyl group, it is considered to form a chemical bond with a hydroxyl group.

  Examples of a method for applying the adhesive layer forming composition 100 on the base material 102 include an inkjet method, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, A spin coating method, a slit scanning method, or the like can be used. Among these methods, the spin coating method is particularly preferable from the viewpoint of applicability, particularly, uniformity of film thickness.

  After applying the adhesive layer forming composition 100 to the base material 102, the solvent (C) contained in the adhesive layer forming composition 100 is volatilized by drying. At this time, at the same time as the solvent (C) is volatilized, the base material 102 may be reacted with the compound (A) or the compound (B), and the compound (A) and the compound (B) may be reacted. Thus, a bond is formed between the base material 102 and the adhesion layer 101, and a bond is formed between the compound (A) and the compound (B) in the adhesion layer 101. The bond between the compound (A) and the compound (B) is assumed to be a sulfide bond formed by any of the following reactions. That is, a dealcoholization reaction between an alkoxyalkyl group of the compound (A) and a thiol group of the compound (B), or a reaction between an alkylol group of the compound (A) and a thiol group of the compound (B) During the dehydration reaction.

  In these reactions, it is preferable to heat. The temperature at the time of the reaction depends on the reactivity between the compound (A) or the compound (B) and the substrate 102, the reactivity between the compound (A) and the compound (B), the compound (A), the compound (B), and the solvent. It can be appropriately selected depending on the boiling point of (C) and the like. Preferably it is 70 to 250 degreeC, More preferably, it is 100 to 220 degreeC, More preferably, it is 140 to 220 degreeC. The drying of the solvent (C), the reaction between the base material 102 and the compound (A) or the compound (B), and the crosslinking reaction between the compound (A) and the compound (B) may be performed at the same temperature. And at different temperatures. That is, these reactions may be performed simultaneously or sequentially.

  The thickness of the adhesion layer 101 formed by disposing the adhesion layer forming composition 100 according to the present embodiment on the substrate 102 varies depending on the intended use, but is, for example, 0.1 nm or more and 100 nm or less. The thickness is more preferably 0.5 nm or more and 60 nm or less, and still more preferably 1 nm or more and 10 nm or less.

  When the adhesion layer forming composition 100 according to the present embodiment is applied on the base material 102 to form the adhesion layer 101, the adhesion layer forming composition 100 is further used on the formed adhesion layer 101. The adhesive layer may be formed by multiple coatings. Further, the surface of the formed adhesion layer 101 is preferably as flat as possible. The surface roughness is preferably 1 nm or less.

  Through the above steps, a laminate including the base material 102 and the polymer layer (the adhesion layer 101) stacked on the base material 102 can be formed. As described above, the polymer layer contains, in the molecule, a sulfide bond generated by a reaction between the alkoxyalkyl group or alkylol group of the compound (A) and the thiol group of the compound (B).

[[2] Arrangement step]
In this step (arrangement step), as shown in FIG. 1B, the above-described photocurable composition 103 is arranged (coated) on the adhesion layer 101 formed on the base material 102 to form a coating film.

  In the present embodiment, examples of the method of disposing the photocurable composition 103 on the substrate 102 include an inkjet method, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, Extrusion coating, spin coating, slit scanning, and the like can be used. Among these methods, the inkjet method is particularly preferable in the photo nanoimprint method. The thickness of the coating film (shape transfer layer) varies depending on the intended use, but is, for example, 0.01 μm or more and 100.0 μm or less.

[[3] Mold contact step]
Next, as shown in FIG. 1C, a mold 104 having a prototype pattern for transferring a pattern shape is brought into contact with the coating film made of the photocurable composition 103 formed in the previous step (arrangement step). (FIG. 1 (c-1)). As a result, (part of) the coating film made of the photocurable composition 103 fills the concave portions of the fine pattern on the surface of the mold 104, and becomes the coating film 105 filled in the fine pattern of the mold (FIG. 1). (C-2)).

  As the mold 104, a mold 104 made of a light-transmitting material may be used in consideration of the next step (light irradiation step). Specific examples of the material of the material constituting the mold 104 include light transparent resin such as glass, quartz, PMMA, and polycarbonate resin, transparent metal vapor-deposited film, flexible film such as polydimethylsiloxane, light cured film, and metal film. Are preferred. However, when a light-transparent resin is used as the material of the material constituting the mold 104, it is necessary to select a resin that does not dissolve in the components contained in the photocurable composition 103. Since the coefficient of thermal expansion is small and the pattern distortion is small, the material of the material forming the mold 104 is particularly preferably quartz.

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

  In order to improve the releasability between the photocurable composition 103 and the surface of the mold 104, the mold 104 is subjected to a surface treatment before this step, which is a mold contacting step between the photocurable composition 103 and the mold 104. You may go. As a method of the surface treatment, a method of applying a release agent to the surface of the mold 104 to form a release agent layer is exemplified.

  Here, the release agent applied to the surface of the mold 104 includes a silicone release agent, a fluorine release agent, a hydrocarbon release agent, a polyethylene release agent, a polypropylene release agent, and a paraffin release agent. Mold release agents, montan release agents, carnauba release agents, and the like. For example, a commercially available coating release agent such as Optool DSX manufactured by Daikin Industries, Ltd. can also be suitably used. One type of release agent may be used alone, or two or more types may be used in combination. Among these, fluorine-based and hydrocarbon-based release agents are particularly preferred.

  In this step (mold contact step), as shown in FIG. 1 (c-1), when the mold 104 and the photocurable composition 103 are brought into contact with each other, the pressure (mold pressure) applied to the photocurable composition 103 is: There is no particular limitation. Usually, it is 0 MPa or more and 100 MPa or less. Among them, the pressure is preferably from 0 MPa to 50 MPa, more preferably from 0 MPa to 30 MPa, even more preferably from 0 MPa to 20 MPa.

  In this step, the time during which the mold 104 is brought into contact with the photocurable composition 103 is not particularly limited. Usually, it is 0.1 to 600 seconds, preferably 0.1 to 300 seconds, more preferably 0.1 to 180 seconds, and more preferably 0.1 to 120 seconds. Is particularly preferred.

  This step can be performed under any conditions of an air atmosphere, a reduced pressure atmosphere, and an inert gas atmosphere.However, since the influence of oxygen or moisture on the curing reaction can be prevented, the reduced pressure atmosphere or the inert It is preferable to use a gas atmosphere. Specific examples of the inert gas that can be used when performing this step under an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various types of chlorofluorocarbon, and the like, or a mixed gas thereof. In the case where this step is performed under a specific gas atmosphere including an air atmosphere, a preferable pressure is 0.0001 to 10 atm.

  The mold contact step may be performed in an atmosphere containing a condensable gas (hereinafter, referred to as “condensable gas atmosphere”). In this specification, a condensable gas refers to a gas that is condensed and liquefied by a capillary pressure generated by a pressure at the time of filling. Specifically, the condensable gas is supplied to the concave portion of the fine pattern formed on the mold 104 and the gap between the mold 104 and the base material 102 or the adhesion layer 101 together with (part of) the coating film 105 in the atmosphere. When the gas is filled, it condenses and liquefies. Note that the condensable gas exists as a gas in the atmosphere before the photocurable composition 103 (shape transfer layer) and the mold 104 come into contact with each other in the mold contacting step (FIG. 1C-1).

  When the mold contacting step is performed in a condensed gas atmosphere, the gas filled in the concave portions of the fine pattern is liquefied, and the bubbles disappear, so that the filling property is excellent. The condensable gas may be dissolved in the photocurable composition 103.

  The boiling point of the condensable gas is not limited as long as it is equal to or lower than the ambient temperature in the mold contact step, but is preferably from -10 ° C to 23 ° C, more preferably from 10 ° C to 23 ° C. In this range, the filling property is further excellent.

  The vapor pressure of the condensable gas at the ambient temperature in the mold contacting step is not limited as long as it is equal to or lower than the mold pressure at the time of stamping in the mold contacting step, but is preferably 0.1 to 0.4 MPa. In this range, the filling property is further excellent. If the vapor pressure at ambient temperature is higher than 0.4 MPa, the effect of eliminating bubbles may not be sufficiently obtained. On the other hand, when the vapor pressure at the ambient temperature is lower than 0.1 MPa, decompression is required, and the apparatus configuration of an imprint apparatus that manufactures a film having a pattern shape using the manufacturing method according to the present embodiment is complicated. Tend.

  The atmosphere temperature in the mold contact step is not particularly limited, but is preferably 20 ° C to 25 ° C.

As the condensable gas, specifically, chlorofluorocarbon (CFC) such as trichlorofluoromethane, fluorocarbon (FC), hydrochlorofluorocarbon (HCFC), 1,1,1,3,3-pentafluoropropane (CHF ₂ CH) ₂ CF ₃ , HFC-245fa, PFP) and other hydrofluorocarbons (HFC), pentafluoroethyl methyl ether (CF ₃ CF ₂ OCH ₃ , HFE-245mc) and other fluorocarbons such as HFE. However, it is not limited to these.

  Of these, 1,1,1,3,3-pentafluoropropane (vapor pressure at 23 ° C. 0.14 MPa, (Boiling point 15 ° C.), trichlorofluoromethane (vapor pressure at 23 ° C. 0.1056 MPa, boiling point 24 ° C.) and pentafluoroethyl methyl ether are preferred, and from the viewpoint of further excellent safety, 1,1,1,3,3 3-Pentafluoropropane is particularly preferred.

  As the condensable gas, one type may be used alone, or two or more types may be mixed and used. As the condensable gas, a mixed gas mixed with a non-condensable gas such as air, nitrogen, carbon dioxide, helium, and argon may be used. As the non-condensable gas mixed with the condensable gas, helium is preferable from the viewpoint of filling properties. Helium can pass through the mold 104. Therefore, when the gas (condensable gas and helium) in the atmosphere is filled together with (part of) the coating film 105 into the concave portion of the fine pattern formed on the mold 104 in the mold contacting step, the condensable gas becomes As it liquefies, helium permeates the mold 104. Therefore, when helium is used as the above-mentioned non-condensable gas, the filling property is excellent.

[[4] Positioning process]
Next, as shown in FIG. 1D, if necessary, the position of the mold 104 and / or the base material 102 is adjusted so that the mold-side positioning mark 106 and the positioning mark 107 of the base material 102 coincide with each other. I do.

[[5] Light irradiation step]
Next, as shown in FIG. 1 (e), in a state where the alignment is performed by the step [4] (positioning step), the contact portion of the photocurable composition 103 with the mold 104 is interposed via the mold 104. Irradiate light. More specifically, the coating film 105 filled in the fine pattern of the mold 104 is irradiated with light via the mold 104 (FIG. 1 (e-1)). Thereby, the coating film 105 filled in the fine pattern of the mold 104 is cured by the irradiated light 108 to become a cured product 109 (FIG. 1 (e-2)).

  Here, light for irradiating the photocurable composition 103 constituting the coating film 105 filled in the fine pattern of the mold 104 is selected according to the sensitivity wavelength of the photocurable composition 103. Specifically, it is preferable to appropriately select and use ultraviolet light having a wavelength of 150 nm or more and 400 nm or less, X-rays, electron beams, or the like.

Among these, the light (irradiation light 108) for irradiating the photocurable composition 103 is particularly preferably ultraviolet light. This is because many of those commercially available as curing assistants (photopolymerization initiators) have sensitivity to ultraviolet light. Examples of the light source that emits ultraviolet light include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a low-pressure mercury lamp, a Deep-UV lamp, a carbon arc lamp, a chemical lamp, a metal halide lamp, a xenon lamp, a KrF excimer laser, an ArF excimer laser, and F _2. An excimer laser and the like are mentioned, and an ultra-high pressure mercury lamp is particularly preferable. The number of light sources used may be one or more. Light irradiation may be performed on the entire surface of the coating film 105 filled in the fine pattern of the mold 104, or may be performed only on a partial region.

  The light irradiation may be performed intermittently a plurality of times on the entire region on the base material 102 or may be continuously performed on the entire region. Furthermore, a partial area A may be irradiated in the first irradiation step, and an area B different from the area A may be irradiated in the second irradiation step.

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

[[6] Release process]
Next, the cured product 109 and the mold 104 are separated from each other. At this time, a cured product pattern 110 having a predetermined pattern shape is formed on the base material 102.

  In this step (release step), as shown in FIG. 1F, the cured product 109 and the mold 104 are separated from each other, and in step [5] (light irradiation step), the fine pattern formed on the mold 104 is removed. A cured product pattern 110 having a pattern shape that becomes a reverse pattern is obtained.

  When the mold contacting step is performed in a condensable gas atmosphere, when the cured product 109 and the mold 104 are separated from each other in the release process, the pressure at the interface where the cured product 109 and the mold 104 come into contact with each other decreases. Accordingly, the condensable gas evaporates. Accordingly, there is a tendency that an effect of reducing a releasing force, which is a force necessary for separating the cured product 109 and the mold 104, is obtained.

  The method of separating the cured product 109 and the mold 104 is not particularly limited as long as a part of the cured film 109 is not physically damaged when separated, and various conditions are not particularly limited. For example, the base material 102 may be fixed and the mold 104 may be moved away from the base material 102 and peeled off. Alternatively, the mold 104 may be fixed and the base material 102 may be moved away from the mold and peeled off. Alternatively, both of them may be pulled in opposite directions to be separated.

  Through a series of steps (manufacturing process) including the above steps [1] to [6], a cured film having a desired concavo-convex pattern shape (pattern shape due to the concavo-convex shape of the mold 104) at a desired position is obtained. Can be. The obtained cured film can be used, for example, as an optical member such as a Fresnel lens or a diffraction grating (including a case where it is used as one member of an optical member). In such a case, an optical member having at least the base material 102 and the cured product pattern 110 arranged on the base material 102 can be provided.

  In the method for manufacturing a film having a pattern shape according to this embodiment, the repeating unit (shot) including the steps [1] to [6] can be repeatedly performed on the same base material 102 a plurality of times. By repeating the repeating unit (shot) comprising the steps [1] to [6] a plurality of times, a plurality of desired concavo-convex pattern shapes (pattern shapes due to the concavo-convex shape of the mold 104) are formed at desired positions on the base material 102. Thus, a cured film 110 can be obtained.

[[7] Remaining film removing step of removing a part of the cured film]
Although the cured product pattern 110 obtained in the step [6] (the releasing step) has a specific pattern shape, a part of the cured film may remain in a region other than a region where the pattern shape is formed. In the following description, a part of such a cured film may be referred to as a residual film. In such a case, as shown in FIG. 1 (g), the cured film (remaining film) in the region to be removed and the adhesive layer 101 below the cured film having the pattern shape are removed. I do. Thus, a cured product pattern 111 having a desired concavo-convex pattern shape (a pattern shape resulting from the concavo-convex shape of the mold 104) can be obtained.

  Here, as a method of removing the remaining film and the adhesion layer 101 thereunder, for example, a method of removing a cured film (remaining film) which is a concave portion of the cured product pattern 110 by etching or the like can be mentioned. Thereby, the surface of the base material 102 can be exposed in the concave portions of the pattern of the cured product pattern 110.

When the cured film in the concave portion of the cured product pattern 110 and the adhesive layer 101 under the cured film are removed by etching, the specific method is not particularly limited. For example, dry etching can be used. A conventionally known dry etching apparatus can be used for the dry etching. The source gas at the time of dry etching is appropriately selected depending on the element composition of the cured film 110 to be subjected to the etching, but CF ₄ , C ₂ F ₆ , C ₃ F ₈ , CCl ₂ F ₂ , CCl ₄ , CBrF ₃ , a halogen-based gas such as BCl ₃ , PCl ₃ , SF ₆ and Cl ₂ , a gas containing an oxygen atom such as O ₂ , CO and CO ₂ , an inert gas such as He, N ₂ and Ar, H ₂ and NH ₃ gas or the like can be used. Note that these gases can be used as a mixture.

  The cured product pattern 111 having a desired concavo-convex pattern shape (pattern shape due to the concavo-convex shape of the mold 104) at a desired position can be obtained by the manufacturing process of the above steps [1] to [7]. An article having the object pattern 111 can be obtained. That is, it is possible to obtain a device component having the base material 102, the adhesive layer 101 formed on the base material 102, and the photocured product (cured product pattern 111) having the uneven pattern formed on the adhesive layer 101. .

  In the device component obtained in the present embodiment, the adhesion layer 101 has a crosslinked structure formed from the compound (A) and the compound (B). When the compound represented by the general formula (1) is used as the compound (A), the adhesion layer 101 is made of 1,3,5-triazine in which the 2-, 4-, and 6-positions are substituted with nitrogen atoms. It has a ring and a sulfide bond in the structure. That is, the device component obtained in the present embodiment is a device component having a substrate and a photocured product having a concavo-convex pattern on the substrate, and an organic layer between the substrate and the photocured product. And the organic layer contains a 1,3,5-triazine ring and a sulfide bond.

  Further, when processing the base material 102 using the obtained cured product pattern 111, a base material processing step (step [8]) described later is performed.

  On the other hand, the obtained cured product pattern 111 can be used as an optical member (including a case where it is used as one member of an optical member) such as a diffraction grating or a polarizing plate to obtain an optical component. In such a case, an optical component having at least the base material 102 and the cured product pattern 111 disposed on the base material 102 can be obtained.

[[8] Substrate processing step]
The cured product pattern 111 having a concavo-convex pattern shape obtained by the method for producing a film having a pattern shape according to the present embodiment can also be used as a film for an interlayer insulating film included in an electronic component such as a semiconductor element. is there. Further, it can be used as a resist film at the time of manufacturing a semiconductor element. The semiconductor element here includes, for example, an LSI, a system LSI, a DRAM, an SDRAM, an RDRAM, a D-RDRAM, and the like, but is not limited thereto.

  When the cured product pattern 111 is used as a resist film, etching is performed on a part of the substrate 102 (the region denoted by reference numeral 112 in FIG. 1G) whose surface is exposed in step [7] (remaining film removal step). Alternatively, ion implantation or the like is performed. At this time, the cured product pattern 111 functions as an etching mask. In addition, by forming an electronic member, a circuit structure 113 (FIG. 1H) based on the pattern shape of the cured product pattern 111 can be formed on the base material 102. Thereby, a circuit board used for a semiconductor element or the like can be manufactured. Further, by connecting the circuit board to a circuit control mechanism of the circuit board, an electronic device such as a display, a camera, and a medical device can be formed.

  Similarly, using the cured product pattern 111 as a resist film, etching or ion implantation is performed to obtain device components such as an optical component, a microfluidic channel structure, and a patterned media structure. it can.

  Similarly, by using the cured product pattern 111 as a mask (resist film), etching or ion implantation can be performed to obtain an optical component.

  Alternatively, an imprint mold can be manufactured by etching a quartz substrate as the substrate 102 using the cured product pattern 111. In this case, the quartz substrate as the substrate 102 may be directly etched using the cured product pattern 111 as a mask. Alternatively, the hard mask material layer may be etched using the cured product pattern 111 as a mask, and the quartz substrate may be etched using the transferred pattern of the hard mask material as a mask. Alternatively, a second cured product made of a second curable material may be formed in the concave portion of the cured product pattern 111, and the quartz substrate may be etched using the second cured product as a mask.

When a part of the substrate whose surface is exposed is etched using the cured product pattern 111 as a mask, dry etching can be used. A conventionally known dry etching apparatus can be used for the dry etching. The source gas at the time of dry etching is appropriately selected depending on the element composition of the cured film to be subjected to the etching, but 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, Cl 2 or the like halogen-containing _gas, O _{2, CO,} a gas containing oxygen atoms such as CO _2, He, of N 2, Ar or the like not An active gas, a gas of H ₂ , NH _{3 or} the like can be used. Fluorine-based gases 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 are preferable. This is because the photocurable composition according to this embodiment has high resistance to dry etching using the fluorine-based gas. Note that these gases can be used as a mixture.

  Although etching and ion implantation have been described as methods for processing the substrate 102 using the cured product pattern 111 as a mask, the method is not limited to this. For example, a plating process or the like can be performed in a state where the cured product pattern 111 is formed on the substrate 102.

  When a circuit board or an electronic component is manufactured, the cured product pattern 111 may be finally removed from the processed base material, but may be left as a component of the element.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the technical scope of the present invention is not limited to the following Examples. All “parts” and “%” used below are based on weight unless otherwise specified.

<(1) Evaluation of curability>
The curability of the adhesive layer forming composition was evaluated by the following method.

(1-1) Preparation of Composition for Forming Adhesion Layer Compound (A) and compound (B) shown below were blended at the weight ratio shown in Table 1, and propylene glycol monomethyl ether acetate (Tokyo) was used as volatile solvent (C). (Manufactured by Kasei Kogyo). Thus, a mixed solution having a total concentration of the compound (A) and the compound (B) of 5% by weight was obtained.

  Next, the obtained mixed solution was filtered with a polytetrafluoroethylene filter having a pore size of 0.2 μm. In this way, Compositions 1 to 11, which are compositions for forming an adhesive layer for evaluation of curability, were prepared.

(Compound (A))
(A-1) Compound having six methoxymethyl groups: hexamethoxymethylmelamine (manufactured by Sanwa Chemical Co., trade name: Nicalac MW-390) (Formula (a))

  (A-2) Compound having four methoxymethyl groups (for comparative example): 1,3,4,6-tetrakis (methoxymethyl) glycoluril (manufactured by Sanwa Chemical, trade name: Nicalac MX-270) (formula (B))

(Compound (B))
(B-1) 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by Showa Denko, Name: Karenz MT NR-1) (Formula (c))

  (B-2) Trimethylolpropane tris (3-mercaptopropionate) (manufactured by Tokyo Kasei Kogyo) (Formula (d))

  (B-3) Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko, trade name: Karenz MT PE-1) (Formula (e))

  (B-4) Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Tokyo Chemical Industry) (formula (f))

(1-2) Formation of Adhesion Layer Each of the prepared compositions 1 to 11 was applied onto a silicon wafer by spin coating. The spin coating conditions were 3000 rpm and 30 seconds. Then, each composition was heated on a hot plate to form an adhesion layer. The heating conditions are shown in Table 2.

(1-3) Evaluation of curability By wiping the surface of the adhesion layer formed in (1-2) with a bencot impregnated with acetone, dissolution or peeling of the adhesion layer was visually checked to evaluate curability. did. In this example, A was evaluated when no dissolution or peeling of the adhesion layer occurred, and B was evaluated when dissolution or peeling occurred even in part. Table 2 summarizes the results.

  Compositions 1 to 7 are compositions using A-1 as compound (A). The compositions 1 to 7 were excellent in curability (Examples 1 to 7).

  On the other hand, Compositions 8 to 11 are compositions using A-2 as compound (A). Compositions 8 to 11 had insufficient curability (Comparative Examples 1 to 4).

  A-1 has six methoxymethyl groups, which are functional groups capable of binding to the thiol group of compound (B). Therefore, it is presumed that the reactivity with the compound (B) is excellent, and the network structure in which the compound (A) and the compound (B) in the adhesion layer formed after the reaction are crosslinked to each other becomes denser. As a result, the compositions 1 to 7 according to the examples were excellent in curability.

  On the other hand, A-2 has four methoxymethyl groups, which are functional groups capable of binding to the thiol group of compound (B). That is, the number of methoxymethyl groups in A-2 is smaller than the number of methoxymethyl groups in A-1. Therefore, it is presumed that A-2 has insufficient reactivity with the compound (B). Further, it is presumed that the network structure in which the compound (A) and the compound (B) in the adhesion layer formed after the reaction are cross-linked to each other is less sparse than when A-1 is used as the compound (A). As a result, Compositions 8 to 11 according to Comparative Examples had insufficient curability.

  A-2 has a carbonyl group in the molecular structure. Since the oxygen atom in the carbonyl group has an electron-withdrawing property, the methoxymethyl group of A-2 has lower reactivity with the thiol group of the compound (B) than the methoxymethyl group of A-1. It is supposed that. This is also presumed to be one reason that the curability of Compositions 8 to 11 was insufficient. On the other hand, A-1 has no carbonyl group in the molecular structure. Therefore, it is considered that the methoxymethyl group of A-1 did not receive the effect of decreasing the reactivity as described above, and the curability of Composition 1 to Composition 7 was excellent.

  As described above, it was found that the compositions 1 to 7 according to this example had sufficient curability. From this, it is considered that the occurrence of pattern peeling defects can be suppressed by forming the adhesion layer using the compositions 1 to 7 according to the examples.

<(2) Evaluation of adhesion>
Next, the adhesion between the substrate and the cured film obtained by curing the photocurable composition was evaluated by the following method.

(2-1) Preparation of Adhesion Layer Forming Composition Compositions 1 to 7, which showed sufficient curability in the above-described curability evaluation, were treated with propylene glycol monomethyl ether acetate (V) as a volatile solvent (C). (Manufactured by Tokyo Chemical Industry Co., Ltd.). Thus, a mixed solution having a total concentration of 0.5% by weight of the compound (A), the compound (B), and the additive component (D) was obtained.

  Next, each of the obtained mixed solutions was filtered with a polytetrafluoroethylene filter having a pore size of 0.2 μm. Thus, Compositions 1 'to 7', which are compositions for evaluating adhesion, were prepared.

(2-2) Preparation of photocurable composition The components (E) (polymerizable compound), component (F) (photopolymerization initiator) and other additional components (G) shown below are weighted as shown in Table 3. A mixed solution was obtained by blending in a ratio. The numbers in Table 3 represent parts by weight.

  Next, the obtained mixed solution was filtered with an ultrahigh molecular weight polyethylene filter having a pore size of 0.2 μm. Thereby, the photocurable composition 1 and the photocurable composition 2 were prepared.

(Component (E): polymerizable compound)
(E-1) Isobornyl acrylate (Kyoeisha Chemical, trade name: IB-XA)
(E-2) Benzyl acrylate (manufactured by Osaka Organic Chemical Industry, trade name: V # 160)
(E-3) Neopentyl glycol diacrylate (Kyoeisha Chemical, trade name: NP-A)
(E-4) Dimethylol tricyclodecane diacrylate (manufactured by Kyoeisha Chemical, trade name: DCP-A)

(Component (F): Photopolymerization initiator)
(F-1) Lucirin TPO (manufactured by BASF) (Formula (g))

(Other components (G))
(G-1) 4,4'-bis (diethylamino) benzophenone (Tokyo Kasei Kogyo)
(G-2) Polyoxyethylene stearyl ether Emulgen 320P (manufactured by Kao) (Formula (h))

(2-3) Formation of Adhesion Layer Each of the prepared compositions 1 ′ to 7 ′ was applied on a silicon wafer by spin coating. The spin coating conditions were 3000 rpm and 30 seconds. Then, each composition was heated on a hot plate to form an adhesion layer. The heating conditions were as follows: composition 1 ′ to composition 3 ′ were heated at 220 ° C. for 30 minutes, and composition 4 ′ to composition 7 ′ were heated at 220 ° C. for 3 minutes. Thereby, adhesion layers having a thickness of 10 nm or less were formed.

(2-4) Curing of the photocurable composition 2 μL of the photocurable composition 1 prepared in (2-2) was dropped on the adhesion layer formed on the silicon wafer formed in (2-3). And placed. Further, a quartz glass having a thickness of 1 mm was covered thereover, and an area of 35 mm × 25 mm was filled with the photocurable composition 1.

Next, light emitted from a UV light source equipped with an ultra-high pressure mercury lamp was irradiated for 200 seconds through quartz glass after passing through an interference filter described later. Thus, the photocurable composition 1 was cured to obtain a cured film. In addition, the interference filter used at the time of light irradiation is VPF-25C-10-15-31300 (made by Sigma Koki). The irradiation light used was ultraviolet light of a single wavelength of 313 ± 5 nm, and the illuminance was 1 mW / cm ² .

  The photocurable composition 2 was also photocured in the same manner as the photocurable composition 1 to obtain a cured film.

(2-5) Evaluation of Adhesion After photocuring, the quartz glass was peeled off, and the presence or absence of peeling of the cured film from the substrate side was visually confirmed. In this example, A was evaluated when the cured film did not peel over the entire area of 35 mm × 25 mm, and B was evaluated when peeling occurred even in a part of the 35 mm × 25 mm area.

  Table 4 summarizes the results.

  Examples 1a to 7a are examples in which an adhesion layer was formed using compositions 1 'to 7' and a cured film was formed using photocurable composition a, respectively. Examples 1b to 7b are examples in which an adhesion layer was formed using compositions 1 'to 7' and a cured film was formed using photocurable composition b, respectively. Comparative Example 5a and Comparative Example 5b are examples in which a photocurable composition a and a photocurable composition b are directly formed on a silicon wafer without forming an adhesion layer, respectively. It is.

  In Examples 1a to 7a and Examples 1b to 7b, no peeling defect occurred. On the other hand, in Comparative Examples 5a and 5b, which are examples in which the adhesion layer according to the present example was not used, peeling defects occurred.

  That is, by using the adhesive layer forming composition of each example, an adhesive layer capable of improving the adhesiveness between the substrate and the cured film can be formed, and the occurrence of pattern peeling defects can be suppressed. it can.

REFERENCE SIGNS LIST 100 adhesive layer forming composition 101 adhesive layer 102 substrate 103 photocurable composition 104 mold 105 coating film 106 mold-side alignment mark 107 substrate-side alignment mark 108 irradiation light 109 photocured product 110 cured film having pattern shape 111 Cured Product Pattern 112 Part of Base Material with Exposed Surface 113 Circuit Structure

Claims (19)

An adhesive layer forming composition,
A compound (A) having at least five of one or both of an alkoxyalkyl group and an alkylol group in one molecule;
A compound (B) having at least two thiol groups in one molecule,
A composition for forming an adhesion layer, comprising: Further comprising a volatile solvent,
The adhesion according to claim 1, wherein the content of the volatile solvent is 70% by mass or more and 99.9% by mass or less when the whole of the composition for forming an adhesion layer is 100% by mass. Layer forming composition.   The adhesion layer forming composition according to claim 1 or 2, wherein the composition does not contain a photopolymerization initiator.   The content of particles having a particle size larger than 0.2 μm is less than 3% by mass when the whole of the adhesive layer forming composition is 100% by mass. The composition for forming an adhesion layer according to any one of the preceding claims. The composition for forming an adhesion layer according to any one of claims 1 to 4, wherein the compound (A) is a compound represented by the following general formula (1).

(In the formula (1), R _{1 to} R ₆ each independently represent any of a hydrogen atom, an alkyl group, an alkoxyalkyl group, or an alkylol group. However, at least five of R _{1 to} R ₆ are alkoxy groups. It is an alkyl group or an alkylol group.)   The compound (A) is selected from pentamethoxymethylmelamine, hexamethoxymethylmelamine, (hydroxymethyl) pentakis (methoxymethyl) melamine, hexaethoxymethylmelamine, hexabutoxymethylmelamine, pentamethylolmelamine, and hexamethylolmelamine. The adhesive layer forming composition according to any one of claims 1 to 5, wherein the composition comprises at least one of the following.   7. The compound according to claim 1, wherein the compound (A) is a compound having at least one of an alkoxyalkyl group and an alkylol group or both in one molecule. The composition for forming an adhesion layer according to claim 1.   The composition for forming an adhesion layer according to any one of claims 1 to 7, wherein the compound (B) has at least three thiol groups in one molecule.   The adhesion layer forming composition according to any one of claims 1 to 8, wherein the compound (B) is a primary thiol.   When the weight fractions of the compound (A) and the compound (B) with respect to the total weight of the composition for forming an adhesion layer are α and β, respectively, α / β is 0.25 or more and 4 or less. The adhesion layer forming composition according to any one of claims 1 to 9.   Assuming that the weight fractions of the compound (A) and the compound (B) with respect to the total weight of the adhesive layer forming composition are α and β, respectively, the sum of α and β is 0.1 or more and 10 or less. The composition for forming an adhesion layer according to any one of claims 1 to 10.   The adhesive layer forming composition according to any one of claims 1 to 11, wherein the adhesive layer forming composition is for photo nanoimprinting. 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 substrate on which the adhesion layer is formed, and contacting the photocurable composition with a mold having a prototype pattern for transferring a pattern shape; A third step;
A fourth step of irradiating the photocurable composition with light to form a cured product;
And a fifth step of separating the cured product and the mold from each other.   The method for producing a cured product pattern according to claim 13, wherein the photocurable composition contains a compound having an acryloyl group or a methacryloyl group.   The method according to claim 13, wherein the first step is a step of arranging the adhesive layer forming composition on a substrate having a hydroxyl group on a surface.   A method for producing an optical component, comprising a step of obtaining a cured product pattern by the method for producing a cured product pattern according to any one of claims 13 to 15. A step of obtaining a cured product pattern by the method for producing a cured product pattern according to any one of claims 13 to 15,
Etching or ion-implanting the substrate using the obtained cured product pattern as a mask.   The method according to claim 17, wherein the circuit board is a circuit board used in a semiconductor device. A step of obtaining a cured product pattern on a base material by the method for producing a cured product pattern according to any one of claims 12 to 15,
Etching the base material using the obtained cured product pattern as a mask .