WO2020059604A1 - Laminated body for imprinting, method for manufacturing laminated body for imprinting, method for forming pattern, and kit - Google Patents

Abstract

In order to achieve a laminated body for imprinting capable of bringing about excellent adhesion to, for example, a substrate of a cured product formed of a photosetting composition for imprinting, and excellent wettability of the photosetting composition for imprinting, a laminated body for imprinting according to the present invention is configured to have: an underlayer film 11 formed of an underlayer-film-forming composition containing a polymer having a radical polymerizable group and a cation polymerizable group; a liquid film 12 that is provided on a surface of the underlayer film 11 and that contains a radical polymerizable compound that is a liquid at 23°C at 1 atmosphere; and a photosetting composition for imprinting 13 that is provided on a surface of the liquid film 12 and that contains a radical polymerizable compound and a photo radical polymerization initiator.

Description

Imprint laminate, method for producing imprint laminate, pattern forming method and kit

The present invention relates to a laminate for imprint. More specifically, the present invention relates to an imprint laminate used for forming a pattern by imprint. The present invention also relates to a method for producing a laminate for imprint, a method for forming a pattern, and a kit.

The imprinting method is based on the development of a well-known embossing technique in optical disk manufacturing, and presses a mold prototype (generally called a mold, stamper, template, etc.) with a concave / convex pattern onto a resist and mechanically This is a technology for precisely transferring a fine pattern by deforming it. Once a mold is made, it is economical because it can easily and repeatedly mold a fine structure such as a nanostructure.In addition, it is a nano-processing technology that reduces harmful wastes and discharges. Application is expected.

In the imprint method, after irradiating light through a light-transmitting mold or a light-transmitting substrate to cure the photocurable composition for imprinting, the mold is peeled off to transfer a fine pattern to the photocured material. is there. Since this method enables imprinting at room temperature, it can be applied to the field of precision processing of ultra-fine patterns such as fabrication of semiconductor integrated circuits. Recently, new developments such as a nanocasting method combining these advantages and a reversal imprint method for producing a three-dimensional laminated structure have been reported.

On the other hand, as the imprint method has become more active, the adhesion between the substrate and the photocurable composition for imprint has come to be viewed as a problem. That is, in the imprint method, after applying the photocurable composition for imprint to the surface of the substrate, and curing the photocurable composition for imprint by irradiating light with the mold in contact with the surface. When the mold is peeled off, the cured product may peel off from the substrate and adhere to the mold in the step of peeling off the mold. This is probably because the adhesion between the substrate and the cured product is lower than the adhesion between the mold and the cured product. Therefore, an attempt has been made to form a lower layer film on a substrate and apply a photocurable composition for imprint thereon to improve the adhesion between the substrate and the cured product (see Patent Document 1).

JP 2014-192178 A

In pattern formation by the imprint method, the cured product formed from the photocurable composition for imprints has good adhesion to the substrate, and the wettability of the photocurable composition for imprints is good. In recent years, it has been desired that these characteristics be compatible at a higher level.

Therefore, an object of the present invention is to provide excellent adhesion to a substrate or the like of a cured product formed from the photocurable composition for imprint, and to provide excellent wettability of the photocurable composition for imprint. An object of the present invention is to provide a laminate for imprint, a method for producing the laminate for imprint, a method for forming a pattern, and a kit.

Based on the above problem, it has been found that the above problem can be solved by using an imprint laminate having a configuration described later. Therefore, the present invention provides the following.
<1> an underlayer film formed from an underlayer film forming composition including a polymer having a radical polymerizable group and a cationic polymerizable group;
A liquid film provided on the surface of the lower film and containing a radically polymerizable compound that is liquid at 23 ° C. and 1 atm;
Provided on the surface of the liquid film, a photocurable composition for imprint containing a radical polymerizable compound and a photoradical polymerization initiator,
A laminate for imprinting, comprising:
<2> The radical polymerizable group of the polymer is a group having an ethylenically unsaturated bond, and the cationic polymerizable group is a group represented by any of the following formulas (T1) to (T4). <1> The laminate for imprints described in 1 above;

In the formula (T1), X ¹ represents O, NR ¹ or S, R ¹ represents a hydrogen atom or an alkyl group, Rt ¹ represents a hydrogen atom or an alkyl group, and a wavy line represents a bond;
In the formula (T2), X ² represents O, NR ² or S, R ² represents a hydrogen atom or an alkyl group, Rt ² represents a hydrogen atom or an alkyl group, and a wavy line represents a bond;
In the formula (T3), X ³ represents O, NR ³ or S, R ³ represents a hydrogen atom or an alkyl group, Rt ³ represents a hydrogen atom or an alkyl group, and a wavy line represents a bond;
In the formula (T4), X ⁴ represents O, NR ⁴ or S, R ⁴ represents a hydrogen atom or an alkyl group, p represents 0 or 1, q represents 0 or 1, and n represents 0 to 2 represents an integer, and a wavy line represents a bond.
<3> The imprint laminate according to <1> or <2>, wherein the composition for forming an underlayer film includes a thermosetting accelerator.
<4> The imprint laminate according to <3>, wherein the thermosetting accelerator is a compound that generates an acid or a cation at a temperature of 100 ° C or higher.
<5> The imprint laminate according to any one of <1> to <4>, wherein the thickness of the liquid film is 5 nm or less.
<6> The imprint laminate according to any one of <1> to <5>, wherein the radical polymerizable compound contained in the liquid film is a polyfunctional radical polymerizable compound.
<7> The ΔHSP value calculated by the following equation (H1) based on the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the photocurable composition for imprint is 10 or less, and the following <1> to <6> The laminate for imprint according to any one of the above;
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 (H1)
ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprint and the dispersion term component of the Hansen solubility parameter vector of the liquid film, and ΔP is the photocurable composition for imprint. Is the difference between the polarity term component of the Hansen solubility parameter vector of the material and the polarity term component of the Hansen solubility parameter vector of the liquid film, and ΔH is the hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprint. And the hydrogen bond term component of the Hansen solubility parameter vector of the liquid film.
<8> a step of forming an underlayer film by applying a composition for forming an underlayer film containing a polymer having a radically polymerizable group and a cationically polymerizable group on a substrate;
Forming a liquid film by applying a liquid film-forming composition containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower layer film;
Applying a photocurable composition for imprints containing a radical polymerizable compound and a photoradical polymerization initiator on the liquid film,
A method for producing a laminate for imprints comprising:
<9> forming an underlayer film by applying a composition for forming an underlayer film including a polymer having a radically polymerizable group and a cationically polymerizable group on a substrate;
Forming a liquid film by applying a liquid film-forming composition containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower layer film;
Applying a photocurable composition for imprints containing a radical polymerizable compound and a photoradical polymerization initiator on the liquid film,
Contacting a mold having a pattern with a photocurable composition for imprinting on a liquid film,
A step of exposing the photocurable composition for imprint in a state where the mold is in contact with the mold,
Step of peeling the mold from the exposed photocurable composition for imprint,
A pattern forming method including:
<10> A kit used for the imprint laminate according to any one of <1> to <7>,
An underlayer film-forming composition containing a polymer having a radically polymerizable group and a cationically polymerizable group,
A liquid film-forming composition containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm;
A photocurable composition for imprints comprising a radically polymerizable compound and a photoradical polymerization initiator.

The present invention provides excellent adhesion of a cured product formed from the photocurable composition for imprints to a substrate or the like, and can provide excellent wettability of the photocurable composition for imprints. A laminate for printing, a method for producing a laminate for imprint, a method for forming a pattern, and a kit can be provided.

It is a schematic diagram of a layered product for imprints of the present invention. It is a figure which shows the state which contacted the photocurable composition for imprints and the mold which has a pattern in the pattern formation method of this invention. FIG. 2 is a schematic view showing an example of a pattern formed by using the pattern forming method of the present invention.

Hereinafter, the contents of the present invention will be described in detail. In this specification, “to” is used to mean that the numerical values described before and after it are included as the lower limit and the upper limit.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate.
In the present specification, “imprint” preferably refers to a pattern transfer having a size of 1 nm to 10 mm, and more preferably refers to a pattern transfer (nanoimprint) having a size of about 10 nm to 100 μm.
In the notation of a group (atomic group) in this specification, the notation of not indicating substituted or unsubstituted includes not only a group having no substituent but also a group having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “light” includes not only light having a wavelength in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared regions, and electromagnetic waves, but also radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. Alternatively, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser can be used. These lights may be monochrome light (single-wavelength light) that has passed through an optical filter, or may be light having different wavelengths (composite light).
The weight average molecular weight (Mw) in the present invention refers to a value measured by gel permeation chromatography (GPC) unless otherwise specified.
The boiling point in the present invention refers to a boiling point at 1 atm (1 atm = 1013.25 hPa).
The temperature in the present invention is 23 ° C. unless otherwise specified.

<Laminate for imprint>
The laminate for imprint of the present invention,
An underlayer film formed from an underlayer film forming composition containing a polymer having a radically polymerizable group and a cationically polymerizable group,
A liquid film provided on the surface of the lower film and containing a radically polymerizable compound that is liquid at 23 ° C. and 1 atm;
Provided on the surface of the liquid film, a photocurable composition for imprint containing a radical polymerizable compound and a photoradical polymerization initiator,
It is characterized by having.

The imprint laminate of the present invention has an underlayer film formed from an underlayer film-forming composition containing a polymer having a radically polymerizable group and a cationically polymerizable group. Since the polymer contained in the underlayer film forming composition has a radical polymerizable group and a cationic polymerizable group, during the formation of the underlayer film, these polymerizable groups contained in the polymer react appropriately, An underlayer film with moderately advanced crosslinking is formed. Since the lower film is appropriately cross-linked, by forming a liquid film containing a predetermined radically polymerizable compound thereon, diffusion of the liquid film into the lower film can be suppressed, and the stability of the liquid film is excellent. And since the imprint photocurable composition is provided on this liquid film, the imprint photocurable composition easily wets and spreads on the lower layer film, The photocurable composition for printing has excellent wettability. Therefore, when the mold is brought into contact with the surface of the photocurable composition for imprints to form a pattern, excellent filling properties of the photocurable composition for imprints into the mold can be provided. In the present invention, the liquid refers to a liquid having a viscosity at 23 ° C. of 100,000 mPa · s or less.
Further, the laminate for imprints of the present invention has a liquid film containing a radically polymerizable compound that is liquid at 23 ° C. and 1 atm on the surface of the lower film. As described above, since the liquid film contains the above radical polymerizable compound, when the photocurable composition for imprints is cured by exposing while pressing the mold, the lower film and the liquid film are hardened. And the reaction between the radical polymerizable compound in the liquid film and the radical polymerizable compound contained in the photocurable composition for imprinting is also presumed to progress, and the liquid film and the lower film Adhesion and the adhesion between the liquid film and the cured product obtained from the photocurable composition for imprints formed thereon can be enhanced. Therefore, the laminate for imprints of the present invention can provide excellent adhesion of a cured product formed from the photocurable composition for imprints to a substrate or the like. Further, since a cured product having excellent adhesion can be formed, the occurrence of peeling defects at the time of mold release can be effectively suppressed.

参照 The imprint laminate of the present invention will be described in more detail with reference to FIG. In FIG. 1, a laminate 10 for imprint of the present invention is formed on a substrate 1. That is, in FIG. 1, the lower film 11 is formed on the substrate 1, and the liquid film 12 is formed on the lower film. Then, the photocurable composition for imprint 13 is disposed on the liquid film 12. The laminate of the lower layer film 11, the liquid film 12, and the photocurable composition for imprint 13 is the laminate for imprint 10 of the present invention.

The material of the substrate 1 on which the laminate for imprint is formed is not particularly limited, and is described in paragraph 0103 of JP-A-2010-109092 (the publication number of the corresponding US application is US2011 / 0183127). For reference, their contents are incorporated herein. Specific examples of the substrate 1 include a silicon substrate, a glass substrate, a quartz substrate, a sapphire substrate, a silicon carbide (silicon carbide) substrate, a gallium nitride substrate, an aluminum substrate, an amorphous aluminum oxide substrate, a polycrystalline aluminum oxide substrate, and GaAsP, A substrate made of GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP, or ZnO may be used. Specific examples of the material of the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate is preferred.

に お い て In the present invention, it is also preferable to use a substrate having a carbon film on the surface as the substrate 1. The carbon film is preferably provided on the outermost layer of the substrate. Examples of the carbon film include an amorphous carbon film and a spin-on carbon film. As an example of the spin-on carbon film, reference can be made to the description in paragraph 0126 of JP-A-2011-164345, the contents of which are incorporated herein.

水 の The contact angle of water on the substrate surface is preferably 1 ° or more, more preferably 20 ° or more, and even more preferably 40 ° or more. It is practical that the upper limit is 90 ° or less.

The thickness of the lower film 11 is preferably 2 nm or more, more preferably 3 nm or more, still more preferably 4 nm or more, and may be 5 nm or more, or may be 7 nm or more. It may be 10 nm or more. Further, the thickness of the lower layer film is preferably 40 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, and may be 15 nm or less. When the film thickness is equal to or more than the lower limit, the wettability of the photocurable composition for imprints can be increased. When the film thickness is equal to or less than the above upper limit, the remaining film after imprinting becomes thin, the thickness unevenness is less likely to occur, and the uniformity of the remaining film can be improved.

表面 The surface free energy of the lower layer film 11 is preferably 30 mN / m or more, more preferably 40 mN / m or more, and further preferably 50 mN / m or more. The upper limit is preferably 200 mN / m or less, more preferably 150 mN / m or less, and even more preferably 100 mN / m or less. The surface free energy can be measured at 23 ° C. using a glass plate using a surface tensiometer “SURFACE TENS-IOMETER” CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.

に お い て In the imprint laminate of the present invention, the underlayer film 11 is formed from a composition for forming an underlayer film containing a polymer having a radically polymerizable group and a cationically polymerizable group. Details of the composition for forming the lower layer film will be described later.

The thickness of the liquid film 12 is preferably 20 nm or less, more preferably 15 nm or less, even more preferably 10 nm or less. Further, the thickness of the liquid film is preferably 2 nm or more. When the film thickness is equal to or more than the lower limit, the wettability of the photocurable composition for imprints can be increased. When the film thickness is equal to or less than the upper limit, occurrence of pattern collapse or the like can be suppressed.

に お い て In the laminate for imprints of the present invention, the liquid film 12 contains a radically polymerizable compound (hereinafter also referred to as a radically polymerizable compound A) which is liquid at 23 ° C. and 1 atm. The liquid film 12 preferably has a content of a non-volatile component (a component other than the solvent) of 0.01% by mass or more, more preferably 0.1% by mass or more. In addition, the content of the radical polymerizable compound A in the liquid film 12 is preferably 50% by mass or more, and more preferably 80% by mass or more.

The liquid film 12 can be formed using a liquid film forming composition containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm. Details of the liquid film forming composition will be described later.

In FIG. 1, the photocurable composition for imprint 13 is disposed only in a part of the surface of the liquid film 12, but may be disposed on the entire surface of the liquid film 12. In FIG. 1, the photocurable composition 13 for imprints is arranged in a dot pattern on the surface of the liquid film 12. However, the photocurable composition 13 for imprints is not particularly limited, and may be in a striped or square shape. , A rectangle, an ellipse, a diamond, and the like. The details of the photocurable composition for imprints will be described later.

<<< underlayer film forming composition >>
Next, the composition for forming an underlayer film used for the imprint laminate of the present invention will be described.

[Specific polymer]
The composition for forming a lower layer film contains a polymer having a radical polymerizable group and a cationic polymerizable group (hereinafter, also referred to as a specific polymer). The specific polymer is a mixture of a polymer having a radical polymerizable group, and having no cationic polymerizable group, and a polymer having a cationic polymerizable group, and having no radical polymerizable group, However, it is preferable that the polymer contains a structural unit having a radically polymerizable group and a structural unit having a cationically polymerizable group. In the specific polymer, the radical polymerizable group and the cationic polymerizable group may be contained in the same constituent unit, but are preferably contained in separate constituent units. That is, the specific polymer is preferably a polymer containing a constituent unit having a radical polymerizable group and a constituent unit having a cationic polymerizable group.

In the specific polymer, the total ratio of the constituent unit having a radical polymerizable group and the constituent unit having a cationic polymerizable group is preferably 50 to 100 mol% of all the constituent units of the specific polymer, and More preferably, it is 100 mol%.
In the specific polymer, the ratio of the constitutional unit having a radical polymerizable group is preferably from 20 to 80 mol%, more preferably from 30 to 70 mol% of all the constitutional units.
In the specific polymer, the proportion of the structural unit having a cationically polymerizable group is preferably from 20 to 80% by mole, more preferably from 30 to 70% by mole of all the structural units.
In the specific polymer, the content of the structural unit having a cationically polymerizable group is preferably from 0.25 to 4.00 mol, more preferably from 0.43 to 2 mol, per mol of the structural unit having a radically polymerizable group. More preferably, it is 0.33 mol.

ラ ジ カ ル Examples of the radical polymerizable group of the specific polymer include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a styrene group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

Examples of the cationic polymerizable group of the specific polymer include a group represented by any of the following formulas (T1) to (T4), an oxazoline group, and the like, and a group represented by any of the following formulas (T1) to (T4). Preferably, the group is

In the formula (T1), X ¹ represents O, NR ¹ or S, R ¹ represents a hydrogen atom or an alkyl group, Rt ¹ represents a hydrogen atom or an alkyl group, and a wavy line represents a bond. X ¹ is preferably O. The alkyl group represented by R ¹ and Rt ¹ preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and still more preferably 1 to 3.

In the formula (T2), X ² represents O, NR ² or S, R ² represents a hydrogen atom or an alkyl group, Rt ² represents a hydrogen atom or an alkyl group, and a wavy line represents a bond. X ² is preferably O. The alkyl group represented by R ² and Rt ² preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and still more preferably 1 to 3.

In the formula (T3), X ³ represents O, NR ³ or S, R ³ represents a hydrogen atom or an alkyl group, Rt ³ represents a hydrogen atom or an alkyl group, and a wavy line represents a bond. X ³ is preferably O. The alkyl group represented by R ³ and Rt ³ preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and still more preferably 1 to 3.

In the formula (T4), X ⁴ represents O, NR ⁴ or S, R ⁴ represents a hydrogen atom or an alkyl group, p represents 0 or 1, q represents 0 or 1, and n represents 0 to 2 represents an integer, and a wavy line represents a bond. X ⁴ is preferably O. The alkyl group represented by R ⁴ and Rt ⁴ preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and still more preferably 1 to 3. p is preferably 0. q is preferably 0. n is preferably 1 or 2.

The specific polymer is represented by at least one of the structural units represented by any of the following formulas (1-1) to (1-6) and one of the following formulas (2-1) to (2-6). It is preferable to include at least one of the constituent units described above.

In the formula (1-1), R ¹¹ represents a substituent, and m1 represents an integer of 1 to 4. If m1 is 2 or more, plural R ¹¹ may be the same, or different, may form two R ¹¹ are bonded to each other ring. However, at least one of m1 R ¹¹ represents a group having a radical polymerizable group.
In the formula (1-2), R ² represents a hydrogen atom or a methyl group, R ¹² represents a substituent, and m2 represents an integer of 1 to 5. When m2 is 2 or more, a plurality of R ¹² may be the same or different, and two R ¹² may be bonded to each other to form a ring. Provided that at least one of m2 amino R ¹² represents a group having a radical polymerizable group.
In the formula (1-3), R ³ represents a hydrogen atom or a methyl group, and R ¹³ represents a group having a radical polymerizable group.
In the formula (1-4), R ⁴ represents a hydrogen atom or a methyl group, and R ¹⁴ represents a group having a radical polymerizable group.
In the formula (1-5), R ¹⁵ represents a group having a radical polymerizable group.
In the formula (1-6), R ¹⁶ and R ¹⁷ each independently represent a substituent, and m6 and m7 each independently represent an integer of 1 to 5. When m6 is 2 or more, a plurality of R ¹⁶ may be the same or different, and two R ¹⁶ may be bonded to each other to form a ring. However, at least one of m6 R ¹⁶ represents a group having a radical polymerizable group. When m7 is 2 or more, a plurality of R ¹⁷ may be the same or different, and two R ¹⁷ may be bonded to each other to form a ring. However, at least one of m7 R ¹⁷ represents a group having a radical polymerizable group.

In the formula (2-1), R ²¹ represents a substituent, and m1a represents an integer of 1 to 4. When m1a is 2 or more, a plurality of R ²¹ may be the same or different, and two R ²¹ may be bonded to each other to form a ring. However, at least one of m1a R ²¹ represents a group having a cationically polymerizable group.
In the formula (2-2), R ^2a represents a hydrogen atom or a methyl group, R ²² represents a substituent, and m2a represents an integer of 1 to 5. If m2a is 2 or more, plural R ²² may be the same, or different, may form two R ²² are bonded to each other ring. Provided that at least one of m2a number of R ²² represents a group having a cationically polymerizable group.
In the formula (2-3), R ^3a represents a hydrogen atom or a methyl group, and R ²³ represents a group having a cationically polymerizable group.
In the formula (2-4), R ^4a represents a hydrogen atom or a methyl group, and R ²⁴ represents a group having a cationically polymerizable group.
In the formula (2-5), R ²⁵ represents a group having a cationically polymerizable group.
In the formula (2-6), R ²⁶ and R ²⁷ each independently represent a substituent, and m6a and m7a each independently represent an integer of 1 to 5. When m6a is 2 or more, a plurality of R ²⁶ may be the same or different, and two R ²⁶ may be bonded to each other to form a ring. Provided that at least one of m6a number of R ²⁶ represents a group having a cationically polymerizable group. When m7a is 2 or more, a plurality of R ²⁷ may be the same or different, and two R ²⁷ may be bonded to each other to form a ring. However, at least one of m7a R ²⁷ represents a group having a cationically polymerizable group.

In the above formula, examples of the substituent represented by R ¹¹ , R ¹² , R ¹⁶ , R ¹⁷ , R ²¹ , R ²² , R ²⁶ , and R ²⁷ include a substituent T described below.
Examples of the group having a radical polymerizable group represented by R ¹¹ to R ¹⁷ include a group represented by the following formula (R-1).
Examples of the group having a cationically polymerizable group represented by R ²¹ to R ²⁷ include a group represented by the following formula (R-2).

-(L ¹ ) _n1- (P ¹ ) _n2 (R-1)
L ¹ is the following linking group L, and is preferably an alkylene group, an arylene group, a (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, or a linking group relating to a combination thereof. n1 is 0 or 1, and 1 is preferred. P ¹ represents a radical polymerizable group. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a styrene group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable. n2 is an integer of 1 to 6, preferably 1 or 2, and more preferably 1. Note that when n2 is 2 or more, it is sufficient that L ¹ is a trivalent or more connecting group, for example, group (1 to 12 carbon atoms are preferable tri- or higher alkane structure, are 1-6 More preferably, it is 1 to 3, more preferably, an alkene structure group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), or an aryl structure group (having 6 to 22 carbon atoms). Is preferable, 6 to 18 are more preferable, and 6 to 10 are more preferable.).

The group represented by the formula (R-1) is preferably a group represented by the following formula (R-1a).

In the formula, R ¹⁰⁰ represents a hydrogen atom or a methyl group, and L ^1a represents a single bond or the following linking group L. L ^1a is preferably an alkylene group, an arylene group, a (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, or a linking group relating to a combination thereof.

-(L ¹¹ ) _n11- (P ¹¹ ) _n12 (R-2)
L ¹¹ is the following linking group L, and is preferably an alkylene group, an arylene group, a (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, or a linking group related to a combination thereof. n11 is 0 or 1, and 1 is preferred. P ¹¹ represents a cationically polymerizable group. Examples of the cationic polymerizable group include groups represented by the above formulas (T1) to (T4). n12 is an integer of 1 to 6, preferably 1 or 2, and more preferably 1. Incidentally, when n12 is 2 or more, it is sufficient that L ¹¹ is a trivalent or more connecting group, for example, group (1 to 12 carbon atoms are preferable tri- or higher alkane structure, are 1-6 More preferably, it is 1 to 3, more preferably, an alkene structure group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6, more preferably 2 to 3), or an aryl structure group (having 6 to 22 carbon atoms). Is preferable, 6 to 18 are more preferable, and 6 to 10 are more preferable.).

(Substituent T)
Examples of the substituent T include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6), and an arylalkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms). , 7 to 11 are more preferred), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms), and an alkynyl group (preferably having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms). More preferably, a hydroxyl group, an amino group (preferably having 0 to 24 carbon atoms, more preferably 0 to 12, and still more preferably 0 to 6), a thiol group, a carboxyl group, an aryl group (e.g. A number of 6 to 22, preferably 6 to 18, more preferably 6 to 10, and an alkoxyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6, To 3), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10), and an acyl group (preferably having 2 to 12 carbon atoms and more preferably 2 to 6 carbon atoms). Preferably 2 to 3, more preferably an acyloxy group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6), and an aryloyl group (preferably having 7 to 23 carbon atoms, 7 to 19). Are more preferable, and 7 to 11 are more preferable), an aryloyloxy group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11), and a carbamoyl group (preferably having 1 to 12 carbon atoms) , 1 to 6, more preferably 1 to 3, and a sulfamoyl group (preferably having 0 to 12 carbon atoms, more preferably 0 to 6, and still more preferably 0 to 3). ), A sulfo group, an alkylsulfonyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3), and an arylsulfonyl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18). , 6 to 10 are more preferable), a heterocyclic group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 2 to 5 and preferably containing a 5- or 6-membered ring), ( (Meth) acryloyl group, (meth) acryloyloxy group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), oxo group (= O), imino group (= NR ^N ), alkylidene group (= C (R ^N ) ₂ ). R ^N is a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms), and is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group. The alkyl, alkenyl, and alkynyl moieties contained in each substituent may be linear or cyclic, and may be linear or branched. When the substituent T is a group that can take a substituent, it may further have a substituent T. For example, the alkyl group may be a halogenated alkyl group, a (meth) acryloyloxyalkyl group, an aminoalkyl group or a carboxyalkyl group. When the substituent is a group capable of forming a salt such as a carboxyl group or an amino group, the group may form a salt.

(Linking group L)
Examples of the linking group L include an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6), and an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6; 2 to 3 are more preferable), alkynylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and still more preferably 2 to 3), (oligo) alkyleneoxy group (of the alkylene group in one structural unit) The number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3; the number of repetitions is preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30), and an arylene group ( Preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 10), an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, a thiocarbonyl group, NR ^N -, and linking groups composed of combinations thereof. The alkylene group may have a substituent T described below. For example, the alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L, excluding hydrogen atoms, is preferably 1 to 50, more preferably 1 to 40, and even more preferably 1 to 30. The number of connecting atoms means the number of atoms located on the shortest path among the atomic groups involved in the connection. For example, in the case of —CH ₂ — (C ＝ O) —O—, the number of atoms involved in the connection is six, and the number excluding the hydrogen atom is four. On the other hand, the shortest atom involved in the connection is -CCO-, which is three. The number of connecting atoms is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6. The alkylene group, alkenylene group, alkynylene group, and (oligo) alkyleneoxy group may be linear or cyclic, and may be linear or branched. When the linking group is a group capable of forming a salt such as —NR ^N —, the group may form a salt. R ^N is a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably having 1 to 6 carbon atoms, and still more preferably having 1 to 3 carbon atoms), and is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group.

It is also preferable that the specific polymer further contains a structural unit that does not contain any of a radical polymerizable group and a cationic polymerizable group (sometimes referred to as “another structural unit”). Other structural units include structural units represented by formulas (21) to (25).

In the formula (21), R ^11b represents a substituent, and m1b represents an integer of 1 to 4. When m1b is 2 or more, a plurality of R ^11b may be the same or different, and two R ^11b may combine with each other to form a ring. However, at least one of m1b R ^11b represents a group represented by the formula (R-3).
In the formula (22), R ^2b represents a hydrogen atom or a methyl group, R ^12b represents a substituent, and m2b represents an integer of 1 to 5. When m2b is 2 or more, a plurality of R ^12b may be the same or different, and two R ^12b may be bonded to each other to form a ring. However, at least one of m2b R ^12b represents a group represented by the formula (R-3).
In the formula (23), R ^3b represents a hydrogen atom or a methyl group, and R ^13b represents a group represented by the formula (R-3).
In the formula (24), R ^4b represents a hydrogen atom or a methyl group, and R ^14b represents a group represented by the formula (R-3).
In the formula (25), R ^15b represents a group represented by the formula (R-3).

^{Examples of the} substituent represented by R ^11b and R ^12b include the substituent T described above and a group represented by the following formula (R-3).

_{^{- (L 5) n8 - (}} T 1) n9 (R-3)
And L ⁵ is a linking group L above, among them an alkylene group, an arylene group, (oligo) alkyleneoxy group, a carbonyl group, an oxygen atom, a linking group according to a combination thereof preferred. n8 is 0 or 1. T ¹ is the above substituent T. Among them, an alkyl group which may be substituted with a halogen atom, an aryl group which may be substituted with a halogen atom, and an arylalkyl group which may be substituted with a halogen atom. preferable. n9 is an integer of 1 to 6, preferably 1 or 2. When n9 is 2 or more, L ⁵ may be a trivalent or more valent connecting group, for example, a trivalent or more alkane structure group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). , 1 to 3 are more preferable), an alkene structure group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 is more preferable), or an aryl structure group (preferably having 6 to 22 carbon atoms). , 6 to 18 are more preferred, and 6 to 10 are even more preferred).

重量 The weight average molecular weight of the specific polymer is preferably 4,000 or more, more preferably 5,000 or more, further preferably 7000 or more, and still more preferably 10,000 or more. The upper limit is preferably 2,000,000 or less, more preferably 15,000,000 or less, and still more preferably 1,000,000 or less. The method for measuring the weight average molecular weight is based on the method described in Examples described later.

具体 Specific examples of the specific polymer include the polymers described in Examples described later. Further, polymers described in paragraphs 0018 to 0041 of JP-A-2014-192178 can also be used.

The content of the specific polymer in the composition for forming an underlayer film is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 0.1% by mass or more. More preferred. The upper limit is preferably 10% by mass or less, more preferably 7% by mass or less, still more preferably 5% by mass or less, even more preferably 4% by mass or less, and 3% by mass. %, Still more preferably 1% by mass or less, or 0.7% by mass or less.
The content of the specific polymer in the non-volatile components of the composition for forming a lower layer film (refer to components other than the solvent in the composition, the same applies hereinafter) is preferably 5% by mass or more, and more preferably 20% by mass or more. Is more preferably 30% by mass or more, further preferably 50% by mass or more, still more preferably 80% by mass or more, and still more preferably 90% by mass or more. , 95% by mass or more, or 99% by mass or more. The upper limit may be 100% by mass. When the amount is equal to or more than the above lower limit, the effect of blending the polymer can be suitably exhibited, and a uniform thin film can be easily prepared. On the other hand, when the content is not more than the above upper limit, the effect of using the solvent is suitably exhibited, and a uniform film can be easily formed over a wide area. Only one specific polymer may be used, or two or more specific polymers may be used. When two or more kinds are used, the total amount is preferably within the above range.

[Thermosetting accelerator]
The composition for forming the lower layer film preferably contains a thermosetting accelerator. According to this aspect, it is easy to form a lower layer film having a high crosslinking density, and it is possible to effectively suppress diffusion of the liquid film provided on the lower layer film into the lower layer film.

(4) The thermosetting accelerator is preferably a compound that generates an acid or a cation at a temperature of 100 ° C. or higher (preferably 100 to 180 ° C., more preferably 120 to 180 ° C., and still more preferably 120 to 160 ° C.).

The thermosetting accelerator is preferably a compound that generates an acid having a pKa of 4 or less, more preferably a compound that generates an acid having a pKa of 3 or less, and most preferably a compound that generates an acid with a pKa of 2 or less. In the present invention, pKa basically indicates pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, pKa described in a chemical handbook or the like can be referred to. The acid having a pKa of 3 or less is preferably a sulfonic acid or a phosphonic acid, and more preferably a sulfonic acid.

Examples of the thermosetting accelerator include compounds that generate a low nucleophilic acid such as sulfonic acid, carboxylic acid and disulfonylimide by heating. The above-mentioned acid is preferably an acid having a pKa of 4 or less, more preferably an acid having a pKa of 3 or less, and still more preferably an acid having a pKa of 2 or less. In the present invention, pKa basically indicates pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement.

Examples of the thermosetting accelerator include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts, with sulfonium salts being preferred. Examples of the sulfonium salt include an alkylsulfonium salt, a benzylsulfonium salt, a dibenzylsulfonium salt, a substituted benzylsulfonium salt, and a benzothiazonium salt. Commercially available thermosetting accelerators include, for example, San Aid SI-60, 100, 110, 150 (all manufactured by Sanshin Chemical Industry Co., Ltd.).

In the present invention, compounds described in paragraphs 0033 to 0047 of JP-A-2017-088866 can also be used as the thermosetting accelerator.

The content of the thermosetting accelerator in the composition for forming a lower layer film is preferably at least 0.0001% by mass, more preferably at least 0.001% by mass, and is at least 0.003% by mass. Is more preferable. The upper limit is preferably 0.03% by mass or less, more preferably 0.02% by mass or less, and even more preferably 0.01% by mass or less.
The content of the thermosetting accelerator in the nonvolatile component of the composition for forming a lower layer film (refers to components other than the solvent in the composition, the same applies hereinafter) is preferably 0.1% by mass or more, and preferably 1% by mass. %, More preferably 3% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.
Further, the content of the thermosetting accelerator is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the specific polymer described above. The lower limit is preferably at least 0.5 part by mass, more preferably at least 1 part by mass, even more preferably at least 3 parts by mass. The upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less. The thermosetting accelerator may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably within the above range.

[solvent]
The composition for forming an underlayer film preferably contains a solvent (hereinafter, sometimes referred to as a "solvent for an underlayer film"). The solvent is preferably a compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less. Usually, the non-volatile components ultimately form the underlying film. The composition for forming an underlayer film preferably contains 99.0% by mass or more of a solvent for an underlayer film, more preferably 99.5% by mass or more, and may be 99.6% by mass or more. When the content of the solvent is within the above range, it is easy to form a thin underlayer film. The solvent may be contained in the composition for forming an underlayer film alone, or may be contained in two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.
The boiling point of the solvent for the lower layer film is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, further preferably 160 ° C. or lower, and more preferably 130 ° C. or lower. Is even more preferable. Although the lower limit is practically 23 ° C., it is more practical that the lower limit is 60 ° C. or higher. By setting the boiling point within the above range, the solvent can be easily removed from the lower layer film, which is preferable.

有機 The solvent for the lower layer film is preferably an organic solvent. The solvent is preferably a solvent having at least one of an ester group, a carbonyl group, a hydroxyl group and an ether group. Among them, it is preferable to use an aprotic polar solvent.

Specific examples include alkoxy alcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate.

Examples of the alkoxy alcohol include methoxyethanol, ethoxyethanol, methoxypropanol (eg, 1-methoxy-2-propanol), ethoxypropanol (eg, 1-ethoxy-2-propanol), and propoxypropanol (eg, 1-propoxy-2-propanol). Propanol), methoxybutanol (eg, 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (eg, 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (Eg, 4-methyl-2-pentanol).

As the propylene glycol monoalkyl ether carboxylate, at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate is preferable, and propylene glycol monomethyl ether acetate ( PGMEA) is particularly preferred.

As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether is preferable.
As the lactate, ethyl lactate, butyl lactate, or propyl lactate is preferred.
As the acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate are preferred.
As the alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
Examples of chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone or methyl amyl ketone is preferred.
As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferable.
As the lactone, γ-butyrolactone (γBL) is preferable.
As the alkylene carbonate, propylene carbonate is preferred.

の 他 In addition to the above components, it is preferable to use an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and still more preferably 7 to 10), and having 2 or less hetero atoms.

Preferred examples of the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, Examples thereof include isobutyl isobutyrate, heptyl propionate, and butyl butanoate. It is particularly preferable to use isoamyl acetate.

溶 剤 It is also preferable to use a solvent having a flash point (hereinafter, also referred to as a p component) of 30 ° C or higher. Such components include propylene glycol monomethyl ether (p component: 47 ° C.), ethyl lactate (p component: 53 ° C.), ethyl 3-ethoxypropionate (p component: 49 ° C.), and methyl amyl ketone (p component: 42 ° C.), cyclohexanone (p component: 30 ° C.), pentyl acetate (p component: 45 ° C.), methyl 2-hydroxyisobutyrate (p component: 45 ° C.), γ-butyrolactone (p component: 101 ° C.) or propylene carbonate (P component: 132 ° C.) is preferred. Of these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.

Among the solvents particularly preferred as the solvent for the lower layer film, alkoxy alcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene Carbonates.

[Alkylene glycol compound]
The composition for forming an underlayer film may contain an alkylene glycol compound. The alkylene glycol compound preferably has from 3 to 1,000 alkylene glycol structural units, more preferably from 4 to 500, still more preferably from 5 to 100. It is more preferable to have 50. The weight average molecular weight (Mw) of the alkylene glycol compound is preferably from 150 to 10,000, more preferably from 200 to 5,000, further preferably from 300 to 3,000, and still more preferably from 300 to 1,000.
Alkylene glycol compounds include polyethylene glycol, polypropylene glycol, their mono or dimethyl ether, mono or dioctyl ether, mono or dinonyl ether, mono or didecyl ether, monostearate, monooleate, monoadipate, and monosuccinate. Acid esters are exemplified, and polyethylene glycol and polypropylene glycol are preferred.
The surface tension at 23 ° C. of the alkylene glycol compound is preferably at least 38.0 mN / m, more preferably at least 40.0 mN / m. Although the upper limit of the surface tension is not particularly limited, it is, for example, 48.0 mN / m or less. By blending such a compound, the wettability of the curable composition for imprints can be further improved.
The surface tension of the alkylene glycol compound is measured at 23 ° C. using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. using a glass plate. The unit is indicated by mN / m. Two samples are prepared for each level, and each sample is measured three times. An arithmetic average value of a total of six times is adopted as the evaluation value.

When blended, the content of the alkylene glycol compound is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less of the nonvolatile component in the composition for forming an underlayer film. More preferably, it is particularly preferably at most 15% by mass. The lower limit can be 0.5% by mass or more, and can be 1% by mass or more. Only one alkylene glycol compound may be used, or two or more alkylene glycol compounds may be used. When two or more kinds are used, the total amount is preferably within the above range.

[Other ingredients]
In addition to the above, the composition for forming a lower layer film may include one or more of a radical polymerization initiator, a polymerization inhibitor, an antioxidant, a leveling agent, a thickener, a surfactant, and the like. With respect to these components, the components described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537 can be used. For the content and the like, the description in the above publication can be referred to.

<< Composition for forming a liquid film >>
Next, the composition for forming a liquid film used in the laminate for imprint of the present invention will be described.

The viscosity of the composition for forming a liquid film is preferably 1,000 mPas or less, more preferably 800 mPas or less, further preferably 500 mPas or less, and more preferably 100 mPas or less. Is more preferred. The lower limit of the viscosity is not particularly limited, but may be, for example, 1 mPa · s or more. The viscosity is measured according to the following method.
The viscosity is measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotary viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34 ′ × R24). The unit is mPa · s. Other details regarding the measurement conform to JISZ8803: 2011. Two samples are prepared for each level, and each sample is measured three times. An arithmetic average value of a total of six times is adopted as the evaluation value.

[Radical polymerizable compound A]
The composition for forming a liquid film contains a radical polymerizable compound (polymerizable compound A) which is liquid at 23 ° C. and 1 atm.

The radical polymerizable compound A preferably has a viscosity at 23 ° C. of 1 to 100,000 mPa · s. The lower limit is preferably 5 mPa · s or more, and more preferably 11 mPa · s or more. The upper limit is preferably 1,000 mPa · s or less, and more preferably 600 mPa · s or less.

The radical polymerizable compound A may be a monofunctional radical polymerizable compound having only one radical polymerizable group in one molecule, or a polyfunctional radical having two or more radical polymerizable groups in one molecule. It may be a polymerizable compound. A monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound may be used in combination. Among them, the radical polymerizable compound A contained in the composition for forming a liquid film preferably contains a polyfunctional radical polymerizable compound from the viewpoint of suppressing pattern collapse, and two to five radical polymerizable groups are contained in one molecule. More preferably, it contains a radical polymerizable compound containing two to four radical polymerizable groups in one molecule, and more preferably contains a radical polymerizable compound containing two to four radical polymerizable groups in one molecule. It is particularly preferable to include a polymerizable compound.

The radical polymerizable compound A has an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, still more preferably having 6 to 10 carbon atoms) and an alicyclic ring (having 3 to 24 carbon atoms, preferably having 3 to 18 carbon atoms). And more preferably 3 to 6), and further preferably an aromatic ring. The aromatic ring is preferably a benzene ring. Further, the molecular weight of the radical polymerizable compound A is preferably from 100 to 900.

ラ ジ カ ル The radically polymerizable group of the radically polymerizable compound A includes a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group and a (meth) acryloyl group, and is preferably a (meth) acryloyl group.

The radically polymerizable compound A is also preferably a compound represented by the following formula (I-1).

L ²⁰ is a 1 + q divalent linking group, for example, a 1 + q divalent alkane group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3), or an alkene structure group (Preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms) ), A group having a heteroaryl structure (preferably having 1 to 22 carbon atoms, more preferably having 1 to 18 carbon atoms, and still more preferably having 1 to 10 carbon atoms. Examples of the hetero atom include a nitrogen atom, a sulfur atom and an oxygen atom. , A 6-membered ring or a 7-membered ring), or a linking group containing a group obtained by combining these. Examples of a group obtained by combining two aryl groups include groups having a structure such as biphenyl, diphenylalkane, biphenylene, and indene. Examples of a combination of a group having a heteroaryl structure and a group having an aryl structure include groups having a structure such as indole, benzimidazole, quinoxaline, and carbazole.
L ²⁰ is preferably a linking group containing at least one selected from an aryl group and a heteroaryl group, and more preferably a link group containing an aryl group.

R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group.

L ²¹ and L ²² each independently represent a single bond or the above-mentioned linking group L, and is preferably a single bond or an alkylene group.
L ²⁰ and L ²¹ or L ²² may form a ring without intervention or through a linking group L. L ²⁰ , L ²¹ and L ²² may have the substituent T described above. A plurality of substituents T may combine to form a ring. When there are a plurality of substituents T, they may be the same or different.
q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 1.

Examples of the radical polymerizable compound A include the compounds described in paragraphs 0017 to 0024 of JP-A-2014-090133 and the examples, the compounds described in paragraphs 0024 to 0089 of JP-A-2005-0090171, and JP-A-2015-070145. The compounds described in paragraphs [0023] to [0037] of the publication and the compounds described in paragraphs [0012] to [0039] of WO2016 / 152597 can also be used.

The content of the radical polymerizable compound A in the composition for forming a liquid film is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass or more. It is more preferred that there be. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less.
The content of the radically polymerizable compound A in the nonvolatile components of the composition for forming a liquid film (refer to components other than the solvent in the composition, the same applies hereinafter) is preferably 50% by mass or more, and 75% by mass. More preferably, it is 90% by mass or more. The upper limit may be 100% by mass. Only one radical polymerizable compound A may be used, or two or more radical polymerizable compounds A may be used. When two or more kinds are used, the total amount is preferably within the above range.
It is also preferable that the non-volatile component of the composition for forming a liquid film comprises substantially only the radical polymerizable compound A. The case where the non-volatile component of the composition for forming a liquid film substantially consists only of the radical polymerizable compound A means that the content of the radical polymerizable compound A in the non-volatile component of the composition for forming a liquid film is 99.9. It is more preferably at least 99.99 mass%, even more preferably only polymerizable compound A.

[solvent]
The composition for forming a liquid film preferably contains a solvent (hereinafter, sometimes referred to as a “solvent for a liquid film”). Examples of the solvent for the liquid film include those described in the section of the solvent for the lower layer described above, and these can be used. The composition for forming a liquid film preferably contains the solvent for a liquid film in an amount of 90% by mass or more, more preferably 99% by mass or more, and may be 99.99% by mass or more.
The boiling point of the liquid film solvent is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, still more preferably 160 ° C. or lower, and 130 ° C. or lower. Is even more preferable. Although the lower limit is practically 23 ° C., it is more practical that the lower limit is 60 ° C. or higher. By setting the boiling point within the above range, the solvent can be easily removed from the liquid film, which is preferable.

[Radical polymerization initiator]
The liquid film forming composition may contain a radical polymerization initiator. Examples of the radical polymerization initiator include a thermal radical polymerization initiator and a photoradical polymerization initiator, and a photoradical polymerization initiator is preferable. As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides Thio compounds, ketone compounds, aromatic onium salts, acetophenone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes and the like. For the details thereof, the description in paragraphs 0165 to 182 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification. Of these, acetophenone compounds, acylphosphine compounds, and oxime compounds are preferred. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-127, IRGACURE-819, IRGACURE-379, IRGACURE-369, IRGACURE-754, IRGACURE-1800, IRGACURE-651, IRGACURE-GAR, IRGACURE-GAR, and IRGACURE-IRGAUREGA -1173 etc. (above, manufactured by BASF), Omnirad 184, Omnirad TPOH, Omnirad 819, Omnirad 1173 (all manufactured by IGM Resins BV).

When the radical polymerization initiator is contained, it is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, and more preferably 2 to 5% by mass of the nonvolatile component of the composition for forming a liquid film. % Is more preferable. When two or more radical polymerization initiators are used, the total amount is preferably within the above range.

[Other ingredients]
In addition to the above, the composition for forming a liquid film may include one or more of a polymerization inhibitor, an antioxidant, a leveling agent, a thickener, a surfactant, and the like.

<<< Photocurable composition for imprint >>>
Next, the photocurable composition for imprints used in the laminate for imprints of the present invention will be described. In the present invention, the photocurable composition for imprints is not particularly limited, and a known photocurable composition for imprints can be used. As the photocurable composition for imprint, one containing at least a radical polymerizable compound and a photoradical polymerization initiator is used.

The viscosity of the photocurable composition for imprints is preferably 20 mPa · s or less, more preferably 15 mPa · s or less, further preferably 11 mPa · s or less, and is 9 mPa · s or less. Is more preferred. The lower limit of the viscosity is not particularly limited, but may be, for example, 5 mPa · s or more. The viscosity is measured according to the following method.
The viscosity is measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotary viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34 ′ × R24). The unit is mPa · s. Other details regarding the measurement conform to JISZ8803: 2011. Two samples are prepared for each level, and each sample is measured three times. An arithmetic average value of a total of six times is adopted as the evaluation value.

The photocurable composition for imprints preferably has a surface tension (γResist) of 28 mN / m or more, more preferably 30 mN / m or more, and even more preferably 32.0 mN / m or more. By using the photocurable composition for imprints having a high surface tension, the capillary force is increased, and the mold pattern can be filled at a high speed with the photocurable composition for imprints. The upper limit of the surface tension is not particularly limited, but is preferably 40 mN / m or less, more preferably 38 mN / m or less, and more preferably 36 mN / m, from the viewpoint of imparting inkjet suitability. m or less. The surface tension of the photocurable composition for imprints is measured according to the following method.
The surface tension was measured at 23 ° C. using a glass plate using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. The unit is shown in mN / m. Two samples were prepared for each level, and each was measured three times. An arithmetic average value of a total of six times is adopted as the evaluation value.

The Onishi parameter of the photocurable composition for imprints is preferably 5 or less, more preferably 4 or less, and even more preferably 3.7 or less. Although the lower limit of the Onishi parameter of the curable composition for imprints is not particularly limited, it may be, for example, 1 or more, or 2 or more.
The Onishi parameter can be determined by substituting the numbers of carbon atoms, hydrogen atoms, and oxygen atoms of all the constituent components of the photocurable composition for imprints into the following formula.
Onishi parameter = sum of the number of carbon, hydrogen and oxygen atoms / (number of carbon atoms-number of oxygen atoms)

The photocurable composition for imprints used in the present invention has a value of ΔHSP calculated by the following formula (H1) based on the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the photocurable composition for imprint. It is preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The lower limit may be zero. When the value of ΔHSP is 10 or less, the effect of the photocurable composition 13 for imprints on droplet expandability can be expected.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 (H1)
ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprinting and the dispersion term component of the Hansen solubility parameter vector of the liquid film, and ΔP is the photocurable composition for imprinting. The difference between the polarity term component of the Hansen solubility parameter vector and the polarity term component of the Hansen solubility parameter vector of the liquid film, ΔH is the hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprinting, The difference in the hydrogen bond term component of the Hansen solubility parameter vector of the film.

The dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprinting is preferably from 8 to 25, more preferably from 10 to 20, and even more preferably from 14 to 18.
The polarity term component of the Hansen solubility parameter vector of the photocurable composition for imprint is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 5.
The hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprint is preferably from 1 to 15, more preferably from 3 to 10, and even more preferably from 3 to 8.

The dispersion term component, the polar term component, and the hydrogen bond term component of the Hansen solubility parameter vector of the liquid film and the photocurable composition for imprinting are respectively set by the methods described in Examples described later. Further, in the present invention, the dispersion term component, the polar term component, and the hydrogen bond term component of the Hansen solubility parameter vector of the liquid film are the dispersion of the Hansen solubility parameter of the non-volatile component (the component other than the solvent) of the liquid film forming composition. The values of the term component, the polar term component, and the hydrogen bond term component are used.

[Radical polymerizable compound]
The photocurable composition for imprint contains a radically polymerizable compound. Examples of the radical polymerizable group included in the radical polymerizable compound include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

The radical polymerizable compound may be a monofunctional radical polymerizable compound having only one radical polymerizable group in one molecule, or a polyfunctional radical polymerizable compound having two or more radical polymerizable groups in one molecule. May be an acidic compound. A monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound may be used in combination. The radical polymerizable compound contained in the photocurable composition for imprint preferably contains a polyfunctional radical polymerizable compound, and contains a radical polymerizable compound containing 2 to 5 radical polymerizable groups in one molecule. More preferably, a radical polymerizable compound containing two to four radical polymerizable groups in one molecule is further preferably contained, and a radical polymerizable compound containing two radical polymerizable groups in one molecule is particularly preferably contained. preferable.

In addition, at least one kind of the radical polymerizable compound contained in the photocurable composition for imprint includes an aromatic ring (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, still more preferably having 6 to 10 carbon atoms) and It preferably contains at least one of an alicyclic ring (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 6 carbon atoms), and further preferably contains an aromatic ring. The aromatic ring is preferably a benzene ring. The molecular weight of the radical polymerizable compound is preferably from 100 to 900.

It is also preferable that at least one of the above radical polymerizable compounds is a compound represented by the following formula (I-1).

L ²⁰ is a 1 + q divalent linking group, for example, a 1 + q divalent alkane group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3), or an alkene structure group (Preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, and still more preferably having 2 to 3 carbon atoms), an aryl group (having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms) ), A group having a heteroaryl structure (preferably having 1 to 22 carbon atoms, more preferably having 1 to 18 carbon atoms, and still more preferably having 1 to 10 carbon atoms. Examples of the hetero atom include a nitrogen atom, a sulfur atom and an oxygen atom. , A 6-membered ring or a 7-membered ring), or a linking group containing a group obtained by combining these. Examples of a group obtained by combining two aryl groups include groups having a structure such as biphenyl, diphenylalkane, biphenylene, and indene. Examples of a combination of a group having a heteroaryl structure and a group having an aryl structure include groups having a structure such as indole, benzimidazole, quinoxaline, and carbazole.
L ²⁰ is preferably a linking group containing at least one selected from an aryl group and a heteroaryl group, and more preferably a link group containing an aryl group.

R ²¹ and R ²² each independently represent a hydrogen atom or a methyl group.

L ²¹ and L ²² each independently represent a single bond or the above-mentioned linking group L, and is preferably a single bond or an alkylene group.
L ²⁰ and L ²¹ or L ²² may form a ring without intervention or through a linking group L. L ²⁰ , L ²¹ and L ²² may have the substituent T described above. A plurality of substituents T may combine to form a ring. When there are a plurality of substituents T, they may be the same or different.
q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, still more preferably 0 or 1, and particularly preferably 1.

Examples of the radical polymerizable compound include the compounds used in the following examples, the compounds described in paragraphs 0017 to 0024 of JP-A-2014-133 and the compounds described in the examples, and the compounds described in paragraphs 0024 to 0089 of JP-A-2005-0090171. The compounds described in paragraphs 0023 to 0037 of JP-A-2015-070145 and the compounds described in paragraphs 0012 to 0039 of WO2016 / 152597 can be exemplified, but the present invention is not limited thereto. Is not to be interpreted.

The radical polymerizable compound is preferably contained in the photocurable composition for imprints in an amount of 30% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and still more preferably 55% by mass or more. It may be 60% by mass or more, and may be 70% by mass or more. Further, the upper limit is preferably less than 99% by mass, more preferably 98% by mass or less, and can be 97% by mass or less.

[Photoradical polymerization initiator]
The photocurable composition for imprints contains a photoradical polymerization initiator. As the photoradical polymerization initiator, any compound can be used as long as it is a compound that generates an active species that polymerizes a radical polymerizable compound by light irradiation. In the present invention, a plurality of photoradical polymerization initiators may be used in combination.

公 知 A known compound can be arbitrarily used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (eg, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides Thio compounds, ketone compounds, aromatic onium salts, acetophenone compounds, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, and the like. For the details thereof, the description in paragraphs 0165 to 182 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification. Of these, acetophenone compounds, acylphosphine compounds, and oxime compounds are preferred. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-127, IRGACURE-819, IRGACURE-379, IRGACURE-369, IRGACURE-754, IRGACURE-1800, IRGACURE-651, IRGACURE-GAR, IRGACURE-GAR, and IRGACURE-IRGAUREGA -1173, etc. (all manufactured by BASF), Omnirad 184, Omnirad TPO H, Omnirad 819, Omnirad 1173 (all manufactured by IGM Resins BV).

The photo-radical polymerization initiator is preferably contained in the photocurable composition for imprints in an amount of 0.01 to 15% by mass, more preferably 0.1 to 12% by mass, and even more preferably 0.2 to 12% by mass. 7% by mass.

[Other components]
The photocurable composition for imprints may further contain a surfactant, a sensitizer, a release agent, an antioxidant, a polymerization inhibitor, and the like. Specific examples of the curable composition for imprints that can be used in the present invention include the compositions described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537. And their contents are incorporated herein. The description of the above publication can also be referred to for the method of preparing the photocurable composition for imprints, and the contents thereof are incorporated in the present specification.

The content of the solvent in the photocurable composition for imprints is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less of the photocurable composition for imprints. It is more preferred that there be.
The photocurable composition for imprinting is preferably a polymer (preferably having a weight average molecular weight of more than 1,000, more preferably having a weight average molecular weight of more than 2,000, even more preferably having a weight average molecular weight of 10,000 or more. (Polymer) is not substantially contained. The phrase "contains substantially no polymer" means that, for example, the content of the polymer is 0.01% by mass or less of the curable composition for imprints, preferably 0.005% by mass or less, and not containing at all. Is more preferred.

<Kit>
Next, the kit of the present invention will be described. The kit of the present invention is a kit used for the imprint laminate of the present invention described above, and a composition for forming an underlayer film including a polymer having a radical polymerizable group and a cationic polymerizable group, at 23 ° C. The composition includes a liquid film forming composition containing a radical polymerizable compound that is liquid at 1 atm, and a photocurable composition for imprint containing a radical polymerizable compound and a photoradical polymerization initiator. The composition for forming a lower layer film, the composition for forming a liquid film, and the photocurable composition for imprinting include those described above, and the preferred ranges are also the same.

<Production method of imprint laminate>
Next, a method for manufacturing the imprint laminate of the present invention will be described.
The method for producing a laminate for imprinting of the present invention includes a step of forming an underlayer film by applying a composition for forming an underlayer film containing a polymer having a radically polymerizable group and a cationically polymerizable group on a substrate; Forming a liquid film by applying a liquid film-forming composition containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm on the film, and forming a radical polymerizable compound and a photoradical polymerization initiator on the liquid film Applying a photocurable composition for imprints, comprising:
including. Hereinafter, each step will be described.

で は In the step of forming the underlayer film, the underlayer film is formed by applying a composition for forming an underlayer film containing a polymer having a radically polymerizable group and a cationically polymerizable group on a substrate. The substrate to which the composition for forming an underlayer film is applied is not particularly limited. The one described in the section of the imprint laminate described above is used. As the composition for forming an underlayer film, those described in the section of the laminate for imprint described above are used. The lower layer film is preferably formed by applying the composition for forming a lower layer film on a substrate in a layered manner. An adhesive film may be provided on the surface of the substrate below the lower film.

適用 The method of applying the composition for forming the underlayer film is not particularly limited, and a generally well-known application method can be adopted. For example, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spin coating, slit scanning, and inkjet printing are exemplified, and spin coating is preferred. After the composition for forming an underlayer film is applied on the substrate in a layered form, preferably, the solvent is volatilized (dried) by heat to form the underlayer film. After drying, it is also preferable to heat (bake) at a temperature of 100 to 300 ° C. (preferably 130 to 260 ° C., more preferably 150 to 230 ° C.). The heating time is preferably 30 seconds to 5 minutes.

Next, a liquid film-forming composition containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm is applied on the lower layer film to form a liquid film. The liquid film is preferably formed by applying the composition for forming a liquid film on the lower film in a layered manner. As the composition for forming a liquid film, those described in the section of the laminate for imprint described above are used.

The method for applying the composition for forming a liquid film is not particularly limited, and a generally well-known application method can be employed. For example, 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, and an ink jet method are exemplified, and a spin coating method is preferable. After the composition for forming a liquid film is applied in a layer on the lower film, it is also preferable to form a liquid film by evaporating (drying) the solvent by heat, preferably. When the solvent is volatilized by heat, the heating temperature is preferably from 80 to 200 ° C, more preferably from 80 to 180 ° C, even more preferably from 80 to 150 ° C. The heating temperature is preferably lower than the temperature at which the polymerizable compound contained in the composition for forming a liquid film reacts and cures. The heating time is preferably 30 seconds to 5 minutes.

Next, a photocurable composition for imprints containing a radical polymerizable compound and a photoradical polymerization initiator is applied on the liquid film. As the photocurable composition for imprint, those described in the section of the laminate for imprint described above are used. The method of applying the photocurable composition for imprinting is not particularly limited, and the description in paragraph 0102 of JP-A-2010-109092 (the publication number of the corresponding US application is US2011 / 0183127) can be referred to. The contents are incorporated herein. The photocurable composition for imprinting is preferably applied to the surface of a liquid film by an inkjet method. Further, the photocurable composition for imprints may be applied by multiple coating. In a method of arranging droplets on the surface of a liquid film by an inkjet method or the like, the amount of the droplets is preferably about 1 to 20 pL, and it is preferable to arrange the droplets on the surface of the liquid film at intervals. The interval between droplets is preferably 10 to 1000 μm. In the case of the inkjet method, the interval between the droplets is the interval between the nozzles of the inkjet.

よ う Thus, the imprint laminate of the present invention can be manufactured.

<Pattern forming method>
Next, the pattern forming method of the present invention will be described.
The pattern forming method of the present invention is a step of forming an underlayer film by applying an underlayer film forming composition containing a polymer having a radically polymerizable group and a cationically polymerizable group on a substrate,
Forming a liquid film by applying a liquid film-forming composition containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower layer film;
Applying a photocurable composition for imprints containing a radical polymerizable compound and a photoradical polymerization initiator on the liquid film,
Contacting a mold having a pattern with a photocurable composition for imprinting on a liquid film,
A step of exposing the photocurable composition for imprint in a state where the mold is in contact with the mold,
A step of peeling the mold from the exposed photocurable composition for imprint,
including. Through these steps, a desired cured product pattern (imprint pattern) is obtained. Hereinafter, the pattern forming method of the present invention will be described with reference to the drawings.

(4) The step of forming the lower layer film, the step of forming the liquid film, and the step of applying the photocurable composition for imprint are the same as those described in the section of the method for producing a laminate for imprint described above. Thus, the imprint laminate shown in FIG. 1 is formed.

Next, as shown in FIG. 2, the photocurable composition for imprint 13 on the liquid film 12 is brought into contact with the mold 20 having a pattern. Specifically, the mold 20 is pressed against the surface of the photocurable composition 13 for imprints.

The mold 20 may be a light-transmitting mold or a light-impermeable mold. When using a light transmissive mold, it is preferable to irradiate the photocurable composition for imprint 13 with light from the mold 20 side. On the other hand, when a light-impermeable mold is used, it is preferable to use a light-transmitting substrate as the substrate 1 and irradiate light from the substrate 1 side. In the present invention, it is more preferable to use a light transmissive mold and irradiate light from the mold 20 side.

A mold that can be used in the present invention is a mold having a pattern to be transferred. The pattern of the mold can be formed according to a desired processing accuracy by, for example, photolithography or electron beam lithography, but the method of manufacturing a mold pattern is not particularly limited in the present invention. Further, a pattern formed by the method for producing a cured product pattern according to a preferred embodiment of the present invention can be used as a mold.
The material constituting the light-transmitting mold used in the present invention is not particularly limited, but may be a light-transmitting resin such as glass, quartz, polymethyl methacrylate (PMMA), or a polycarbonate resin, a transparent metal vapor-deposited film, or polydimethylsiloxane. Examples thereof include a flexible film, a photocurable film, and a metal film, and quartz is preferable.
The non-light-transmitting mold material used when a light-transmitting substrate is used in the present invention is not particularly limited, but may be any material having a predetermined strength. Specific examples include ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. And are not specifically restricted.

When the photocurable composition for imprint 13 on the liquid film 12 is brought into contact with the mold 20 having a pattern, the mold pressure is preferably set to 10 atm or less. By setting the mold pressure to 10 atm or less, the mold 20 and the substrate 1 are less likely to be deformed, and the pattern accuracy tends to be improved. It is also preferable because the pressure is low and the device tends to be reduced in size.
It is also preferable that the contact between the photocurable composition for imprint 13 and the mold 20 is performed in an atmosphere containing a helium gas, a condensable gas, or both a helium gas and a condensable gas.

Next, the photocurable composition for imprint 13 is exposed while the mold 20 is in contact with the photocurable composition for imprint 13. The irradiation amount at the time of exposure may be sufficiently larger than the minimum irradiation amount necessary for curing the photocurable composition 13 for imprints. The irradiation amount required for curing the photocurable composition for imprint 13 is determined as appropriate by examining the consumption of unsaturated bonds of the photocurable composition for imprint 13 and the like. The type of light used for the exposure is not particularly limited, but ultraviolet light is exemplified. In addition, the substrate temperature during the exposure is usually room temperature, but the exposure may be performed while heating to increase the reactivity. If a vacuum state is set as a pre-exposure stage, it is effective in preventing air bubbles from being mixed, suppressing a decrease in reactivity due to oxygen being mixed, and improving the adhesion between the mold 20 and the photocurable composition 13 for imprint. Light irradiation may be performed in the state. The preferable degree of vacuum at the time of exposure is in the range of 10 ^-1 Pa to normal pressure.
At the time of exposure, the exposure illuminance is preferably in the range of 1 to 500 mW / cm ² , and more preferably in the range of 10 to 400 mW / cm ² . The exposure time is not particularly limited, but is preferably 0.01 to 10 seconds, and more preferably 0.5 to 1 second. Exposure amount is preferably in a range of 5 ~ 1000mJ / cm ^2, and more preferably in the range of 10 ~ 500mJ / cm ^2.

(4) After the exposure, if necessary, a step of applying heat to the photocurable composition for imprint 13 after the exposure to further cure the composition may be included. The heating temperature is preferably from 150 to 280 ° C, more preferably from 200 to 250 ° C. The heating time is preferably from 5 to 60 minutes, more preferably from 15 to 45 minutes.

Next, the mold 20 is peeled off from the exposed photocurable composition for imprints (FIG. 3). In this manner, a pattern having a shape following the pattern of the mold 20 (hereinafter, also referred to as a cured product pattern) is formed. The obtained cured product pattern can be used for various applications as described below. The present invention is particularly advantageous in that a fine pattern on the order of nanometers can be formed, and a pattern having a size of 50 nm or less, particularly 30 nm or less can be formed. The lower limit of the size of the cured product pattern formed by the method for producing a cured product pattern is not particularly limited, but may be, for example, 1 nm or more.

<Application of cured product pattern>
The pattern (cured product pattern) formed by the pattern forming method of the present invention can be used as a permanent film used for a liquid crystal display (LCD) or the like, or as an etching resist (lithographic mask) for manufacturing a semiconductor element. . In particular, the present invention discloses a circuit board manufacturing method including a step of obtaining a pattern (cured product pattern) by a pattern forming method according to a preferred embodiment of the present invention. Further, in the method of manufacturing a circuit board according to a preferred embodiment of the present invention, a step of performing etching or ion implantation on the substrate using the pattern (cured product pattern) obtained by the above-described pattern forming method as a mask, and forming an electronic member And a step of carrying out. The circuit board is preferably a semiconductor element. That is, the present invention discloses a method for manufacturing a semiconductor device including the above pattern forming method. Further, the present invention discloses a method of manufacturing an electronic device, comprising: a step of obtaining a circuit board by the method of manufacturing a circuit board; and a step of connecting the circuit board and a control mechanism that controls the circuit board. Further, by forming a grid pattern on a glass substrate of a liquid crystal display device by using the pattern forming method of the present invention, it is possible to reduce the reflection and absorption and reduce the cost of a polarizing plate having a large screen size (for example, 55 inches or more than 60 inches). Can be manufactured. For example, a polarizing plate described in JP-A-2015-132825 or WO2011 / 132649 can be manufactured. One inch is 25.4 mm.

The pattern (cured product pattern) formed by the pattern forming method of the present invention is also useful as an etching resist (lithographic mask). When a cured product pattern is used as an etching resist, first, a pattern (cured product pattern) is formed on a substrate by applying the pattern forming method of the present invention, and the obtained cured product pattern is used as an etching mask. To etch the substrate. By etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF _{4 in} the case of dry etching, a pattern can be formed on the substrate according to a desired cured product pattern. it can.

The pattern (cured material pattern) formed by the pattern forming method of the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state imaging device, an LED (light emitting diode), an organic EL (organic electroluminescence), and the like. Light emitting devices, optical devices such as liquid crystal displays (LCD), optical components such as diffraction gratings, relief holograms, optical waveguides, optical filters, microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizing plates, Flat panel display members such as polarizing elements, optical films, pillars, etc., nano-bio devices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, micropatterns using self-assembly of block copolymers (Directed self-assembly, DSA) can also be preferably used in the preparation of the guide patterns, etc. for.

The present invention will be described more specifically with reference to the following examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below.

<Method for measuring weight molecular weight (Mw)>
The weight average molecular weight (Mw) of the polymer was defined as a value in terms of polystyrene according to gel permeation chromatography (GPC measurement). The apparatus used was HLC-8220 (manufactured by Tosoh Corporation), and the columns used were a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). . The eluent used was THF (tetrahydrofuran). For detection, an RI (Refractive Index) detector was used.

<Calculation of Hansen solubility parameter>
The Hansen solubility parameters of the liquid film and the curable composition for imprints were calculated using HSP calculation software HSPiP. Specifically, by inputting the structural formula of each compound contained in the liquid film and the curable composition for imprints into the software in SMILES format, the Hansen solubility parameter of the liquid film and the curable composition for imprints is input. A variance term component (hereinafter, also referred to as D component), a polar term component (hereinafter, also referred to as P component), and a hydrogen bond term component (hereinafter, also referred to as H component) of the vector were calculated. The distance between the Hansen solubility parameters (ΔHSP) between the photocurable composition for imprinting and the liquid film was calculated by applying the calculated Hansen solubility parameters to the following equation.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5
ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprint and the dispersion term component of the Hansen solubility parameter vector of the liquid film, and ΔP is the photocurable composition for imprint. Is the difference between the polarity term component of the Hansen solubility parameter vector of the material and the polarity term component of the Hansen solubility parameter vector of the liquid film, and ΔH is the hydrogen bond term component of the Hansen solubility parameter vector of the photocurable composition for imprint. And the hydrogen bond term component of the Hansen solubility parameter vector of the liquid film.
As the Hansen solubility parameter of the liquid film, a Hansen solubility parameter of a non-volatile component (a component other than the solvent) of the composition for forming a liquid film was used.

<Measurement of viscosity>
The viscosity was measured by using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34 ′ × R24) while adjusting the temperature of the sample cup to 23 ° C. The unit was shown in mPa · s. Regarding the viscosity (ηUL) of the nonvolatile component of the composition for forming an underlayer film for imprint, the viscosity was measured using a composition in which components other than the solvent were mixed. Other details regarding the measurement conformed to JISZ8803: 2011. Two samples were prepared for each level, and each was measured three times. The arithmetic average value of six times in total was adopted as the evaluation value.
(Synthesis of polymer)
<Synthesis of P-1>
Propylene glycol monomethyl ether acetate (PGMEA) (28.4 g) was added to a three-necked flask with N ₂ flow, and the mixture was heated to 90 ° C. Glycidyl Methacrylate (manufactured by NOF Corporation, 28.4 g, 0.2 mol) and a photoradical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-601, 1.1 g, 4.8 mmol) were added to PGMEA (28. 4 g), and the resulting mixture was added dropwise over 2 hours at a temperature not exceeding 95 ° C. in the flask, followed by aging at 90 ° C. for 4 hours. Then, it cooled to 25 degreeC. Methanol (570 g) was added to another three-necked flask, cooled to 10 ° C., and stirred. The reaction solution in the flask was added dropwise at a temperature not exceeding 15 ° C. over 30 minutes, and the mixture was stirred for 1 hour. Thereafter, the mixture was stopped for 1 hour and filtered under reduced pressure. The target compound (intermediate P-1A) was synthesized by drying the obtained powder under reduced pressure.
Next, PGMEA (40.8 g), Intermediate P-1A (20.0 g, 0.14 mol), Acrylic Acid (Tokyo Kasei Kogyo Co., Ltd., 5.0 g, 70 mmol) were placed in a three-necked flask with N ₂ flow. ), Tetraethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., 0.1 g, 0.7 mmol) and 4-OH-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd., 1.72 mg, 0.01 mmol), and the mixture was added at 90 ° C. Aging was performed for 7 hours. Then, it cooled to 25 degreeC. Diisopropyl ether (250 g) and methanol (50 g) were added to another three-necked flask, cooled to 0 ° C., and stirred. The reaction solution in the flask was added dropwise at a temperature not exceeding 5 ° C. over 30 minutes, followed by stirring for 1 hour. Thereafter, the mixture was stopped for 1 hour and filtered under reduced pressure. The target compound (P-1) was synthesized by drying the obtained powder under reduced pressure.

<Synthesis of P-2 to P18, H-1, and H-2>
P-2 to P-18, H-1, and H-2 were synthesized in the same manner as in the synthesis of P-1.

<Preparation of composition for forming lower layer film>
Each of the compounds shown in the following table was mixed, and subjected to two-stage filtration with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 μm and a PTFE filter having a pore size of 0.003 μm to obtain a composition X-1 for forming an underlayer film. ~ X-26 was prepared.

The raw materials described in the above table are as follows.
(polymer)
P-1: Polymer having the following structure (Mw = 20,000)
P-2: Polymer having the following structure (Mw = 30,000)
P-3: Polymer having the following structure (Mw = 50,000)
P-4: Polymer having the following structure (Mw = 10,000)
P-5: Polymer having the following structure (Mw = 20,000)
P-6: Polymer having the following structure (Mw = 80,000)
P-7: Polymer having the following structure (Mw = 100,000)
P-8: Polymer having the following structure (Mw = 20,000)
P-9: Polymer having the following structure (Mw = 50,000)
P-10: Polymer having the following structure (Mw = 20,000)
P-11: Polymer having the following structure (Mw = 40,000)
P-12: Polymer having the following structure (Mw = 20,000)
P-13: Polymer having the following structure (Mw = 40,000)
P-14: Polymer having the following structure (Mw = 7,000)
P-15: Polymer having the following structure (Mw = 200,000)
P-16: Polymer having the following structure (Mw = 20,000)
P-17: Polymer having the following structure (Mw = 30,000)
P-18: Polymer having the following structure (Mw = 150,000)
H-1: Polymer having the following structure (Mw = 20,000)
H-2: Polymer having the following structure (Mw = 20,000)

(Additive)
T-1: Sun-Aid SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd.)
T-2: Omnirad 819 (manufactured by IGM Resins BV)
T-3: IRGACURE OXE01 (manufactured by BASF)
T-4: Omnirad 1173 (manufactured by IGM Resins BV)

(solvent)
PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether GBL: γ-butyrolactone

<Preparation of composition for forming liquid film>
Each compound shown in the following table was mixed, and subjected to two-stage filtration with a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 μm and a PTFE filter having a pore size of 0.003 μm to obtain a composition W-1 for forming a liquid film. ~ W-29 was prepared. The Hansen solubility parameters of the nonvolatile components of the composition for forming a liquid film are shown in the following table.

The raw materials described in the above table are as follows.

(Additive)
T-1: Sun-Aid SI-150L (manufactured by Sanshin Chemical Industry Co., Ltd.)
T-5: Omnirad TPO H (manufactured by IGM Resins BV)
T-6: Omnirad 184 (manufactured by IGM Resins BV)
T-7: BLAUNON SR-705 (manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene stearyl ether)

(solvent)
PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether GBL: γ-butyrolactone

<Preparation of photocurable composition for imprint>
Various compounds having the structural formulas shown in Table 3 were mixed, and two-stage filtration was performed using a polytetrafluoroethylene (PTFE) filter having a pore size of 0.1 μm and a PTFE filter having a pore size of 0.003 μm to obtain a photocurable composition for imprint. Products V-1 to V-6 were prepared.

The Hansen solubility parameters of the photocurable composition for imprints are as follows.

<Calculation of ΔHSP value of Hansen solubility parameter of liquid film and Hansen solubility parameter of photocurable composition for imprint>
The Hansen solubility parameters of the liquid film and the photocurable composition for imprints were calculated using HSP calculation software HSPiP. Specifically, by inputting the structural formula of each compound contained in the liquid film and the photocurable composition for imprints into the software in the SMILES format, the Hansen of the liquid film and the photocurable composition for imprints is input. Each component (ΔD, ΔP, ΔH) of the solubility parameter was calculated. As the Hansen solubility parameter of the liquid film, a Hansen solubility parameter of a non-volatile component (a component other than the solvent) of the composition for forming a liquid film was used.
The ΔHSP value of the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the photocurable composition for imprint was calculated by applying the calculated Hansen solubility parameter to the following equation.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5

<Evaluation>

<Evaluation of adhesion>
A composition for forming an underlayer film shown in the following table was spin-coated on a silicon wafer, heated for 1 minute using a hot plate at 220 ° C., and the solvent was dried to form an underlayer film having a thickness of 5 nm. Next, the surface of the lower layer film was spin-coated with a liquid film forming composition shown in the following table, heated for 1 minute using a hot plate at 100 ° C., and the solvent was dried to obtain a liquid having a film thickness shown in the following table. A film was formed. The thicknesses of the lower layer film and the liquid film were measured by an ellipsometer and an atomic force microscope.
On the surface of the liquid film obtained above, a photocurable composition for imprints, temperature-controlled to 25 ° C., as shown in the following table, was applied at 1 pL / nozzle using an inkjet printer DMP-2831, manufactured by FUJIFILM Dymatics. And the droplets were applied to the surface of the liquid film so that the droplets were arranged in a square array at intervals of about 100 μm. Next, a quartz mold (rectangular line / space pattern (1/1), line width 60 nm, groove depth 100 nm, line edge roughness 3.5 nm) is pressed into contact with the photocurable composition for imprint on the liquid film. The mold was filled with the photocurable composition for imprinting. Further, after exposing from the mold side under a condition of 300 mJ / cm ² using a high-pressure mercury lamp, the pattern was transferred to the photocurable composition for imprints by removing the mold.
The pattern transferred to the photocurable composition for imprinting was observed using an optical microscope (manufactured by Olympus, STM6-LM), and the peeling failure of the pattern was evaluated based on the following criteria.
A: No peeling failure was observed in the entire pattern.
B: Peeling failure was observed in less than 10% of the pattern.
C: Peeling failure was observed in an area of 10% or more of the pattern.

<Evaluation of wettability>
A composition for forming an underlayer film shown in the following table was spin-coated on a silicon wafer, heated for 1 minute using a hot plate at 220 ° C., and the solvent was dried to form an underlayer film having a thickness of 5 nm. Next, the surface of the lower layer film was spin-coated with a liquid film forming composition shown in the following table, heated for 1 minute using a hot plate at 100 ° C., and the solvent was dried to obtain a liquid having a film thickness shown in the following table. A film was formed. The thicknesses of the lower layer film and the liquid film were measured by an ellipsometer and an atomic force microscope. In addition, in Comparative Example 5 using the liquid film forming composition W-2, a solid film was formed.
The surface of the liquid film obtained above (the surface of the lower layer film for Comparative Example 3 and the surface of the solid film for Comparative Example 5) was subjected to a temperature adjustment to 25 ° C. and the photocurable composition for imprints shown in the following table. Was ejected in a droplet amount of 1 pL per nozzle using an inkjet printer DMP-2831, manufactured by Fuji Film Dimatics, and the droplets were applied to the surface of the liquid film so as to form a square array at intervals of about 100 μm. . Next, a quartz substrate was pressed against the photocurable composition for imprint on the liquid film to flatten the photocurable composition for imprint. Further, after exposing from the mold side under a condition of 300 mJ / cm ² using a high-pressure mercury lamp, the quartz substrate was peeled off to obtain a flat film.
The flat film surface was observed using an optical microscope (Olympus STM6-LM), and the wettability was evaluated according to the following criteria.
A: In the imprint area, no unfilled area (area in which the cured product of the photocurable composition for imprint does not exist) did not occur.
B: In some regions of the imprint area, unfilling at the inkjet droplet boundary was confirmed.
C: Unfilling at the boundary of the inkjet droplet was confirmed over the entire surface of the imprint area.
D: An area where a flat film was not formed because the ink-jet droplets were not connected to each other was confirmed.

As is clear from the above results, the examples were excellent in the evaluation of wettability and adhesion.
On the other hand, in Comparative Examples 1 and 2, in which a polymer containing only one of a radically polymerizable group and a cationically polymerizable group was used as the underlayer film forming composition, the adhesion was insufficient. In Comparative Example 3 in which no liquid film was provided, the wettability was insufficient. Comparative Example 4 using the liquid film-forming composition containing no polymerizable compound had insufficient adhesion. Comparative Example 5, in which a solid film was formed instead of the liquid film, had insufficient wettability.

The value of ΔHSP in the above table is the distance between Hansen solubility parameters (ΔHSP) between the photocurable composition for imprinting and the liquid film, and was calculated by the method described above.

1: substrate 10: laminate for imprint 11: lower film 12: liquid film 13: photocurable composition for imprint 20: mold

Claims (10)

1. An underlayer film formed from an underlayer film forming composition containing a polymer having a radically polymerizable group and a cationically polymerizable group,
   A liquid film containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm provided on the surface of the lower film;
   Provided on the surface of the liquid film, a photocurable composition for imprints containing a radical polymerizable compound and a photoradical polymerization initiator,
   A laminate for imprinting, comprising:
2. The radical polymerizable group contained in the polymer is a group having an ethylenically unsaturated bond, and the cationic polymerizable group is a group represented by any of the following formulas (T1) to (T4). The laminate for imprints described above;
   

   

   In the formula (T1), X ¹ represents O, NR ¹ or S, R ¹ represents a hydrogen atom or an alkyl group, Rt ¹ represents a hydrogen atom or an alkyl group, and a wavy line represents a bond;
   In the formula (T2), X ² represents O, NR ² or S, R ² represents a hydrogen atom or an alkyl group, Rt ² represents a hydrogen atom or an alkyl group, and a wavy line represents a bond;
   In the formula (T3), X ³ represents O, NR ³ or S, R ³ represents a hydrogen atom or an alkyl group, Rt ³ represents a hydrogen atom or an alkyl group, and a wavy line represents a bond;
   In the formula (T4), X ⁴ represents O, NR ⁴ or S, R ⁴ represents a hydrogen atom or an alkyl group, p represents 0 or 1, q represents 0 or 1, and n represents 0 to 2 represents an integer, and a wavy line represents a bond.
3. The imprinted laminate according to claim 1 or 2, wherein the composition for forming an underlayer film contains a thermosetting accelerator.
4. 4. The imprint laminate according to claim 3, wherein the thermosetting accelerator is a compound that generates an acid or a cation at a temperature of 100 ° C. or higher. 5.
5. (5) The laminate for imprint according to any one of (1) to (4), wherein the thickness of the liquid film is 5 nm or less.
6. The imprint laminate according to any one of claims 1 to 5, wherein the radical polymerizable compound contained in the liquid film is a polyfunctional radical polymerizable compound.
7. The ΔHSP value calculated by the following equation (H1) based on the Hansen solubility parameter of the liquid film and the Hansen solubility parameter of the photocurable composition for imprinting is 10 or less. The laminate for imprints described in the above item;
   ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 (H1)
   ΔD is the difference between the dispersion term component of the Hansen solubility parameter vector of the photocurable composition for imprinting and the dispersion term component of the Hansen solubility parameter vector of the liquid film, and ΔP is the light for imprinting. The difference between the polarity term component of the Hansen solubility parameter vector of the curable composition and the polarity term component of the Hansen solubility parameter vector of the liquid film, wherein ΔH is the Hansen solubility parameter vector of the photocurable composition for imprint. And the hydrogen bond term component of the Hansen solubility parameter vector of the liquid film.
8. A step of forming an underlayer film by applying an underlayer film forming composition containing a polymer having a radically polymerizable group and a cationically polymerizable group on a substrate,
   Forming a liquid film by applying a liquid film-forming composition containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower film;
   A step of applying a photocurable composition for imprints containing a radical polymerizable compound and a photoradical polymerization initiator on the liquid film,
   A method for producing a laminate for imprints comprising:
9. A step of forming an underlayer film by applying an underlayer film forming composition containing a polymer having a radically polymerizable group and a cationically polymerizable group on a substrate,
   Forming a liquid film by applying a liquid film-forming composition containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm on the lower film;
   A step of applying a photocurable composition for imprints containing a radical polymerizable compound and a photoradical polymerization initiator on the liquid film,
   Contacting a mold having a pattern with the photocurable composition for imprint on the liquid film,
   Exposing the imprinting photocurable composition in a state where the mold is in contact with the mold,
   Peeling the mold from the exposed photocurable composition for imprint,
   A pattern forming method including:
10. A kit used for the imprint laminate according to any one of claims 1 to 7,
    An underlayer film-forming composition containing a polymer having a radically polymerizable group and a cationically polymerizable group,
    A liquid film-forming composition containing a radical polymerizable compound that is liquid at 23 ° C. and 1 atm;
    A photocurable composition for imprints comprising a radically polymerizable compound and a photoradical polymerization initiator.

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