JP6754344B2 - Composition for forming underlayer film for imprint, kit, laminate, method for manufacturing laminate, method for manufacturing cured product pattern, method for manufacturing circuit board - Google Patents

Description

The present invention relates to a composition for forming an underlayer film for imprinting, a kit, a laminate, a method for producing a laminate, a method for producing a cured product pattern, and a method for producing a circuit board.

In the imprint method, the curable composition is photocured by irradiating light through a light-transmitting mold or a light-transmitting substrate, and then the mold is peeled off to transfer a fine pattern to the photo-cured product. Since this method enables imprinting at room temperature, it can be applied to the field of precision processing of ultrafine patterns such as the fabrication of semiconductor integrated circuits. Recently, new developments such as a nanocasting method that combines the above advantages and a reversal imprint method for producing a three-dimensional laminated structure have been reported.
As a method for applying a curable composition for imprinting, inkjet coating has been studied (for example, Patent Document 1). By adopting the inkjet coating, the coating amount can be adjusted according to the density of the imprint pattern, and a uniform imprint pattern can be secured.
Improving throughput is one of the technical issues in introducing the imprint process into industrial applications such as semiconductor lithography. In order to improve the throughput, it is necessary to improve the filling property of the imprint pattern. Therefore, the development of a technique aimed at improving the wettability (fluidity) of the curable composition for imprinting is underway (Patent Documents 2 to 4).

Special Table 2005-533393 Japanese Unexamined Patent Publication No. 2017-055108 Japanese Unexamined Patent Publication No. 2009-0831172 International Publication No. 2016/152600 Pamphlet

Under such circumstances, an object of the present invention is to improve the wettability of the curable composition for imprinting and the filling property into a mold (template). It is an object of the present invention to provide a novel composition for forming an underlayer film for imprint, a kit, a laminate, a method for producing a laminate, a method for producing a cured product pattern, and a method for producing a circuit board. In addition, as a result of improved fillability in the mold, in the nanoimprint process, which is a preferable usage pattern, high-speed processing can be realized and throughput can be improved. Compositions, kits, and laminates for forming an underlayer film for imprinting. , A method for manufacturing a laminate, a method for manufacturing a cured product pattern, and a method for manufacturing a circuit board.

As a result of studies by the present inventor based on the above problems, it has been found that the above problems can be solved by defining the components and physical properties of the composition for forming an underlayer film for imprinting. Specifically, the above-mentioned problems were solved by the following means <1>, preferably by <2> to <24>.
<1> A composition for forming an underlayer film for imprint, which comprises compound α, compound β, and a compound that is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower, and is for forming the underlayer film for imprint. The total content of compound α contained in the composition is larger than the total content of compound β, and the content of the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower is the composition for forming an underlayer film for imprint. Viscosity at 23 ° C. of the composition for forming an underlayer film for imprint, which is 99.0% by mass or more of the compound and is composed of a component excluding a compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower. Is 5 to 1000 mPa · s, and is used for the underlayer film of the curable composition for imprint, which has a larger surface tension than the compound β and a smaller surface tension than the compound α. ..
<2> The surface tension of the curable composition for imprint is the surface tension of the composition excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower. The composition for forming an underlayer film for imprint according to <1>, which is larger than the above.
<3> The surface tension of the composition for forming an underlayer film for imprint, which is liquid at 23 ° C. and is composed of the components excluding the compound having a boiling point of 250 ° C. or lower, is 38.0 mN / m or less. The composition for forming an underlayer film for imprint according to <2>.
<4> Maximum amount of the curable composition for imprinting The maximum amount of the composition consisting of the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. The composition for forming an underlayer film for imprint according to any one of <1> to <3>, wherein | ΔHSP |, which is the distance between the Hansen solubility parameters and the components, is 4.5 or less;
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5
ΔD: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in the variance term components of the HSP vector of
ΔP: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in polarity term component of HSP vector of
ΔH: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in hydrogen bond term component of HSP vector.
<5> The composition for forming an underlayer film for imprint according to any one of <1> to <4>, wherein the compound β contains a compound having a surface tension of 38.0 mN / m or less.
<6> The total content of the compound β is 45% by mass or less of the composition consisting of the composition excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in the composition for forming an underlayer film for imprinting. The composition for forming an underlayer film for imprint according to any one of <1> to <5>.
<7> At least one curable composition for imprint is contained in a composition composed of components excluding a compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in the composition for forming an underlayer film for imprinting. The composition for forming an underlayer film for imprint according to any one of <1> to <6>, which is a compound having a binding group with.
<8> At least one compound contained in the composition consisting of the components excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in the composition for forming an underlayer film for imprint is a compound containing an aromatic ring. The composition for forming an underlayer film for imprint according to any one of <1> to <7>.
<9> The composition for forming an underlayer film for imprint according to any one of <1> to <8>, wherein the composition for forming an underlayer film for imprint contains a photopolymerization initiator.
<10> A kit having a composition for forming an underlayer film for imprint and a curable composition for imprint, which comprises compound α, compound β, and a compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower. The total content of the compound α contained in the composition for forming the lower layer film for imprint is larger than the total content of the compound β, and the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower. A compound having a content of 99.0% by mass or more of the above composition for forming an underlayer film for imprint, which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the above composition for forming an underlayer film for imprinting. The composition composed of the removed components has a viscosity at 23 ° C. of 5 to 1000 mPa · s, and the curable composition for imprint has a larger surface tension than the compound β and a smaller surface tension than the compound α. kit.
<11> The surface tension of the curable composition for imprint is the surface tension of the composition excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower. The kit according to <10>, which is larger than.
<12> The surface tension of the composition for forming an underlayer film for imprint, which is liquid at 23 ° C. and is composed of the components excluding the compound having a boiling point of 250 ° C. or lower, is 38.0 mN / m or less. The kit according to <11>.
<13> Maximum amount of the curable composition for imprinting The maximum amount of the composition consisting of the components excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. The kit according to any one of <10> to <12>, wherein | ΔHSP |, which is the distance between the Hansen solubility parameters and the component, is 4.5 or less;
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5
ΔD: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in the variance term components of the HSP vector of
ΔP: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in polarity term component of HSP vector of
ΔH: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in hydrogen bond term component of HSP vector.
<14> The kit according to any one of <10> to <13>, wherein the compound β contains a compound having a surface tension of 38.0 mN / m or less.
<15> The total content of the compound β is 45% by mass or less of the composition consisting of the composition excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in the composition for forming an underlayer film for imprinting. The kit according to any one of <10> to <14>.
<16> At least one curable composition for imprint is contained in a composition comprising a component which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower excluding a compound in the composition for forming an underlayer film for imprinting. The kit according to any one of <10> to <15>, which is a compound having a binding group with.
<17> At least one compound contained in the composition consisting of the components excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in the composition for forming an underlayer film for imprint is a compound containing an aromatic ring. The kit according to any one of <10> to <16>.
<18> The kit according to any one of <10> to <17>, wherein the composition for forming an underlayer film for imprint contains a photopolymerization initiator.
<19> A laminate formed from the kit according to any one of <10> to <18>, the lower layer film formed from the composition for forming an underlayer film for imprint, and the imprint. A laminate having an imprint layer formed from a curable composition for use and located on the surface of the underlayer film.
<20> A method for producing a laminate using the kit according to any one of <10> to <18>, wherein the surface of the underlayer film formed from the above-mentioned composition for forming an underlayer film for imprinting. A method for producing a laminate, which comprises applying a curable composition for imprinting to.
<21> The method for producing a laminate according to <20>, wherein the curable composition for imprint is applied to the surface of the underlayer film by an inkjet method.
<22> Further, the step of applying the composition for forming an imprint underlayer film on the substrate in a layered manner is included, and the composition for forming an imprinting underlayer film applied in the layered manner is heated at 40 to 70 ° C. The method for producing a laminate according to <20> or <21>, which comprises the above.
<23> A method for producing a cured product pattern using the kit according to any one of <10> to <18>, wherein a composition for forming an underlayer film for imprinting is applied onto a substrate. An underlayer film forming step for forming an underlayer film, an application step of applying a curable composition for imprinting to the surface of the underlayer film, the curable composition for imprinting, and a pattern for transferring a pattern shape. A mold contacting step of bringing the molds into contact with each other, a light irradiation step of irradiating the curable composition for imprinting with light to form a cured product, and a mold separating step of separating the cured product from the mold. A method for producing a cured product pattern having.
<24> A method for manufacturing a circuit board, which comprises a step of obtaining a cured product pattern by the manufacturing method according to <23>.

According to the present invention, the wettability of the curable composition for imprinting and the filling property into a mold can be improved. As a result, it has become possible to provide a novel composition for forming an underlayer film for imprint, a kit, a laminate, a method for producing a laminate, a method for producing a cured product pattern, and a method for producing a circuit board. Further, as a result of the improved filling property into the mold, it is possible to realize a high-speed processing process in the nanoimprint process, which is a preferable usage pattern, and to improve the throughput.

It is a side view schematically explaining the wetting spread of a droplet according to a preferable embodiment of the present invention. It is a side view schematically explaining the wetting spread of a droplet according to a preferable embodiment of the present invention (continuation of FIG. 1 and an enlarged view of a portion II of FIG. 1). It is a side view schematically explaining the wetting spread of a droplet according to a preferable embodiment of the present invention (continued with FIG. 2). It is a top view which shows typically the state of the wetting spread of the curable composition for imprint when the curable composition for imprint is applied to the surface of the underlayer film with low wettability by an inkjet method. It is a process explanatory drawing which shows an example of the manufacturing process in the case of forming a cured product pattern, and using the obtained cured product pattern for processing a substrate by etching.

The contents of the present invention will be described in detail below. In addition, in this specification, "~" is used in the meaning that the numerical values described before and after it are included as the lower limit value and the upper limit value.
As used herein, "(meth) acrylate" refers to acrylate and methacrylate.
As used herein, "imprint" preferably refers to a pattern transfer having a size of 1 nm to 10 mm, and more preferably a pattern transfer having a size of about 10 nm to 100 μm (nanoimprint).
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, an “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 wavelengths 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 rays (EUV), and X-rays. Further, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. As these lights, monochrome light (single wavelength light) that has passed through an optical filter may be used, or light having a plurality of different wavelengths (composite light) may be used.
Unless otherwise specified, the weight average molecular weight (Mw) in the present invention refers to those measured by gel permeation chromatography (GPC).
Unless otherwise specified, the temperature in the present invention is 23 ° C.
The boiling point in the present invention means the boiling point at 1 atm (1 atm = 1013.25 hPa).

The composition for forming an underlayer film for imprint of the present invention is a composition for forming an underlayer film for imprint containing compound α, compound β, and a compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower. Therefore, the total content of compound α contained in the composition for forming an underlayer film for imprint is larger than the total content of compound β, and the content of the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower. The amount is 99.0% by mass or more of the composition for forming an underlayer film for imprint, and the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less is excluded from the composition for forming an underlayer film for imprint. For the underlayer film of the curable composition for imprint, which has a viscosity of 5 to 1000 mPa · s at 23 ° C. and has a higher surface tension than the compound β and a lower surface tension than the compound α. It is characterized by being used. That is, the composition for forming an imprint underlayer film of the present invention satisfies the following conditions (i) to (v).
(I) In (ii) containing compound α, compound β, and a compound that is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower (hereinafter, this compound may be referred to as “underlayer film solvent”). The total content (Wα) of the compound α contained in the composition for forming the underlayer film for printing is larger than the total content (Wβ) of the compound β; that is, the relationship of Wα> Wβ is established (iii). The content of the compound is 99.0% by mass or more of the composition for forming the lower layer film for imprint (iv) From the component (nonvolatile component) excluding the solvent for the lower layer film in the composition for forming the lower layer film for imprint. The surface tension (γResist) of the curable composition for imprint applied on the underlayer film having a viscosity of 5 to 1000 mPa · s at 23 ° C. of the composition is higher than the surface tension (γβ) of the compound β. Is also large and smaller than the surface tension (γα) of the compound α; that is, the relationship of the following formula (1) holds γα>γTest> γβ ... formula (1)
However, when there are a plurality of compounds α, the relationship of the above formula (1) may be established with the surface tension γα of the compound having the highest content among the plurality of compounds α, and the composition for forming an underlayer film may be used. It is more preferable that the relationship of the above formula (1) holds for the compound α contained in an amount of 90% by mass or more (more preferably 95% by mass or more, still more preferably 100% by mass). The same applies to the compound β, as long as the relationship of the above formula (1) is established with the surface tension γβ of the compound having the highest content among the plurality of compound βs, 90 included in the composition for forming an underlayer film. It is more preferable that the relationship of the above formula (1) holds for the compound β having a mass% or more (more preferably 95% by mass or more, still more preferably 100% by mass).

The reason why the problem of the present invention could be solved by satisfying the above conditions for the composition for forming an imprint underlayer film of the present invention is presumed as follows. This will be described with reference to the drawings showing preferred embodiments of the present invention. It goes without saying that the configuration of the present invention is not limited to the form described in the drawings.
1 to 3 are side views schematically illustrating the wettability and spread of droplets according to a preferred embodiment of the present invention. FIG. 2 shows an enlarged portion of FIG. 1 II. FIG. 1 shows a state in which the lower layer film 35 is already arranged on the substrate 34. For the formation of the underlayer film 35, the composition for forming the underlayer film for imprint according to the preferred embodiment of the present invention is used. Droplets (at the time of ejection) 32 of the curable composition for imprinting are ejected from the inkjet nozzle 31. The ejected droplets land on the underlayer film 35 of the substrate (landing droplets 33). In a preferred embodiment of the present invention, a specific amount of compound α (not shown) and compound β39 are contained in the underlayer film (FIG. 2). The landing droplet 33 gets wet and spreads in the surface direction due to the wettability imparted to the lower layer film (wetting and spreading direction 36). At this time, according to the preferred embodiment of the present invention, it is presumed that the compound β in the underlayer film moves toward the landing droplet 33 due to its surface tension (see the thin arrow in FIG. 2). As a result, the compound β of the composition for forming the lower layer film for imprint segregates at the flow interface, reduces the interfacial tension of the mixed liquid flow part (particularly the droplet flow tip part 33b), and is on the substrate (or the lower layer film). Wetability is improved. Further, since the interfacial tension of the composition for forming the lower layer film for imprint is reduced, it also contributes to the improvement of the stability of the formed film. Not only the above-mentioned compound β39 but also the compound α having a higher surface tension is dissolved in the wet and spread droplets. A droplet 33a in which the components of the underlayer film (compounds α and β) are mixed is formed (see FIG. 3). In this way, the compounds α and β of the composition for forming the underlayer film for imprint are compatible with the curable composition for imprint. This compatible solution has a higher interfacial tension than the original curable composition for imprinting, and is a capillary force that contributes to filling the template pattern and filling the template / substrate (or underlayer) gap. Rise. Therefore, it is considered that high-speed and accurate pattern filling becomes possible.

FIG. 4 is a plan view schematically showing a state in which the curable composition for imprint is wetted and spread when the curable composition for imprint is applied to the surface of the underlayer film by an inkjet method. When the curable composition for imprint is applied by the inkjet (IJ) method, for example, as shown in the figure, droplets of the curable composition 22 for imprint are dropped on the surface of the underlayer film 21 at equal intervals. (Fig. 4 (a)). When the mold is brought into contact with the mold, the droplets spread on the underlayer film 21 and become film-like curable compositions for imprint 22a, 22b, 22c (FIGS. 4 (b) and 4 (c), (D)). However, if the curable composition for imprint does not spread uniformly, for example, when the wet spread stops in FIG. 4C, the state of the curable composition for imprint 22b is completely on the underlayer film 21. A film that does not spread to the surface is formed. That is, there may be a region 23 having a thin film thickness or no film. In this case, the pattern of the mold is not sufficiently filled with the curable composition for imprinting, and the imprinting layer is formed with no pattern. For example, when etching is performed using the pattern of the imprint layer having a defect or an insufficient thickness in such a part as a mask, a region 23 having a thin film thickness or a region without a film and a region 22b other than the film thickness 22b. Etching unevenness occurs, and it becomes difficult to uniformly etch and transfer the desired pattern shape over the entire surface of the imprint region.
On the other hand, according to the composition for forming an imprint underlayer film of the present invention, the interfacial tension between the underlayer film formed thereby and the imprint curable composition is improved, and the wettability is improved. Therefore, the curable composition for imprint 22c is more reliably spread to every corner of the state shown in FIG. 4 (d). As a result, the curable composition for imprinting is accurately and sufficiently filled in the mold throughout, and good patterning with no unevenness in thickness can be achieved in the formed imprinting layer. In addition, improved filling property enables high-speed imprinting, which can lead to improvement in throughput.
In the above description, the mechanism of action according to the preferred embodiment of the present invention has been described by giving an example of applying the curable composition for imprinting on the underlayer film by the inkjet method, but the present invention is limited thereto. It is not interpreted as. For example, even in screen coating and spin coating, good wettability and excellent filling property lead to advantages in processing and product quality, and the effects of the invention can be suitably exhibited.

<Composition for forming an underlayer film for imprint>
The composition for forming an underlayer film for imprint according to the present invention contains a compound (solvent for an underlayer film) which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in a proportion of 99.0% by mass or more, and further described above. It contains a composition (nonvolatile component) composed of components excluding the solvent for the underlayer film. Usually, the non-volatile component finally forms the underlayer film.

<< Non-volatile component >>
The non-volatile component of the underlayer film forming composition for imprint is a liquid at 23 ° C., and the compound (Compound α) having a surface tension higher than the surface tension (γReist) of the curable composition for imprint and the surface more than γReist. Includes compounds with low tension (compound β). Further, such non-volatile components are usually in a liquid state at room temperature (eg, 23 ° C.) and do not easily volatilize by heating. Therefore, it is possible to form an underlayer film in a liquid state at room temperature.

<<< Compound α >>>
The surface tension (γα) of the compound α is larger than the surface tension (γResid) of the curable composition for imprint described later and the surface tension (γβ) of the compound β. The surface tension (γα) of compound α is not particularly limited, but is preferably 35.0 mN / m or more, more preferably 36.0 mN / m or more, and further preferably 37.0 mN / m or more. preferable. The upper limit is preferably 60.0 mN / m or less, more preferably 50.0 mN / m or less, further preferably 45.0 mN / m or less, and 43.0 mN / m or less. Is even more preferable. When the composition for forming an underlayer film for imprint contains two or more kinds of compounds α, it is preferable that the component having the highest content satisfies the above surface tension, and the compound α contained in the composition for forming an underlayer film for imprint It is preferable that 90% by mass or more (more preferably 95% by mass or more, further preferably 100% by mass) satisfies the above surface tension (hereinafter, the same applies to the physical properties of compound α).
The difference (γα-γReist) between the surface tension (γα) of the compound α and the surface tension (γReist) of the curable composition for imprinting is not particularly limited, but is preferably 1.0 mN / m or more. It is more preferably 0 mN / m or more, and further preferably 2.5 mN / m or more. The upper limit is preferably 25.0 mN / m or less, more preferably 15.0 mN / m or less, further preferably 10.0 mN / m or less, and 7.0 mN / m or less. Is even more preferable.
The difference (γα-γβ) between the surface tension of compound α (γα) and the surface tension of compound β (γβ) is not particularly limited, but is preferably 0.5 mN / m or more, preferably 1.0 mN / m or more. It is more preferably 5.0 mN / m or more, further preferably 10.0 mN / m or more, and may be 20.0 mN / m or more. The upper limit is preferably 30.0 mN / m or less, and more preferably 25.0 mN / m or less.
The surface tension shall be a value measured by the measuring method in the examples described later.

As described in detail later, compound α preferably has a group having a binding group with a curable composition for imprint, preferably a polymerizable group, and more preferably an ethylenically unsaturated group. As the ethylenically unsaturated group, a vinyl group, an allyl group, a phenylvinyl group and a (meth) acryloyl group (these exemplary substituents are referred to as an ethylenically unsaturated group E) are preferable.

The compound α is a compound containing an aromatic ring (preferably 7 to 50 carbon atoms, more preferably 7 to 40 carbon atoms, further preferably 7 to 30 carbon atoms) and a compound containing an aromatic heterocyclic ring (preferably 7 to 50 carbon atoms). 7 to 40 is more preferable, 7 to 30 is more preferable), an alicyclic compound (7 to 50 carbon atoms is preferable, 7 to 40 is more preferable, 7 to 30 is more preferable), and a (poly) alkyleneoxy group is contained. It is preferably a compound (7 to 40 carbon atoms is preferable, 7 to 30 is more preferable, and 7 to 20 is more preferable). Of these, compounds containing an aromatic ring and compounds containing a (poly) alkyleneoxy group are more preferable. Here, the (poly) alkyleneoxy group means that it may be either an alkyleneoxy group or a polyalkyleneoxy group.
As the aromatic ring contained in the compound containing the aromatic ring, the number of carbon atoms is preferably 6 to 22, more preferably 6 to 18, and even more preferably 6 to 10. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a phenanthrene ring, a fluorene ring, an acenaphthylene ring, a biphenylene ring, an inden ring, an indan ring, a triphenylene ring, a pyrene ring, a chrysene ring, and a perylene ring. , Tetrahydronaphthylene ring (hereinafter, an example of this aromatic ring is referred to as aromatic ring aCy) and the like. Of these, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable. The aromatic ring may have a structure in which a plurality of aromatic rings are linked, and examples thereof include a biphenyl ring and a bisphenyl ring.
As the aromatic heterocycle, the number of carbon atoms is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 5. Specific examples thereof include thiophene ring, furan ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, tetrazole ring, thiazole ring, oxazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, isoindole ring, and indole. Ring, indazole ring, purine ring, quinolidine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinazoline ring, cinnoline ring, carbazole ring, aclysin ring, phenazine ring, phenothiazine ring, phenoxazine ring, etc. An example of the above is referred to as ring hCy).
The alicyclic has preferably 3 to 22 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms. Specific examples thereof include cyclopropane ring, cyclobutane ring, cyclobutene ring, cyclopentane ring, cyclohexane ring, cyclohexene ring, cycloheptane ring, cyclooctane ring, dicyclopentadiene ring, tetrahydrodicyclopentadiene ring, octahydronaphthalene ring, and the like. Examples thereof include a decahydronaphthalene ring, a hexahydroindane ring, a bornan ring, a norbornene ring, a norbornene ring, an isobornane ring, a tricyclodecane ring, a tetracyclododecane ring, and an adamantane ring (the above examples are referred to as ring fCy). These rings aCy, hCy, and fCy are collectively referred to as ring Cz.
The number of repetitions of the alkyleneoxy group of the (poly) alkyleneoxy group-containing compound is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3. The number of carbon atoms of the alkylene group in the structural repeating unit is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
A compound containing an aromatic ring, a compound containing an aromatic heterocycle, and a (poly) alkyleneoxy group-containing compound are groups having a covalent bond with a component of a curable composition for imprint at the terminal, preferably a polymerizable group. More preferably, it has an ethylenically unsaturated group. As the ethylenically unsaturated group, a vinyl group, an allyl group, a phenylvinyl group and a (meth) acryloyl group (these exemplary substituents are referred to as an ethylenically unsaturated group E) are preferable.
The compound α is preferably a compound represented by the following formula (1) or (2).

In the formula (1), Ar is an aromatic ring (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, more preferably 6 to 10 carbon atoms) or an aromatic heterocycle (carbon) having a structure in which a plurality of aromatic rings are linked. Numbers 1 to 12 are preferable, 1 to 6 are more preferable, and 1 to 5 are even more preferable), a structure in which an aromatic ring and an aromatic heterocycle are linked, a structure in which a plurality of aromatic heterocycles are linked, or an alicyclic ring. (Preferably having 3 to 22 carbon atoms, more preferably 4 to 18 and even more preferably 6 to 10), a structure in which an alicyclic ring and an aromatic ring are linked, a structure in which an alicyclic ring and an aromatic heterocycle are linked, or It has a structure in which a plurality of alicyclic rings are connected. In the connection of each ring, the linking group L described later may intervene. Specific examples of the aromatic ring include the above-mentioned aromatic ring aCy. Examples of aromatic heterocycles include the above hCy example. Examples of the alicyclic include the above-mentioned example of fCy. Ar may have the following substituent T as long as the effect of the present invention is exhibited. Substituents T may be attached to each other with or without linking group L to form a ring. Further, Ar or the substituent T may be bonded to the linking groups L ¹ and L ² with or without the linking group L to form a ring. Examples of the linking groups L ¹ and L ² include the linking group L described later. Among them, L ¹ is preferably an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms). L ² is O, NR ^N, S are preferred, O is more preferable. Y ¹ is an ethylenically unsaturated group, and examples thereof include the above-mentioned ethylenically unsaturated group E, and among them, a (meth) acryloyl group is preferable. n1 represents an integer of 1 to 6, preferably an integer of 1 to 4, preferably 2 or 3.

式中、Ａｒ¹は芳香族環、芳香族複素環、または脂環であり、その好ましい例としては、芳香族環ａＣｙ、芳香族複素環ｈＣｙ、脂環ｆＣｙが挙げられる。Ａは連結基であり、連結基Ｌの例が挙げられ、−ＣＨ₂−、−Ｏ−、−Ｓ−、−ＳＯ₂−、およびハロゲン原子（特にフッ素原子）で置換されてもよい−Ｃ（ＣＨ₃）₂−からなる群から選択される２価の基であることが好ましい。Ａｒ¹で表される芳香族環は置換基Ｔを有していてもよい。置換基Ｔは複数あるとき互いに結合して、あるいは連結基Ｌを介してまたは介さずに式中の環Ａｒ¹と結合して環を形成していてもよい。また、置換基Ｔは、連結基Ａや上記連結基Ｌ¹，Ｌ²と連結基Ｌを介してまたは介さずに結合して環を形成していてもよい。＊はＬ¹との結合位置を表す。ｎ３〜ｎ６はそれぞれ独立に１〜３の整数であり、２または３であることが好ましく、１がより好ましい。 Examples of the structure in which a plurality of aromatic rings, aromatic heterocycles, or alicyclic rings are linked include the following formulas AR-1 or AR-2.

In the formula, Ar ¹ is an aromatic ring, an aromatic heterocycle, or an alicyclic ring, and preferred examples thereof include an aromatic ring aCy, an aromatic heterocyclic ring hCy, and an alicyclic ring fCy. A is a linking group, and examples of the linking group L are given, which may be substituted with -CH _2- , -O-, -S-, -SO _2- , and a halogen atom (particularly a fluorine atom) -C. It is preferably a divalent group selected from the group consisting of (CH ₃ ) ₂ −. The aromatic ring represented by Ar ¹ may have a substituent T. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to the ring Ar ¹ in the formula with or without the linking group L to form a ring. Further, the substituent T may be bonded to the linking group A or the linking groups L ¹ and L ² with or without the linking group L to form a ring. * Represents the bonding position with L ¹ . n3 to n6 are independently integers of 1 to 3, preferably 2 or 3, and more preferably 1.

In formula (2), Y ³ and Y ⁴ independently have an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 6 carbon atoms) and an aryl group (6 to 22 carbon atoms). It is preferably 6-18, more preferably 6-10), or an ethylenically unsaturated group. As the ethylenically unsaturated group, an example of the ethylenically unsaturated group E is preferable. Among them, at least one of Y ³ and Y ⁴ is preferably an ethylenically unsaturated group (preferably an ethylenically unsaturated group E). Examples of the linking group L ³ include the linking group L described later. Among them, O, NR ^N (R ^N is preferably 1 to 12 hydrogen atom or an alkyl group (carbon atoms, more preferably 1 to 6, more preferably 1 to 3, represents a more preferred) is a methyl group.), S is preferable, and O is more preferable. L ⁴ is a linear or branched alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 6 carbon atoms), a linear or branched alkaneylene group (preferably 2 to 12 carbon atoms). 2 to 6 are more preferable, and 2 to 3 are even more preferable). L ⁴ may have a substituent T. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to Y ³ , Y ⁴ , L ³ , L ⁴ in the formula with or without the linking group L to form a ring. n2 is an integer of 1 to 6, with an integer of 1 to 4 being preferred, and 3 or 4 being more preferred.

The linking group L is a linear or branched alkylene group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms), an arylene group (preferably 6 to 22 carbon atoms, 6 to 18 carbon atoms). , 6-10 is even more preferred), -O-, -S-, -SO _2- , -CO-, -NR ^N- , and linking groups for combinations thereof. The alkylene group may have the following substituent T. For example, the alkylene group may be a fluorinated alkylene group having a fluorine atom. The number of atoms contained in the linking group L is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6.

As the substituent T, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 1 to 6 carbon atoms) and a cycloalkyl group (preferably 3 to 24 carbon atoms, 3 to 12 carbon atoms are more preferable). 3, 3 to 6 are more preferable), an aralkyl group (7 to 21 carbon atoms are preferable, 7 to 15 are more preferable, 7 to 11 are more preferable), an alkenyl group (2 to 24 carbon atoms are preferable, 2 to 12 are preferable). More preferably, 2 to 6 are more preferable), cycloalkenyl group (3 to 24 carbon atoms are preferable, 3 to 12 is more preferable, 3 to 6 is more preferable), hydroxyl group, amino group (carbon number 0 to 24). , 0-12 is more preferred, 0-6 is more preferred), thiol group, carboxyl group, aryl group (6-22 carbon atoms are preferred, 6-18 is more preferred, 6-10 is even more preferred). An acyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3), an acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms). ), Allylloyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, further preferably 7 to 11), allylloyloxy group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, 7 to 19). 11 is more preferred), carbamoyl group (preferably 1-12 carbon atoms, more preferably 1-6, more preferably 1-3), sulfamoyl group (preferably 0-12 carbon atoms, more preferably 0-6). 0 to 3 are more preferable), a sulfo group, an alkylsulfonyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3), an arylsulfonyl group (preferably 6 to 22 carbon atoms). Includes a 5- or 6-membered ring, preferably 6-18, more preferably 6-10), a heterocyclic group (preferably 1-12 carbon atoms, more preferably 1-8, even more preferably 2-5). it is preferable), (meth) acryloyl group, (meth) acryloyloxy group, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), oxo (= O), imino (= NR ^N) , alkylidene group _{^{(= C (R N) 2}} ) , and the like. ^RN is synonymous with the above. The alkyl and alkenyl moieties contained in each substituent may be linear or branched, and may be chain or cyclic. When the substituent T is a group capable of taking a substituent, it may further have a substituent T. For example, the alkyl group may be an alkyl halide 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.

The molecular weight of compound α is not particularly limited, but is preferably 1000 or less, more preferably 800 or less, further preferably 600 or less, and even more preferably 400 or less. It is practical that the lower limit is 100 or more.

The blending amount of the compound α is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass in the non-volatile components of the composition for forming an underlayer film for imprinting. % Or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more. There is no particular upper limit, but 99.99% by mass or less is practical. By setting this amount in the above range, the effect of increasing the interfacial tension of the mixed solution with the curable composition for imprinting can be sufficiently obtained, and good filling property can be ensured, which is preferable.
The compound α may be used alone or in combination of two or more. When a plurality of products are used, the total amount is preferably in the above range.

<<< Compound β >>>
The surface tension (γβ) of compound β is lower than the surface tension (γResist) of the curable composition for imprinting and the surface tension (γα) of compound α. The surface tension (γβ) of compound β is preferably 5.0 mN / m or more, more preferably 10.0 mN / m or more, and even more preferably 15.0 mN / m or more. The upper limit is preferably 38.0 mN / m or less, more preferably 36.0 mN / m or less, further preferably 33.0 mN / m or less, and 30.0 mN / m or less. It is even more preferably 27.0 mN / m or less, and even more preferably 24.0 mN / m or less. When the composition for forming an underlayer film for imprint contains two or more kinds of compounds β, it is preferable that the component having the highest content satisfies the above surface tension, and the compound β contained in the composition for forming an underlayer film for imprint It is preferable that 90% by mass or more (more preferably 95% by mass or more, still more preferably 100% by mass) satisfies the above surface tension (hereinafter, the same applies to the physical properties of compound β).
The difference between the surface tension (γβ) of the compound β and the surface tension (γReist) of the curable composition for imprinting (γReist-γβ) is not particularly limited, but is preferably 1.0 mN / m or more, preferably 2.0 mN. It is more preferably / m or more, more preferably 3.0 mN / m or more, further preferably 5.0 mN / m or more, and even more preferably 9.0 mN / m or more. The upper limit is preferably 30.0 mN / m or less, more preferably 25.0 mN / m or less, further preferably 20.0 mN / m or less, and 15.0 mN / m or less. Is even more preferable.
The surface tension shall be a value measured by the measuring method in the examples described later.

As described in detail later, the compound β preferably has a group having a binding group with a curable composition for imprint, preferably a polymerizable group, and more preferably an ethylenically unsaturated group. As the ethylenically unsaturated group, a vinyl group, an allyl group, a phenylvinyl group, and a (meth) acryloyl group are preferable.

Compound β preferably has a hydrophobic structure.

The compound constituting the compound β is not particularly limited, and specific examples thereof include acrylates having a long-chain hydrocarbon structure (6 to 40 carbon atoms) such as lauryl (meth) acrylate, myristyl (meth) acrylate, and stearyl (meth) acrylate. , 8 to 30, more preferably 10 to 20), 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, pentafluorophenyl (meth). Fluorine-containing (meth) acrylates such as acrylates, 2,2,3,3,4,5,5-octafluoro-1,6-hexyldi (meth) acrylates (preferably 5-40 carbon atoms, 6-30 carbon atoms). Is more preferable, 8 to 20 is more preferable; the number of fluorine atoms is preferably 1 to 20, 2 to 10 is more preferable, and 2 to 8 is more preferable), HYPERTECH series (manufactured by Nissan Chemical Industries, Ltd.), Surflon. Fluorine-containing materials such as the series (manufactured by AGC Simichemical) and the Megafuck series (DIC Co., Ltd.) (preferably a fluorine-containing atomic polymer compound having the following molecular weight) and the like can be mentioned.
When the compound β is a (meth) acrylate, it may be an acrylate or a methacrylate, but an acrylate is preferable.

The compound β is preferably a compound represented by the following formula (3) or (4).

In formula (3), R ³¹ is a hydrogen atom or a methyl group. L ³¹ is a linking group L, among others O, S, NR ^N are preferred. m3 is an integer of 1-3. R ³² is an m3 valent group, a linear or branched alkane structure group (preferably 2 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, still more preferably 6 to 25 carbon atoms), a linear or branched alkene structure. Group (preferably 2 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, further preferably 6 to 25 carbon atoms), linear or branched alkyne structure group (preferably 2 to 40 carbon atoms, 4 to 30 carbon atoms more preferably). , 6 to 25 are more preferable). R ³² may have a substituent T, preferably substituted with, for example, a fluorine atom. The number of substitutions of fluorine atoms is preferably 1 to 24, more preferably 1 to 12, and even more preferably 1 to 6. When there are a plurality of substituents T, they may be bonded to each other, or may be bonded to R ³² in the formula with or without a linking group L to form a ring.

In formula (4), R ⁴¹ and R ⁴² are independently hydrogen atoms or methyl groups, respectively. m4 and m5 each independently represent an integer of 0 to 60, and an integer of 5 to 50 is preferable. However, both are never 0. m6 represents an integer of 0 to 20, with an integer of 2 to 18 being preferred. L ⁴¹ is a linking group synonymous with L ³¹ . Rf is a fluoroalkyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 10; the number of fluorine atoms is preferably 1 to 20, more preferably 1 to 10 and 1 to 8). More preferable). L ⁴² represents a linear or branched alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms) or a linear or branched alkaneylene group. R ⁴³ is a hydrogen atom, a cyclic or chain (linear or branched) alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 6), cyclic or chain (linear). Or branched) fluoroalkyl groups (preferably 1-12 carbon atoms, more preferably 1-6, even more preferably 1-3; the number of fluorine atoms is preferably 1-20, more preferably 1-10, 1-10. 8 is more preferable).

The molecular weight of the compound β is not particularly limited, but it may be a low molecular weight compound or a high molecular weight compound.
In the case of a low molecular weight compound such as an acrylic acid ester, it is preferably 5,000 or less, more preferably 3,000 or less, further preferably 1,000 or less, and further preferably 800 or less. It is preferably 500 or less, and even more preferably 500 or less. As a lower limit, it is practical that it is 100 or more.
In the case of a polymer compound such as an acrylic polymer, the weight average molecular weight is preferably 1,000 or more, more preferably 3,000 or more, and further preferably 5,000 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.

The blending amount of the compound β is not particularly limited, but is preferably 45% by mass or less, more preferably 20% by mass or less, and 15% by mass or less among the non-volatile components of the composition for forming an underlayer film for imprinting. It is even more preferably 10% by mass or less, further preferably 5% by mass or less, and even more preferably 3% by mass or less. The lower limit is not particularly determined, but for example, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, and 1% by mass. % Or more is more preferable.
The blending amount of the compound β with respect to 100 parts by mass of the compound α is preferably less than 100 parts by mass, more preferably 80 parts by mass or less, further preferably 30 parts by mass or less, and 20 parts by mass or less. It is more preferably 10 parts by mass or less, further preferably 5 parts by mass or less, further preferably 4 parts by mass or less, and particularly preferably 3 parts by mass or less. .. The lower limit is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.5 parts by mass or more, and 1 part by mass or more. Is more preferable.
As the compound β, one kind may be used or a plurality of compounds may be used. When a plurality of products are used, the total amount is preferably in the above range.
By setting the compounding amount of the compound β in the above range, the interfacial tension of not only the flow interface but also the mixed solution itself is not reduced when mixed with the curable composition for imprinting, and the capillary force is maintained high, which is sufficient. It is preferable because the filling property can be ensured.

<<< Compounds with binding groups >>>
At least one contained in a composition (nonvolatile component) consisting of components excluding a solvent for an underlayer film (a compound that is liquid at 23 ° C. and has a boiling point of 250 ° C. or less) in the composition for forming an underlayer film for imprint. Is preferably a compound having a binding group with a curable composition for imprint. In the present invention, at least one of the compound α and the compound β is preferably a compound having a binding group to the curable composition for imprint, and 90% by mass or more of the total amount of the compound α and the compound β is 90% by mass or more. It is preferably a compound having a binding group with the curable composition for imprint, and more preferably 95% by mass or more is a compound having a binding group with the curable composition for imprint, 98 mass by mass. It is more preferable that% or more is a compound having a binding group with a curable composition for imprint. The upper limit may be 100% by mass.
Examples of such a bonding group include a polymerizable group, an ethylenically unsaturated group (referring to a group containing an ethylenically unsaturated bond), an epoxy group and the like, and an ethylenically unsaturated group is preferable. Examples of the ethylenically unsaturated group include the above-mentioned ethylenically unsaturated group E. The compound having the above-mentioned binding group may contain two or more kinds of binding groups in one molecule, or may contain two or more kinds of binding groups of the same type. The compound having the binding group is preferably a compound containing 1 to 3 binding groups in one molecule, and more preferably a compound containing two binding groups.
Further, the compound having a binding group with the curable composition for imprint preferably has a molecular weight of 200 to 1000, and more preferably 200 to 900.

The compounds having a binding group used in the present invention include the compounds used in Examples described later, and the polymerizable compounds S-1 to S-22 and M-1 to described in the section on curable compositions for imprinting described later. Examples include M-29.

The compound having a binding group is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 98% by mass or more of the non-volatile component. The upper limit may be 100% by mass.
Only one kind of compound having a binding property may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.

<<< Compounds containing aromatic rings >>>
It is preferable that at least one of the non-volatile components in the composition for forming an underlayer film for imprinting is a compound containing an aromatic ring. The compound containing an aromatic ring is preferably a compound corresponding to the compound α or compound β, and more preferably a compound corresponding to the compound α is a compound containing an aromatic ring. The aromatic ring aCy is exemplified as the aromatic ring in the compound containing the aromatic ring.

<<< alkylene glycol compound >>>
The non-volatile component may contain an alkylene glycol compound. The alkylene glycol compound preferably has 3 to 1000 alkylene glycol constituent units, more preferably 4 to 500, still more preferably 5 to 100, and 5 to 100. It is more preferable to have 50 of them. The weight average molecular weight (Mw) of the alkylene glycol compound is preferably 150 to 10000, more preferably 200 to 5000, further preferably 300 to 3000, and even more preferably 300 to 1000.
The alkylene glycol compounds are polyethylene glycol, polypropylene glycol, these mono or dimethyl ethers, mono or dioctyl ethers, mono or dinonyl ethers, mono or didecyl ethers, monostearate esters, monooleic acid esters, monoadiponic acid esters, monosuccinates. Acid esters are exemplified, and polyethylene glycol and polypropylene glycol are preferable.
The surface tension of the alkylene glycol compound at 23 ° C. is preferably 38.0 mN / m or more, and more preferably 40.0 mN / m or more. The upper limit of the surface tension is not particularly specified, but is, for example, 48.0 mN / m or less. By blending such a compound, the wettability of the curable composition for imprint provided directly above the underlayer film can be further improved.

When the alkylene glycol compound is contained, it is 40% by mass or less, preferably 30% by mass or less, more preferably 20% by mass or less, and 5 to 15% by mass of the non-volatile component. More preferred.
Only one kind of alkylene glycol compound may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.

<<< Polymerization Initiator >>>
The non-volatile component may contain a polymerization initiator. Examples of the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator, but a photopolymerization initiator is preferable from the viewpoint of improving the cross-linking reactivity with the curable composition for imprinting. As the photopolymerization initiator, a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable. Further, in the present invention, a plurality of types of photopolymerization initiators may be used in combination.

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 such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP-A-2016-0273557 can be referred to, and the contents thereof are incorporated in the present specification.
Examples of the acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (trade names: all manufactured by BASF) can be used.

The content of the photopolymerization initiator used in the composition for forming an underlayer film for imprint is, for example, 0.01 to 15% by mass, preferably 0.1 to 12% of the non-volatile components when blended. It is by mass, more preferably 0.2 to 7% by mass. When two or more kinds of photopolymerization initiators are used, the total amount thereof is within the above range.

<<< Other non-volatile components >>>
In addition to the above compounds, the non-volatile components to be blended in the composition for forming an underlayer film for imprint include a thermal polymerization initiator, a polymerization inhibitor, an antioxidant, a leveling agent, a thickener, a surfactant and the like. It may contain one kind or two or more kinds.
As the thermal polymerization initiator and the like, in addition to the components described in Examples described later, each component described in JP2013-036027, JP2014-090133, and JP2013-189537 should be used. Can be done. Regarding the content and the like, the description in the above publication can be taken into consideration.
Further, in the present invention, the composition for forming an underlayer film for imprinting may be configured to be substantially free of a surfactant. The term "substantially free" means that the amount is 0.1% by mass or less of the non-volatile component in the composition for forming an underlayer film for imprinting.

<<< Viscosity (ηUL) >>>
In the composition for forming an imprint underlayer film of the present invention, the viscosity (ηUL) of the component (nonvolatile component) excluding the solvent for the underlayer film is 1000 mPa · s or less, preferably 600 mPa · s or less. , 200 mPa · s or less, more preferably 100 mPa · s or less, further preferably 50 mPa · s or less, 30 mPa · s or less, and further 15 mPa · s or less. It may be. The lower limit of the viscosity (ηUL) is 5 mPa · s or more, preferably 7 mPa · s or more, 8 mPa · s or more, and further 9 mPa · s or more.
By setting this viscosity (ηUL) in the above range, it is possible to obtain an underlayer film exhibiting appropriate wettability, which is preferable.
The viscosity of the non-volatile component of the composition for forming an underlayer film for imprinting is measured according to the method described in Examples described later.

<<< Surface tension (γUL) >>>
The surface tension (γUL) of the component (nonvolatile component) excluding the solvent for the underlayer film of the composition for forming the underlayer film for imprint is preferably 5.0 mN / m or more, and is 10.0 mN / m or more. It is more preferably 15.0 mN / m or more, further preferably 20.0 mN / m or more, and even more preferably 23.0 mN / m or more. The upper limit of the surface tension (γUL) is preferably 40.0 mN / m or less, more preferably 38.0 mN / m or less, further preferably 37.0 mN / m or less, and 36.0 mN or less. It is more preferably / m or less, and may be 30.0 mN / m or less.
The surface tension (γUL) of the non-volatile component of the composition for forming an underlayer film for imprint is preferably larger than the surface tension (γReist) of the curable composition for imprint, and the difference is more preferably within a specific range. preferable. This difference (γReist-γUL) is preferably 1.0 mN / m or more, more preferably 2.0 mN / m or more, and further preferably 3.0 mN / m or more. The upper limit is not particularly limited, but it is practical that it is 10.0 mN / m or less.
By setting the surface tension of γUL in the above range, a sufficient difference in interfacial tension with the curable composition for imprint can be sufficiently secured, and better residual film uniformity can be achieved.
The surface tension of the non-volatile component of the composition for forming an underlayer film for imprinting is measured according to the method described in Examples described later.

<< Hansen solubility parameter >>
The composition for forming an underlayer film for imprinting of the present invention comprises the Hansen solubility parameter of the maximum amount component of the component (nonvolatile component) excluding the solvent for the underlayer film and the maximum amount component of the curable composition for imprinting. The distance between the Hansen solubility parameters (values defined by the following formulas (2) and (3)) is preferably 4.5 or less, more preferably 4.3 or less, and 4.2 or less. Is even more preferable, 2.0 or less is more preferable, and 1.0 or less is even more preferable. The lower limit may be 0.
｜ ΔHSP ｜ ≦ 4.5 Formula (2)
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5 Formula (3)
ΔD: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in the variance term components of the HSP vector of
ΔP: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in polarity term component of HSP vector of
ΔH: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in hydrogen bond term component of HSP vector.
The Hansen solubility parameter of the non-volatile component of the curable composition for imprint and the composition for forming the underlayer film for imprint is set by the method shown in the examples below.

The Hansen solubility parameter (HSP) vector of the non-volatile component in the composition for forming the underlayer film for imprint:
(I) The dispersion term component (d component) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and preferably 16.0 to 18.5. More preferred;
(Ii) The polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and preferably 4.0 to 5.0. More preferred;
(Iii) The hydrogen bond term component (h component) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5. Is even more preferable.
The dispersion term component, the polar term component, and the hydrogen bond term component of the HSP vector of the non-volatile component are each set by the methods described in Examples described later.

The ratio of the components (nonvolatile components) other than the solvent for the underlayer film in the composition for forming the underlayer film for imprint is preferably 1% by mass or less, more preferably 0.5% by mass or less. It may be 0.4% by mass or less. As a lower limit value, it is practical that it is 0.01% by mass or more. The non-volatile component may contain only one kind, or may contain two or more kinds. When two or more types are contained, the total amount is preferably in the above range.

<< Solvent for Underlayer Membrane >>
The composition for forming an underlayer film for imprinting used in the present invention contains a compound (solvent for an underlayer film) which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in a proportion of 99.0% by mass or more. Usually, the non-volatile component finally forms the underlayer film. The composition for forming the underlayer film for imprint preferably contains 99.5% by mass or more of the solvent for the underlayer film, and may be 99.6% by mass or more. In the present invention, the liquid means that the viscosity at 23 ° C. is 100,000 mPa · s or less.
Only one type of solvent may be contained in the composition for forming an underlayer film for imprinting, or two or more types may be contained. When two or more kinds are contained, the total amount is preferably within the above range.
The boiling point of the solvent for the underlayer 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 130 ° C. or lower. Is even more preferable. The lower limit is 23 ° C, but it is practical that it is 60 ° C or higher. By setting the boiling point in the above range, the solvent can be easily removed from the underlayer film, which is preferable.

The solvent for the underlayer 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.

As specific examples, alkoxy alcohols, propylene glycol monoalkyl ether carboxylates, propylene glycol monoalkyl ethers, lactic acid esters, acetate esters, alkoxypropionic acid esters, chain ketones, cyclic ketones, lactones, and alkylene carbonates are selected.

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

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 is used. It is particularly preferable to have.

Further, as the propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
As the lactate ester, ethyl lactate, butyl lactate, or propyl lactate is preferable.
As the acetic acid ester, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl acetate, or 3-methoxybutyl acetate are preferable.
As the alkoxypropionic acid ester, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
Examples of chain ketones include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, and acetylacetone. Acetylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone or methyl amyl ketone are preferred.
As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferable.
As the lactone, γ-butyrolactone is preferable.
Propylene carbonate is preferred as the alkylene carbonate.

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 even more preferably 7 to 10) and having a heteroatom number of 2 or less.

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

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

Among the preferred solvents for the underlayer film, water, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate (PGMEA), ethoxyethyl propionate, cyclohexanone, 2-heptanone, γ-butyrolactone, butyl acetate, propylene At least one selected from the group consisting of glycol monomethyl ether (PGME), ethyl lactate and 4-methyl-2-pentanol, and selected from the group consisting of 1-methoxy-2-propanol, PGMEA and butyl acetate. At least one is more preferred.

A conventionally known storage container can be used as the storage container for the composition for forming the underlayer film for imprinting. In addition, as a storage container, a multi-layer bottle in which the inner wall of the container is composed of 6 kinds of 6 layers of resin, or 6 kinds of resin of 7 layers structure is used for the purpose of suppressing the mixing of impurities into raw materials and compositions. It is also preferable to use a bottle. As such a container, for example, the container described in JP-A-2015-123351 can be cited.

<Curing composition for imprint>
Next, the curable composition for imprint that can be used in the present invention will be described. The curable composition for imprint is not particularly specified, and a known curable composition for imprint can be used, and it is preferable that the curable composition for imprint contains at least a polymerizable compound.

<<<viscosity>>>
The viscosity of the curable composition for imprinting is preferably 20.0 mPa · s or less, more preferably 15.0 mPa · s or less, further preferably 11.0 mPa · s or less, 9 It is more preferably 0.0 mPa · s or less. The lower limit of the viscosity is not particularly limited, but can be, for example, 5.0 mPa · s or more. Viscosity is measured according to the method described in Examples described below.

<< Surface tension >>
The surface tension (γResist) of the curable composition for imprint is preferably 30.0 mN / m or more, and more preferably 31.0 mN / m or more. By using the curable composition for imprint having a high surface tension, the capillary force is increased, and the curable composition for imprint can be filled into the mold pattern at high speed. The upper limit of the surface tension is not particularly limited, but is preferably 40.0 mN / m or less, preferably 38.0 mN / m, from the viewpoint of imparting the relationship with the underlying film and the suitability for inkjet. It is more preferably 36.0 mN / m or less, and may be 36.0 mN / m or less. The surface tension of the curable composition for imprinting is measured according to the method described in Examples described later.

<< Onishi Parameter >>
The Onishi parameter of the curable composition for imprint is preferably 5.0 or less, more preferably 4.0 or less, and further preferably 3.7 or less. The lower limit of the Onishi parameter of the curable composition for imprint is not particularly specified, but may be, for example, 1.0 or more, and further may be 2.0 or more. The Onishi parameter is calculated by the method described in Examples described later.

<< Content rate, etc. >>
In the present invention, the content of the solvent in the curable composition for imprint is preferably 5% by mass or less, more preferably 3% by mass or less, and 1% by mass. The following is more preferable.
The curable composition for imprinting is a polymer (preferably a polymer having a weight average molecular weight of more than 1,000, more preferably a weight average molecular weight of more than 2,000, still more preferably a weight average molecular weight of 10,000 or more. ) Can be substantially not contained. The term "substantially free of polymer" means, for example, that the content of the polymer is 0.01% by mass or less of the curable composition for imprinting, preferably 0.005% by mass or less, and not at all. Is more preferable.

<< Polymerizable compound >>
The curable composition for imprint preferably contains a polymerizable compound, and the polymerizable compound contained in the curable composition for imprint is a polyfunctional polymerizable compound even if it is a monofunctional polymerizable compound. Alternatively, it may be a mixture of both. Further, at least a part of the polymerizable compound contained in the curable composition for imprint is preferably liquid at 23 ° C., and 15% by mass or more of the polymerizable compound contained in the curable composition for imprint is 23. More preferably, it is liquid at ° C.
The polymerizable compound preferably contains a ring structure, and more preferably contains an aromatic ring or an aromatic heterocycle.

<<< Monofunctional Polymerizable Compound >>>
The molecular weight of the monofunctional polymerizable compound used in the curable composition for imprint is preferably 50 or more, more preferably 100 or more, still more preferably 150 or more. The molecular weight is also preferably 1,000 or less, more preferably 800 or less, further preferably 300 or less, still more preferably 270 or less. Volatility tends to be suppressed by setting the molecular weight to the above lower limit value or more. By setting the molecular weight to the above upper limit or less, the viscosity tends to be reduced.
The boiling point of the monofunctional polymerizable compound used in the curable composition for imprinting is preferably 85 ° C. or higher, more preferably 110 ° C. or higher, and even more preferably 130 ° C. or higher. Volatility can be suppressed by setting the boiling point to the above lower limit value or more. The upper limit of the boiling point is not particularly specified, but for example, the boiling point can be 350 ° C. or lower.

The type of the polymerizable group contained in the monofunctional polymerizable compound used in the curable composition for imprint is not particularly specified, but an ethylenically unsaturated group, an epoxy group and the like are exemplified, and an ethylenically unsaturated group is preferable. Examples of the ethylenically unsaturated group include the above-mentioned example of the ethylenically unsaturated group E. Among them, the (meth) acryloyl group is preferable, and the acryloyl group is more preferable.

The type of atom constituting the monofunctional polymerizable compound used in the curable composition for imprint is not particularly specified, but it is composed only of atoms selected from carbon atom, oxygen atom, hydrogen atom and halogen atom. Is preferable, and it is more preferable that the atom is composed of only an atom selected from a carbon atom, an oxygen atom and a hydrogen atom.

A preferred first embodiment of the monofunctional polymerizable compound used in the curable composition for imprinting is a compound having a linear or branched hydrocarbon chain having 4 or more carbon atoms.
The hydrocarbon chain in the present invention represents an alkyl chain, an alkenyl chain, or an alkynyl chain, and an alkyl chain or an alkenyl chain is preferable, and an alkyl chain is more preferable.
In the present invention, the alkyl chain represents an alkyl group and an alkylene group. Similarly, the alkenyl chain represents an alkenyl group and an alkenylene group, and the alkynyl chain represents an alkynyl group and an alkynylene group. Among these, a linear or branched alkyl group or alkenyl group is more preferable, a linear or branched alkyl group is further preferable, and a linear alkyl group is further preferable.
The linear or branched hydrocarbon chain (preferably an alkyl group) has 4 or more carbon atoms, preferably 6 or more carbon atoms, more preferably 8 or more carbon atoms, further preferably 10 or more carbon atoms, and further preferably 10 or more carbon atoms. 12 or more is more preferable. The upper limit of the number of carbon atoms is not particularly specified, but may be, for example, 25 or less carbon atoms.
The straight-chain or branched hydrocarbon chain may contain an ether group (−O−), but it is preferable that the linear or branched hydrocarbon chain does not contain an ether group from the viewpoint of improving releasability.
By using a monofunctional polymerizable compound having such a hydrocarbon chain, the elastic modulus of the cured product (pattern) is reduced and the releasability is improved with a relatively small amount of addition. Further, when a monofunctional polymerizable compound having a linear or branched alkyl group is used, the interfacial energy between the mold and the cured product (pattern) can be reduced, and the releasability can be further improved.
Preferred hydrocarbon groups of the monofunctional polymerizable compound used in the curable composition for imprint include (1) to (3).
(1) A linear alkyl group having 8 or more carbon atoms (2) A branched alkyl group having 10 or more carbon atoms (3) An alicyclic, aromatic ring or aromatic ring substituted with a linear or branched alkyl group having 1 or more carbon atoms. Heterocycle

(1) Linear alkyl group having 8 or more carbon atoms The linear alkyl group having 8 or more carbon atoms is more preferably 10 or more carbon atoms, further preferably 11 or more carbon atoms, and further preferably 12 or more carbon atoms. Further, the carbon number of 20 or less is preferable, the carbon number of 18 or less is more preferable, the carbon number of 16 or less is further preferable, and the carbon number of 14 or less is further preferable.
(2) Branched alkyl group having 10 or more carbon atoms The branched alkyl group having 10 or more carbon atoms is preferably 10 to 20 carbon atoms, more preferably 10 to 16 carbon atoms, and further preferably 10 to 14 carbon atoms. 10 to 12 carbon atoms are more preferable.
(3) Alicyclic ring, aromatic ring or aromatic heterocycle substituted with a linear or branched alkyl group having 1 or more carbon atoms The linear or branched alkyl group having 1 or more carbon atoms is more composed of a linear alkyl group. preferable. The number of carbon atoms of the alkyl group is preferably 14 or less, more preferably 12 or less, and even more preferably 10 or less.
The alicyclic ring, the aromatic ring or the aromatic heterocyclic ring may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. In the case of condensed rings, the number of rings is preferably two or three. The ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. Specific examples of the ring include the above-mentioned ring Cz.

The monofunctional polymerizable compound used in the curable composition for imprint is preferably a compound in which a linear or branched hydrocarbon chain having 4 or more carbon atoms and a polymerizable group are directly bonded or via a linking group. , A compound in which any one of the groups (1) to (3) above is directly bonded to a polymerizable group is more preferable. Examples of the linking group include -O-, -C (= O)-, -CH _2- or a combination thereof. Examples of the monofunctional polymerizable compound used in the present invention include (1) a linear alkyl (meth) acrylate in which a linear alkyl group having 8 or more carbon atoms and a (meth) acryloyloxy group are directly bonded. preferable.

Ｒ¹²は、アルキル基（炭素数１〜３６が好ましく、１〜３０がより好ましく、１〜２４がさらに好ましい）、脂環（炭素数３〜２４が好ましく、３〜１２がより好ましく、３〜６がさらに好ましい）、芳香族環（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０がさらに好ましい）および芳香族複素環（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜５がさらに好ましい）から選ばれる少なくとも１種、またはそれらの組合せによる基を表す。Ｒ¹¹は水素原子またはメチル基を表す。Ｌ¹¹は単結合または上記連結基Ｌを表し、アルキレン基またはアルケニレン基が好ましい。Ｒ¹²とＬ¹¹は連結基Ｌを介してまたは介さずに結合して環を形成していてもよい。Ｒ¹²、Ｌ¹¹は上記置換基Ｔを有していてもよい。置換基Ｔは複数が結合して環を形成してもよく、Ｒ¹²と結合して、またはＬ¹¹と結合して環を形成してもよい。置換基Ｔが複数あるとき互いに同じでも異なっていてもよい。Ｒ¹²における脂環、芳香族環または芳香族複素環の好ましい範囲は、上記環Ｃｚと同様である。 The monofunctional polymerizable compound is preferably a compound represented by the following formula (I-1).

R ¹² has an alkyl group (preferably 1 to 36 carbon atoms, more preferably 1 to 30 carbon atoms, further preferably 1 to 24 carbon atoms), an alicyclic ring (preferably 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, 3 to 24 carbon atoms). 6 is more preferred), aromatic rings (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are even more preferred) and aromatic heterocycles (2-12 carbons are preferred, 2-6 are preferred). It represents a group of at least one selected from (more preferably, more preferably 2 to 5), or a combination thereof. R ¹¹ represents a hydrogen atom or a methyl group. L ¹¹ represents a single bond or the linking group L, and an alkylene group or an alkaneylene group is preferable. R ¹² and L ¹¹ may be bonded with or without the linking group L to form a ring. R ¹² and L ¹¹ may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring, or may be bonded to R ¹² or L ¹¹ to form a ring. When there are a plurality of substituents T, they may be the same or different from each other. The preferred range of the alicyclic ring, aromatic ring or aromatic heterocycle in R ¹² is the same as that of the ring Cz.

Examples of the monofunctional polymerizable compound of the first embodiment include the following groups 1 and 2. However, it goes without saying that the present invention is not limited thereto. Also, the first group is more preferable than the second group.
Group 1

Group 2

A preferred second embodiment of the monofunctional polymerizable compound used in the curable composition for imprinting is a compound having a cyclic structure. As the cyclic structure, a monocyclic ring or a fused ring having 3 to 8 membered rings is preferable. The number of rings constituting the fused ring is preferably two or three. The annular structure is more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. Also, a single ring is more preferable.
The number of cyclic structures in one molecule of the polymerizable compound may be one or two or more, but one or two is preferable, and one is more preferable. In the case of a fused ring, the fused ring is considered as one cyclic structure.

Examples of the monofunctional polymerizable compound of the second embodiment include the following compounds. However, it goes without saying that the present invention is not limited thereto.

In the present invention, a monofunctional polymerizable compound other than the above monofunctional polymerizable compound may be used as long as the gist of the present invention is not deviated, and monofunctional among the polymerizable compounds described in JP-A-2014-170949. Polymerizable compounds are exemplified and these contents are included herein.

When contained, the content of the monofunctional polymerizable compound used in the curable composition for imprint with respect to the total polymerizable compound is preferably 6% by mass or more, more preferably 8% by mass or more, still more preferably 10% by mass or more. , 12% by mass or more is more preferable. Further, the content is more preferably 60% by mass or less, and may be 55% by mass or less.
In the present invention, only one type of monofunctional polymerizable compound may be contained, or two or more types may be contained. When two or more kinds are contained, the total amount is preferably within the above range.

<<< Polyfunctional polymerizable compound >>>
The polyfunctional polymerizable compound used in the curable composition for imprint is not particularly specified, but preferably contains at least one of an alicyclic ring, an aromatic ring and an aromatic heterocycle, and the aromatic ring and the aromatic ring. More preferably, it contains at least one heterocycle. A compound containing at least one of an alicyclic ring, an aromatic ring and an aromatic heterocycle may be referred to as a ring-containing polyfunctional polymerizable compound in the following description.

The molecular weight of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is preferably 1,000 or less, more preferably 800 or less, further preferably 500 or less, still more preferably 350 or less. .. By setting the upper limit of the molecular weight to 1,000 or less, the viscosity tends to be reduced. The lower limit of the molecular weight is not particularly specified, but can be, for example, 200 or more.

The number of polymerizable groups contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprinting is 2 or more, preferably 2 to 7, more preferably 2 to 4, further preferably 2 or 3. 2 is more preferable.

The type of the polymerizable group contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is not particularly specified, but ethylenically unsaturated groups, epoxy groups and the like are exemplified, and the ethylenically unsaturated group is used. preferable. Examples of the ethylenically unsaturated group include the above-mentioned ethylenically unsaturated group E, and a (meth) acryloyl group is more preferable, and an acryloyl group is further preferable. One molecule may contain two or more kinds of polymerizable groups, or may contain two or more kinds of polymerizable groups of the same type.

The types of atoms constituting the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint are not particularly specified, but are composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms and halogen atoms. It is more preferable that the atom is composed of only an atom selected from a carbon atom, an oxygen atom and a hydrogen atom.

The ring contained in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring. In the case of condensed rings, the number of rings is preferably two or three. The ring is preferably a 3- to 8-membered ring, more preferably a 5-membered ring or a 6-membered ring, and even more preferably a 6-membered ring. Further, the ring may be an alicyclic ring, an aromatic ring or an aromatic heterocycle, but is preferably an aromatic ring or an aromatic heterocycle, and more preferably an aromatic ring. .. Specific examples of the ring include an example of the ring Cz.
The number of rings in the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint may be one or two or more, but one or two is preferable, and one is more preferable. .. In the case of a fused ring, the fused ring is considered as one.
The structure of the ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is (polymerizable group)-(single bond or divalent linking group)-(divalent group having a ring)-(single bond). Alternatively, it is preferably represented by a divalent linking group)-(polymerizable group). Here, as the linking group, an alkylene group is more preferable, and an alkylene group having 1 to 3 carbon atoms is further preferable.

Ｑは、脂環（炭素数３〜２４が好ましく、３〜１２がより好ましく、３〜６がさらに好ましい）、芳香族環（炭素数６〜２２が好ましく、６〜１８がより好ましく、６〜１０がさらに好ましい）および芳香族複素環（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜５がさらに好ましい）から選ばれる少なくとも１種を有する１＋ｑ価の基を表す。Ｒ²¹およびＲ²²はそれぞれ独立に水素原子またはメチル基を表す。Ｌ²¹およびＬ²²はそれぞれ独立に単結合または上記連結基Ｌを表す。ＱとＬ²¹またはＬ²²は連結基Ｌを介してまたは介さずに結合して環を形成していてもよい。Ｑ、Ｌ²¹およびＬ²²は上記置換基Ｔを有していてもよい。置換基Ｔは複数が結合して環を形成してもよく、Ｑと結合して、またはＬ²¹またはＬ²²と結合して環を形成してもよい。置換基Ｔが複数あるとき互いに同じでも異なっていてもよい。Ｑにおける脂環、芳香族環または芳香族複素環の好ましい範囲は、上記環Ｃｚと同様である。ｑは１〜５の整数であり、１〜３の整数が好ましく、１または２がより好ましく、１がさらに好ましい。
Ｑは、複数の脂環、複数の芳香族環、複数の芳香族複素環、脂環と芳香族環、脂環と芳香族複素環、芳香族環と芳香族複素環が連結した構造を有していてもよい。芳香族環が連結した構造としては、上記式ＡＲ−１またはＡＲ−２の構造が挙げられる。 The ring-containing polyfunctional polymerizable compound used in the curable composition for imprint is preferably represented by the following formula (I-2).

Q is an alicyclic ring (preferably 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, further preferably 3 to 6 carbon atoms), an aromatic ring (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6 to 6). It represents a 1 + q-valent group having at least one selected from (10 is more preferred) and aromatic heterocycles (2-12 carbon atoms are preferred, 2-6 are more preferred, 2-5 are even more preferred). R ²¹ and R ²² independently represent a hydrogen atom or a methyl group, respectively. L ²¹ and L ²² each independently represent a single bond or the linking group L. Q and L ²¹ or L ²² may be bonded with or without a linking group L to form a ring. Q, L ²¹ and L ²² may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring, Q may be bonded to each other, or L ²¹ or L ²² may be bonded to form a ring. When there are a plurality of substituents T, they may be the same or different from each other. The preferable range of the alicyclic ring, the aromatic ring or the aromatic heterocycle in Q is the same as that of the ring Cz. q is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
Q has a structure in which a plurality of alicyclics, a plurality of aromatic rings, a plurality of aromatic heterocycles, an alicyclic and an aromatic ring, an alicyclic and an aromatic heterocycle, and an aromatic ring and an aromatic heterocycle are linked. You may be doing it. Examples of the structure in which the aromatic rings are linked include the structure of the above formula AR-1 or AR-2.

第２群

Examples of the polyfunctional polymerizable compound used in the curable composition for imprint include the following groups 1 and 2. However, it goes without saying that the present invention is not limited to these. The first group is more preferable.
Group 1

Group 2

Ｌ³⁰は、直鎖もしくは分岐のアルカン構造の基（炭素数１〜１２が好ましく、１〜６がより好ましく、１〜３がさらに好ましい）、直鎖もしくは分岐のアルケン構造の基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３がさらに好ましい）、直鎖もしくは分岐のアルキン構造の基（炭素数２〜１２が好ましく、２〜６がより好ましく、２〜３がさらに好ましい）から選ばれる少なくとも１種を有する１＋ｒ価の基を表す。Ｒ²⁵およびＲ²⁶はそれぞれ独立に水素原子またはメチル基を表す。Ｌ²⁵およびＬ²⁶はそれぞれ独立に単結合または上記連結基Ｌを表す。Ｌ³⁰とＬ²⁵またはＬ²⁶とは連結基Ｌを介してまたは介さずに結合して環を形成していてもよい。Ｌ²⁵、Ｌ²⁶およびＬ³⁰は上記置換基Ｔを有していてもよい。置換基Ｔは複数が結合して環を形成してもよく、他の連結基と結合して環を形成してもよい。置換基Ｔが複数あるとき互いに同じでも異なっていてもよい。ｒは１〜４の整数であり、１〜３の整数が好ましく、１または２がより好ましく、１がさらに好ましい。なお、Ｌ³⁰にはヘテロ連結基（Ｏ、Ｓ、ＮＲ^N）が介在していてもよい。ヘテロ連結基が介在する数は、Ｌ³⁰の炭素数１〜６個に１つの割合であることが好ましい。 The curable composition for imprint may contain a polyfunctional polymerizable compound other than the ring-containing polyfunctional polymerizable compound. As the other polyfunctional polymerizable compound, a compound represented by the following formula (I-3) is preferable.

L ³⁰ is a linear or branched alkane structure group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), or a linear or branched alkene structure group (carbon number 2). ~ 12, preferably 2-6, more preferably 2-3), linear or branched alkyne-structured groups (preferably 2-12 carbon atoms, more preferably 2-6, further preferably 2-3. Represents a 1 + r-valent group having at least one selected from). R ²⁵ and R ²⁶ independently represent a hydrogen atom or a methyl group, respectively. L ²⁵ and L ²⁶ each independently represent a single bond or the linking group L. L ³⁰ and L ²⁵ or L ²⁶ may be bonded to each other with or without a linking group L to form a ring. L ²⁵ , L ²⁶ and L ³⁰ may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring, or may be bonded to another linking group to form a ring. When there are a plurality of substituents T, they may be the same or different from each other. r is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1. Incidentally, hetero linking groups in ^{L 30 (O, S, NR} N) may be interposed. The number of heterolinking groups intervening is preferably 1 in 1 to 6 carbon atoms of L ³⁰ .

Examples of other polyfunctional polymerizable compounds used in the curable composition for imprint include polyfunctional polymerizable compounds having no ring among the polymerizable compounds described in JP-A-2014-170949. The contents of are included herein. More specifically, for example, the following compounds are exemplified.

The polyfunctional polymerizable compound is preferably contained in an amount of 30% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, based on the total polymerizable compound in the curable composition for imprint. It is more preferably 55% by mass or more, 60% by mass or more, and further 70% by mass or more. Further, the upper limit value is preferably less than 95% by mass, more preferably 90% by mass or less, and may be 85% by mass or less.
The curable composition for imprint may contain only one type of polyfunctional polymerizable compound, or may contain two or more types. When two or more kinds are contained, the total amount is preferably within the above range.

The curable composition for imprint used in the present invention preferably contains 85% by mass or more of the composition as a polymerizable compound, more preferably 90% by mass or more of the polymerizable compound, and 93% by mass or more. More preferably, it is a polymerizable compound.

The Hansen solubility parameter (HSP) vector of the maximum amount component of the curable composition for imprint:
(I) The dispersion term component (d component) is preferably 14.0 to 20.0, more preferably 15.0 to 19.0, and preferably 16.0 to 18.5. More preferred;
(Ii) The polar term component (p component) is preferably 3.5 to 8.0, more preferably 3.8 to 6.0, and preferably 4.0 to 5.0. More preferred;
(Iii) The hydrogen bond term component (h component) is preferably 4.0 to 8.0, more preferably 4.7 to 7.0, and 5.2 to 6.5. Is even more preferable.
The dispersion term component, the polar term component, and the hydrogen bond term component of the HSP vector of the non-volatile component are each set by the methods described in Examples described later.

<< Other ingredients >>
The curable composition for imprint may contain additives other than the polymerizable compound. Other additives may include surfactants, sensitizers, mold release agents, antioxidants, polymerization inhibitors and the like.
Specific examples of the curable composition for imprint that can be used in the present invention include the compositions described in Examples described later, JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013. The compositions described in 189537 are exemplified and their contents are incorporated herein by reference. Further, the description of the above-mentioned publication can be taken into consideration for the preparation of the curable composition for imprint and the method for forming the film (pattern forming layer), and these contents are incorporated in the present specification.

A conventionally known storage container can be used as the storage container for the curable composition for imprint used in the present invention. In addition, as a storage container, a multi-layer bottle in which the inner wall of the container is composed of 6 kinds of 6 layers of resin, or 6 kinds of resin of 7 layers structure is used for the purpose of suppressing the mixing of impurities into raw materials and compositions. It is also preferable to use a bottle. As such a container, for example, the container described in JP-A-2015-123351 can be cited.

<Kit>
In the present invention, it is also preferable to prepare a kit having an imprint underlayer film forming composition and an imprint curable composition satisfying the above conditions (i) to (v). The preferable ranges of the physical properties and component compositions of the underlayer film forming composition for imprinting, the physical properties and component composition of the curable composition for imprinting, and the relationship between the two compositions are the same as described above.

<Laminate and its manufacturing method>
A preferred embodiment of the kit of the present invention is a laminate formed from this kit. The laminate of the present embodiment includes an imprint film formed from the composition for forming an imprint underlayer film and an imprint layer formed from the imprint curable composition and located on the surface of the underlayer film. It is preferable to have. The production method is not particularly limited, but a production method including applying the curable composition for imprint to the surface of the underlayer film formed from the composition for forming the underlayer film for imprint using the above kit. Can be mentioned. At this time, the curable composition for imprinting is preferably applied to the surface of the underlayer film by the inkjet method (IJ method). Further, the method for producing the laminate includes a step of applying the composition for forming an imprint underlayer film on a substrate in a layered manner, and applying the composition for forming an imprint underlayer film applied in a layered manner at 40 to 70 ° C. It is preferable to include heating at (preferably 50 to 65 ° C.).

<Cured product pattern and its manufacturing method>
The method for producing a cured product pattern according to a preferred embodiment of the present invention is a method for producing a cured product pattern using the above kit, in which a composition for forming an underlayer film for imprinting is applied onto a substrate. An underlayer film forming step for forming an underlayer film, an application step of applying a curable composition for imprinting to the surface of the underlayer film, the curable composition for imprinting, and a pattern for transferring the pattern shape. A mold contacting step of bringing the molds into contact with each other, a light irradiation step of irradiating the curable composition for imprint with light to form a cured product, and a mold separating step of separating the cured product from the mold. Has.
Hereinafter, a method for forming a cured product pattern (a method for producing a cured product pattern) will be described with reference to FIG. It goes without saying that the configuration of the present invention is not limited by the drawings.

<< Underlayer film forming process >>
In the lower layer film forming step, as shown in FIG. 5 (2), the lower layer film 2 is formed on the substrate 1. The underlayer film is preferably formed by applying the composition for forming an imprint lower layer film on a substrate in a layered manner. The underlayer film may be formed directly on the surface of the substrate 1, or may be provided with an adhesive film on the surface of the substrate 1. When an adhesive film is provided, it is preferable to provide an underlayer film on the surface of the adhesive film. As the adhesive film, for example, a film formed from the composition for forming an imprint lower layer film described in JP-A-2014-24322 can be used as the adhesive film.

The method for applying the composition for forming an underlayer film for imprinting on a substrate is not particularly specified, and a generally well-known application method can be adopted. Specifically, as the application method, 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 scan method, or an inkjet method. Is exemplified, and the spin coating method is preferable.
Further, after applying the composition for forming an imprint lower layer film on the substrate in a layered manner, the solvent is preferably volatilized (dried) by heat to form a thin film lower layer film. It is preferable to heat (bake) the composition for forming an imprint underlayer film applied in layers at 30 to 90 ° C. (preferably 40 ° C. or higher and 70 ° C. or lower). The heating time can be 30 seconds to 5 minutes.

The thickness of the underlayer film 2 is preferably 2 nm or more, more preferably 3 nm or more, further preferably 4 nm or more, 5 nm or more, or 7 nm or more. The thickness of the underlayer film is preferably 40 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, 15 nm or less, and further 10 nm or less. May be good. By setting the film thickness to the above lower limit value or more, the expandability (wetting property) of the curable composition for imprinting on the lower film is improved, and a uniform residual film can be formed after imprinting. By setting the film thickness to the above upper limit value or less, the residual film after imprinting becomes thin, uneven film thickness is less likely to occur, and the uniformity of the residual film tends to be improved.

The material of the substrate is not particularly specified, and the description in paragraph 0103 of JP2010-109092 (the publication number of the corresponding US application is US2011 / 199592) can be referred to, and these contents are incorporated in the present specification. Is done. In the present invention, a silicon substrate, a glass 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, GaP, AlGaAs, InGaN, and GaN. , AlGaN, ZnSe, AlGa, InP, or ZnO. Specific examples of the material of the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and bariumborosilicate glass. In the present invention, a silicon substrate is preferable.

<< Application process >>
In the application step, for example, as shown in FIG. 5 (3), the imprintable curable composition 3 is applied to the surface of the underlayer film 2.
The method of applying the curable composition for imprint is not particularly specified, and the description in paragraph 0102 of JP-A-2010-109092 (the publication number of the corresponding US application is US2011 / 199592) can be referred to. Is incorporated herein by reference. The curable composition for imprinting is preferably applied to the surface of the underlayer film by an inkjet method. Further, the curable composition for imprint may be applied by multiple coating. In a method of arranging droplets on the surface of the lower layer 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 lower layer film at intervals. The droplet interval is preferably 10 to 1000 μm. In the case of the inkjet method, the droplet interval is the arrangement interval of the inkjet nozzles.
Further, the volume ratio of the lower layer film 2 to the film-like curable composition for imprint 3 applied on the lower layer film is preferably 1: 1 to 500, and more preferably 1: 10 to 300. It is preferably 1:50 to 200, more preferably 1:50 to 200.
Further, the method for producing a laminate of the present invention is a method for producing a laminate using the kit of the present invention, in which the surface of the underlayer film formed from the composition for forming the underlayer film for imprint is cured for imprinting. Including applying a sex composition. Further, the method for producing a laminate of the present invention includes a step of applying the composition for forming an underlayer film for imprinting in a layered manner on a substrate, and the composition for forming an underlayer film for imprinting applied in the layered manner is 30 It is preferable to include heating (baking) at ~ 90 ° C. (preferably 40 ° C. or higher and 70 ° C. or lower). The heating time can be 30 seconds to 5 minutes.

<< Mold contact process >>
In the mold contact step, for example, as shown in FIG. 5 (4), the imprint curable composition 3 and the mold 4 having a pattern for transferring the pattern shape are brought into contact with each other. By going through such a step, a desired cured product pattern (imprint pattern) can be obtained.
Specifically, the mold 4 is pressed against the surface of the film-like curable composition for imprint 3 in order to transfer a desired pattern to the film-like curable composition for imprint.

The mold may be a light-transmitting mold or a light-impermeable mold. When a light-transmitting mold is used, it is preferable to irradiate the curable composition 3 with light from the mold side. On the other hand, when a light-impermeable mold is used, it is preferable to use a light-transmitting substrate as the substrate and irradiate light from the substrate side. In the present invention, it is more preferable to use a light-transmitting mold and irradiate light from the mold side.
The mold that can be used in the present invention is a mold having a pattern to be transferred. The pattern possessed by the mold can be formed according to a desired processing accuracy by, for example, photolithography or an electron beam drawing method, but the mold pattern manufacturing method is not particularly limited in the present invention. Further, the pattern formed by the cured product pattern manufacturing method of the present invention can also be used as a mold.
The material constituting the light-transmitting mold used in the present invention is not particularly limited, but is limited to glass, quartz, polymethylmethacrylate (PMMA), light-transmitting resin such as polycarbonate resin, transparent metal vapor-deposited film, polydimethylsiloxane, and the like. 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 the 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. It is not particularly restricted.

In the method for producing a cured product pattern, the mold pressure is preferably 10 atm or less when performing imprint lithography using a curable composition for imprinting. By setting the mold pressure to 10 atm or less, the mold and the substrate 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. The mold pressure is preferably selected from a range in which the uniformity of mold transfer can be ensured while the residual film of the curable composition for imprint corresponding to the convex portion of the mold is reduced.
It is also preferable that the contact between the curable composition for imprint and the mold is performed in an atmosphere containing helium gas or condensable gas, or both helium gas and condensable gas.

<< Light irradiation process >>
In the light irradiation step, the curable composition for imprint is irradiated with light to form a cured product. The irradiation amount of light irradiation in the light irradiation step may be sufficiently larger than the minimum irradiation amount required for curing. The irradiation amount required for curing is appropriately determined by examining the consumption amount of unsaturated bonds of the curable composition for imprinting.
The type of light to be irradiated is not particularly specified, but ultraviolet light is exemplified.
Further, in the imprint lithography applied to the present invention, the substrate temperature at the time of light irradiation is usually room temperature, but light irradiation may be performed while heating in order to enhance the reactivity. If a vacuum state is used as a pre-stage of light irradiation, it is effective in preventing air bubbles from being mixed in, suppressing a decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for imprinting. You may irradiate with light. Further, in the above-mentioned method for producing a cured product pattern, the preferable degree of vacuum at the time of light irradiation is in the range of 10 ^-1 Pa to normal pressure.
In photoexposure, the light intensity is preferably in the range of 1 to 500 mW / cm ^2, and more preferably in the range of 10~400mW / 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 to 500 mJ / cm ^2.
In the above-mentioned method for producing a cured product pattern, a film-like curable composition for imprinting (pattern forming layer) is cured by light irradiation, and then, if necessary, heat is applied to the cured pattern to further cure it. It may include steps. The temperature for heat-curing the curable composition for imprinting after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C. The time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.

<< Mold release process >>
In the mold release step, the cured product and the mold are separated from each other (FIG. 5 (5)). The obtained cured product pattern can be used for various purposes as described later.
That is, the present invention discloses a laminate having a cured product pattern formed from the curable composition for imprinting on the surface of the underlayer film. The film thickness of the pattern forming layer made of the curable composition for imprint used in the present invention varies depending on the intended use, but is about 0.01 μm to 30 μm.
Further, as described later, etching or the like can be performed.

<Cured product pattern and its application>
As described above, the cured product pattern formed by the above-mentioned cured product pattern manufacturing method is used as a permanent film used in a liquid crystal display (LCD) or the like, or as an etching resist (lithography mask) for manufacturing a semiconductor element. Can be done.
In particular, the present invention discloses a method for manufacturing a circuit board, which includes a step of obtaining a cured product pattern by the method for producing a cured product pattern of the present invention. Further, the circuit board manufacturing method of the present invention includes a step of etching or ion-implanting the substrate using the cured product pattern obtained by the above-mentioned cured product pattern manufacturing method as a mask, and a step of forming an electronic member. You may be doing it. The circuit board is preferably a semiconductor element. Further, the present invention discloses a method for manufacturing an electronic device having a step of obtaining a circuit board by the method for manufacturing a circuit board and a step of connecting the circuit board and a control mechanism for controlling the circuit board.
Further, a grid pattern is formed on the glass substrate of the liquid crystal display device by using the pattern formed by the above-mentioned cured product pattern manufacturing method, and there is little reflection or absorption, and a large screen size (for example, 55 inches, more than 60 inches) polarization. It is possible to manufacture the plate at low cost. For example, the polarizing plates described in JP-A-2015-132825 and WO2011 / 132649 can be manufactured. In addition, 1 inch is 25.4 mm.
As shown in FIGS. 5 (6) and 5 (7), the cured product pattern formed in the present invention is also useful as an etching resist (mask for lithography). When the cured product pattern is used as an etching resist, first, a silicon substrate (silicon wafer or the like) on which a thin film such as SiO ₂ is formed is used as the substrate, and the cured product pattern manufacturing method is used on the substrate, for example. Form a fine cured product pattern on the order of nano or micron. The present invention is particularly advantageous in that a nano-order fine pattern 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 above-mentioned cured product pattern manufacturing method is not particularly specified, but can be, for example, 1 nm or more.
Further, the present invention includes a step of obtaining a cured product pattern on a substrate by the method for producing a cured product pattern of the present invention, and a step of etching the substrate using the obtained cured product pattern. A method for manufacturing an imprint mold is also disclosed.
A desired cured product pattern can be formed on the substrate by etching with an etching gas such as hydrogen fluoride in the case of wet etching and CF _{4 in} the case of dry etching. The cured product pattern has particularly good etching resistance to dry etching. That is, the pattern formed by the cured product pattern manufacturing method is preferably used as a mask for lithography.

Specifically, the pattern formed in the present invention includes a recording medium such as a magnetic disk, a light receiving element such as a solid-state imaging element, a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence), and a liquid crystal display. Optical devices such as liquid crystal displays, diffraction grids, relief holograms, optical waveguides, optical filters, optical components such as microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizing plates, polarizing elements, optical films, Flat panel display members such as pillars, nanobiodevices, immunoanalytical chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, and fine pattern formation (directed self-assembly) using self-assembly of block copolymers, It can be preferably used for producing a guide pattern or the like for DSA).

Hereinafter, the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Examples 1-11, Comparative Examples 1-5
<Preparation of composition for forming underlayer film>
Each compound shown in Table 1 or Table 2 (nonvolatile components: A-1 to A-9, B-1 to B-2, solvent C-1 to C-3) is blended, and a poly having a pore size of 0.1 μm is blended. Two-stage filtration was carried out using a tetrafluoroethylene (PTFE) filter and a PTFE filter having a pore size of 0.003 μm to prepare a composition for forming an underlayer film for imprint shown in Examples and Comparative Examples.

<Preparation of curable composition for imprint>
The compounds shown in Table 3 are mixed with various compounds having structural formulas, and 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxylfree radical (manufactured by Tokyo Kasei) is added as a polymerization inhibitor. Of these, 200 mass ppm (0.02 mass%) was added to the total amount of the polymerizable compound. This was 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 prepare a curable composition for imprinting.

<Measurement of surface tension>
The surface tension of each composition or compound was measured at 23 ° C. using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Surface Science Co., Ltd. and a glass plate. The unit is expressed in mN / m. Regarding the surface tension (γUL) of the non-volatile component of the composition for forming an underlayer film for imprinting, the surface tension was measured with a composition in which a component other than the solvent was mixed. Two samples were prepared for each level and measured three times each. The arithmetic mean value of a total of 6 times was adopted as the evaluation value. When the compound was a solid, the surface tension of the solution adjusted to a concentration of 1% by mass in PGMEA at 23 ° C. was defined as the surface tension of the compound. If it is insoluble in PGMEA at 23 ° C. at a concentration of 1% by mass, a solvent having a surface tension of 30 mN / m or more may be selected. Specifically, when cyclohexanone and cyclohexane are insoluble, γ-butyrolactone is used, and when γ-butyrolactone is also insoluble, ethyl lactate and ethyl lactate are insoluble, ethylene glycol is used.

<Measurement of viscosity>
The viscosity was measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotational viscometer RE85L manufactured by Toki Sangyo Co., Ltd. and a standard cone rotor (1 ° 34'x R24). The unit is mPa · s. Regarding the viscosity (ηUL) of the non-volatile component of the composition for forming an underlayer film for imprinting, the viscosity was measured with a composition in which components other than the solvent were mixed. Other details regarding the measurements were in accordance with JISZ8803: 2011. Two samples were prepared for each level and measured three times each. The arithmetic mean value of a total of 6 times was adopted as the evaluation value.

<Calculation of distance between Hansen solubility parameters (ΔHSP)>
The Hansen solubility parameter was calculated with the HSP calculation software HSPiP.
By inputting the structural formula of each compound into the above software in the SMILES format, each component (ΔD, ΔP, ΔH) of the Hansen solubility parameter vector was calculated. The distance between Hansen solubility parameters (ΔHSP) was calculated by applying the calculated Hansen solubility parameter to the following formula.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5
The Hansen solubility parameter vector of the component of the curable composition for imprint and the non-volatile component of the composition for forming the underlayer film for imprint is calculated for the compound having the largest amount (maximum amount component) contained in each composition. The value was adopted (when the compounding amount was the same, the calculated value of the compound having a high surface tension was adopted).

<Onishi parameters>
The non-volatile components of the curable composition for imprint were obtained by substituting the numbers of carbon atoms, hydrogen atoms and oxygen atoms of all the components into the following formulas.
Onishi Parameter = Sum of the number of carbon atoms, hydrogen atoms and oxygen atoms / (number of carbon atoms-number of oxygen atoms)

<Formation of adhesion layer and underlayer film / film thickness stability>
The composition for forming an adhesive layer shown in Example 6 of JP-A-2014-24322 is spin-coated on a silicon wafer and heated for 1 minute using a hot plate at 220 ° C. to form an adhesive layer having a thickness of 5 nm. did. Next, the composition for forming an imprint underlayer film shown in Table 1 or Table 2 is spin-coated on the surface of the adhesion layer, and heated using a hot plate under the baking conditions shown in Table 1 or Table 2, and the adhesion layer is formed. An underlayer film was formed on top. The film thickness (FT1) of the underlayer film was measured by an ellipsometer and an atomic force microscope.
Further, the wafer on which the underlayer film was formed was left at room temperature for 60 hours, and the film thickness (FT2) was measured again to confirm the film thickness difference (ΔFT = | FT1-FT2 |) from that immediately after coating.
A: ΔFT ≤ 0.5 nm
B: 0.5 nm <ΔFT ≤ 1.0 nm
C: ΔFT> 1.0 nm
D: Not measurable (no thin film formed after 60 hours)

<Evaluation of wettability of IJ (injection) droplets>
On the surface of the underlayer film obtained above, a curable composition for imprint V1 to V3 shown in Table 3 whose temperature was adjusted to 23 ° C. was applied to an inkjet made by Fujifilm Dimatics. Using a printer DMP-2831, the droplets were discharged at a droplet amount of 6 pL per nozzle, and the droplets were applied to the surface of the underlayer film in a square arrangement at intervals of about 880 μm. The shape of the droplet 3 seconds after the application was photographed, and the diameter of the droplet was measured. Two samples were used per level, and each was measured three times. The arithmetic mean value of a total of 6 times was adopted as the evaluation value.
A: Average diameter of IJ droplets> 500 μm
B: 400 μm <Average diameter of IJ droplets ≤ 500 μm
C: 320 μm <Average diameter of IJ droplets ≤ 400 μm
D: Average diameter of IJ droplets ≤ 320 μm

<Evaluation of residual film uniformity>
On the surface of the underlayer film obtained above, any of the curable compositions V1 to V3 for imprint whose temperature was adjusted to 23 ° C. was applied to 6 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics. The droplets were ejected in a droplet amount, and the droplets were applied onto the lower film so as to form a square arrangement at intervals of about 100 μm to form a pattern forming layer. Next, a quartz mold (a line pattern having a line width of 20 nm and a depth of 50 nm) was pressed against the pattern forming layer under a He atmosphere (replacement rate of 90% or more), and the curable composition for imprint was filled in the mold. When 10 seconds had passed after the stamping, the mold was exposed from the mold side using a high-pressure mercury lamp under the condition of 300 mJ / cm ² , and then the mold was peeled off to transfer the pattern to the pattern forming layer.
After that, with respect to the pattern forming layer portion, a part between the layers between the substrate and the adhesion layer is peeled off with a marking stick to deposit the silicon wafer surface, and the imprint residual film (the film thickness between the pattern bottom portion and the substrate surface) is removed. It was measured with an atomic force microscope (AFM). 30 points were measured in the same shot, and 3σ of the total thickness (residual film) of the adhesive film, the lower layer film, and the pattern bottom was calculated.
A: 3σ ≤ 1.5
B: 1.5 <3σ≤3.0
C: 3.0 <3σ≤5.0
D: 3σ> 5.0

<Evaluation of resolution>
On the surface of the underlayer film obtained above, any of the curable compositions V1 to V3 for imprint whose temperature was adjusted to 25 ° C. was applied to 6 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics. The droplets were ejected in a droplet amount, and the droplets were applied onto the lower film so as to form a square arrangement at intervals of about 100 μm to form a pattern forming layer. Next, a quartz mold (a line pattern having a line width of 28 nm and a depth of 60 nm) was pressed against the pattern forming layer under a He atmosphere (replacement rate of 90% or more), and the curable composition for imprint was filled in the mold. When 10 seconds had passed after the stamping, the mold was exposed from the mold side using a high-pressure mercury lamp under the condition of 150 mJ / cm ² , and then the mold was peeled off to transfer the pattern to the pattern forming layer. The presence or absence of pattern shape collapse of the transferred pattern was confirmed by observation with a scanning electron microscope (SEM).
A: No pattern collapse or rough pattern edge was confirmed.
B: There was no pattern collapse, but pattern edge roughness was confirmed.
C: Collapse was confirmed in a part of the pattern transfer region.
D: Collapse was confirmed over the entire pattern transfer region.

<Evaluation of filling property>
On the surface of the underlayer film obtained above, the curable composition for imprint shown in Table 3 whose temperature was adjusted to 23 ° C. was applied to a liquid of 1 pL per nozzle using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics. The droplets were discharged in a droplet amount and applied to the surface of the underlayer film so that the droplets were arranged in a square at intervals of about 100 μm to form a layered curable composition for imprinting. Next, a quartz substrate was pressed against the pattern forming layer to flatten the curable composition for imprinting. Further, after exposure from the mold side using a high-pressure mercury lamp under the condition of 300 mJ / cm ² , a flat film was obtained by peeling off the quartz substrate.
The surface of the flat film was observed using an optical microscope (STM6-LM manufactured by Olympus), and the filling property was evaluated according to the following criteria.
A: In the imprint area, no unfilled region (region in which no cured product of the curable composition for imprint exists) was generated.
B: Unfilling at the boundary of the inkjet droplet was confirmed in a part of the imprint area.
C: Unfilling at the boundary of the inkjet droplet was confirmed over the entire surface of the imprint area.
D: It was confirmed that the inkjet droplets were not connected to each other and a flat film could not be formed.

<Evaluation of etching resistance>
On the surface of the underlayer film obtained above, a curable composition for imprint whose temperature was adjusted to 23 ° C. was applied to the surface of the underlayer film by using an inkjet printer DMP-2831 manufactured by Fujifilm Dimatics with a droplet amount of 6 pL per nozzle. The droplets were discharged and applied to the surface of the underlayer film so that the droplets were arranged in a square at intervals of about 100 μm, and the curable composition for imprint was layered. Next, a quartz substrate (without a pattern) was pressed against the layered curable composition for imprinting in a helium atmosphere (substitution rate of 90% by volume or more). When 10 seconds have passed after imprinting, the mold is exposed from the mold side using a high-pressure mercury lamp under the condition of 300 mJ / cm ² , and then the mold is peeled off to form a thin film (film thickness of about 300 nm) of the curable composition for imprinting. ) Was obtained.
The above sample was introduced into an etching apparatus (Centura-DPS manufactured by Applied Materials), and etching was performed under the following conditions.
The surface state of the thin film after etching was observed with a non-contact interference microscope.
A: There was no uneven film thickness, and the entire surface was uniformly etched.
B: The IJ droplet boundary in a part of the region was excessively etched, causing uneven film thickness.
C: The IJ droplet boundary was excessively etched over the entire surface, causing uneven film thickness.

About the description in Table 1 or Table 2:
The blending amount of A-1 to A-12, B-1 and B-2 is by mass.
The viscosities are all measured values at 23 ° C. and the unit is mPa · s.
The surface tensions are all measured values at 23 ° C. and the unit is mN / m.
γUL is the surface tension (mN / m) in the composition of the components excluding the solvent (C-1 to C-3) in the composition for forming the underlayer film for imprint.
γResit is the surface tension of the curable composition for imprinting.
The d component, the p component, and the h component represent the dispersion term component D, the polar term component P, and the hydrogen bond term component H of the HSP vector, respectively.
The viscosity ηUL of the non-volatile component of the composition for forming an underlayer film for imprint is the viscosity (mPa · s) of the component excluding the solvent (C-1 to C-3) in the composition.

Ａ−８：ＨＹＰＥＲＴＥＣＨ ＦＡ−Ｅ−５０（日産化学工業株式会社）（Ｍｗ：８，０００）
含フッ素ポリマー表面改質剤（Fluoro Polymeric Surface Modifier）
Ａ−９：メガファック Ｆ−５５６（ＤＩＣ株式会社）

A-8: HYPERTECH FA-E-50 (Nissan Chemical Industries, Ltd.) (Mw: 8,000)
Fluoro Polymeric Surface Modifier
A-9: Mega Fvck F-556 (DIC Corporation)

Ａ−１０

Ａ−１１

Ａ−１２

A-10

A-11

A-12

Polymerization initiator

Solvent for underlayer film C-1: 1-methoxy-2-propanol (boiling point: 120 ° C)
C-2: Propylene glycol monomethyl ether acetate (boiling point: 146 ° C)
C-3: Butyl acetate (boiling point: 126 ° C)

About the description in Table 3:
The boiling points are all measured values at 1 atm (1 atm = 1013.25 hPa), and the unit is ° C.
The blending amount of each compound is parts by mass.
The d component, the p component, and the h component represent the dispersion term component D, the polar term component P, and the hydrogen bond term component H of the HSP vector, respectively.

As is clear from the above results, it can be seen that the composition for forming an underlayer film for imprint of the present invention has improved wettability with respect to the curable composition for imprint and exhibits excellent filling property (Examples 1 to 17). ). In particular, when the compounding ratio of the compound α and the compound β is within a specific range, it can be seen that the characteristics are further enhanced (Examples 1 to 6, 8 and 9). On the other hand, those that did not satisfy the conditions (i) to (v) such as the blending of the compounds α and β specified in the present invention were inferior in wettability and filling property (Comparative Examples 1 to 6). Further, according to the composition for forming an underlayer film for imprint according to a preferred embodiment of the present invention, the film thickness stability and the uniformity of the residual film are excellent, and the resolution and processing resistance required for processing are improved. It can be seen that good performance can be obtained (Examples 1 to 17).

1 Substrate 2 Underlayer film 3 Imprint curable composition 4 Mold 21 Underlayer film 22 Imprint curable composition 22a, 22b, 22c Membrane-like curable composition for imprint 23 Thin or no film Area 31 Nozzle 32 Droplets (at the time of ejection)
33 droplets (after landing)
33a Droplets mixed with the underlayer film component 33b Droplet flow tip 34 Substrate 35 Underlayer film 36 Droplet wetting and spreading direction 39 Compound β

Claims (26)

A composition for forming an underlayer film for imprint, which comprises compound α, compound β, and a compound that is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower.
The total content of compound α contained in the composition for forming an underlayer film for imprint is larger than the total content of compound β.
The content of the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower is 99.0% by mass or more of the composition for forming an underlayer film for imprinting.
The composition for forming an underlayer film for imprint has a viscosity at 23 ° C. of 5 to 1000 mPa · s, which is composed of a component excluding a compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower.
The content of the compound α is 50% by mass or more in the non-volatile component of the composition for forming an underlayer film for imprinting.
The content of the compound β is 0.01% by mass or more in the non-volatile component of the composition for forming an underlayer film for imprinting.
The difference (γTest-γβ) between the surface tension (γβ) of the compound β and the surface tension (γReist) of the curable composition for imprinting is 1.0 mN / m or more.
The compound β is a compound having a polymerizable group.
A composition for forming an imprint lower layer film, which is used for the lower layer film of an imprint curable composition having a higher surface tension than the compound β and a lower surface tension than the compound α. The content of the compound α is 60% by mass or more in the non-volatile component of the composition for forming an underlayer film for imprint, and the content of the compound β is 0 in the non-volatile component of the composition for forming an underlayer film for imprint. .1 mass% or more, and the difference (γReist-γβ) between the surface tension (γβ) of the compound β and the surface tension (γReist) of the curable composition for imprint is 3.0 mN / m or more. The composition for forming an underlayer film for imprint according to 1. The surface tension of the curable composition for imprint is larger than the surface tension of the composition composed of the components excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in the composition for forming an underlayer film for imprint. , The composition for forming an underlayer film for imprint according to claim 1 or 2 . The surface tension of the composition comprising components boiling a liquid at 23 ° C. is excluding compounds of 250 ° C. or less of the imprint underlayer film forming composition, or less 38.0mN / m, according to claim 3 The composition for forming an underlayer film for imprint according to. The maximum amount component of the curable composition for imprint and the maximum amount component of the composition excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. The composition for forming an underlayer film for imprint according to any one of claims 1 to 4 , wherein the distance between Hansen solubility parameters | ΔHSP | is 4.5 or less.
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5
ΔD: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in the variance term components of the HSP vector of
ΔP: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in polarity term component of HSP vector of
ΔH: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in hydrogen bond term component of HSP vector. The composition for forming an underlayer film for imprint according to any one of claims 1 to 5 , wherein the compound β contains a compound having a surface tension of 38.0 mN / m or less. The claim that the total content of the compound β is 45% by mass or less of the composition comprising the composition excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in the composition for forming an underlayer film for imprinting. The composition for forming an underlayer film for imprint according to any one of 1 to 6 . At least one of the composition for forming an underlayer film for imprint, which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower excluding the compound, is bonded to the curable composition for imprint. The composition for forming an underlayer film for imprint according to any one of claims 1 to 7 , which is a compound having a sex group. Claimed that at least one contained in the composition consisting of the components excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in the composition for forming an underlayer film for imprint is a compound containing an aromatic ring. Item 8. The composition for forming an underlayer film for imprint according to any one of Items 1 to 8 . The composition for forming an underlayer film for imprint according to any one of claims 1 to 9 , wherein the composition for forming an underlayer film for imprint contains a photopolymerization initiator. A kit having a composition for forming an underlayer film for imprint and a curable composition for imprint, which comprises compound α, compound β, and a compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower. ,
The total content of compound α contained in the composition for forming an underlayer film for imprint is larger than the total content of compound β.
The content of the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower is 99.0% by mass or more of the composition for forming an underlayer film for imprinting.
The composition for forming an underlayer film for imprint has a viscosity at 23 ° C. of 5 to 1000 mPa · s, which is composed of a component excluding a compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower.
The content of the compound α is 50% by mass or more in the non-volatile component of the composition for forming an underlayer film for imprinting.
The content of the compound β is 0.01% by mass or more in the non-volatile component of the composition for forming an underlayer film for imprinting.
The difference (γTest-γβ) between the surface tension (γβ) of the compound β and the surface tension (γReist) of the curable composition for imprinting is 1.0 mN / m or more.
The compound β is a compound having a polymerizable group.
The curable composition for imprint is a kit having a higher surface tension than the compound β and a lower surface tension than the compound α. The content of the compound α is 60% by mass or more in the non-volatile component of the composition for forming an underlayer film for imprint, and the content of the compound β is 0 in the non-volatile component of the composition for forming an underlayer film for imprint. .1 mass% or more, and the difference (γReist-γβ) between the surface tension (γβ) of the compound β and the surface tension (γReist) of the curable composition for imprint is 3.0 mN / m or more. The kit according to 11. The surface tension of the curable composition for imprint is larger than the surface tension of the composition composed of the components excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in the composition for forming an underlayer film for imprint. , The kit according to claim 11 or 12 . The surface tension of the composition comprising components boiling a liquid at 23 ° C. is excluding compounds of 250 ° C. or less of the imprint underlayer film forming composition, or less 38.0mN / m, according to claim 11 Or the kit according to 12 . The maximum amount component of the curable composition for imprint and the maximum amount component of the composition excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. The kit according to any one of claims 11 to 14 , wherein the distance between Hansen solubility parameters | ΔHSP | is 4.5 or less;
ΔHSP = (4.0 × ΔD ² + ΔP ² + ΔH ² ) ^0.5
ΔD: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in the variance term components of the HSP vector of
ΔP: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in polarity term component of HSP vector of
ΔH: Maximum amount component of the composition consisting of the maximum amount component of the curable composition for imprint and the component excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. Difference in hydrogen bond term component of HSP vector. The kit according to any one of claims 11 to 15 , wherein the compound β contains a compound having a surface tension of 38.0 mN / m or less. Claim that the total content of the compound β is 45% by mass or less of the composition comprising the composition excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less in the composition for forming an underlayer film for imprinting. The kit according to any one of 11 to 16 . At least one of the composition for forming an underlayer film for imprint, which is liquid at 23 ° C and excludes a compound having a boiling point of 250 ° C or less, is bonded to the curable composition for imprint. The kit according to any one of claims 11 to 17 , which is a compound having a sex group. Claimed that at least one contained in the composition consisting of the components excluding the compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or lower in the composition for forming an underlayer film for imprint is a compound containing an aromatic ring. Item 2. The kit according to any one of Items 11 to 18 . The kit according to any one of claims 11 to 19 , wherein the composition for forming an underlayer film for imprint contains a photopolymerization initiator. A laminate formed from the kit of any one of claims 11 to 20,
A laminate having an imprint film formed from the composition for forming an imprint underlayer film and an imprint layer formed from the curable composition for imprinting and located on the surface of the underlayer film. A method of producing a laminate by using a kit according to any one of claims 11 to 20, the surface of the underlayer film formed from the imprint underlayer film forming composition, for imprints A method for producing a laminate, which comprises applying a curable composition. The method for producing a laminate according to claim 22 , wherein the curable composition for imprint is applied to the surface of the underlayer film by an inkjet method. Furthermore, the step of applying the composition for forming an imprint lower layer film on a substrate in a layered manner is included, and the step of applying the composition for forming an imprint lower layer film applied in a layered manner is heated at 40 to 70 ° C. The method for producing a laminate according to claim 22 or 23 . A method of producing a cured product pattern using a kit according to any one of claims 11 to 20, on a substrate, forming a lower layer by applying the imprint underlayer film forming composition A lower layer film forming step, an application step of applying a curable composition for imprinting to the surface of the lower layer film, the curable composition for imprinting, and a mold having a pattern for transferring the pattern shape. A cured product pattern having a mold contacting step of contacting, a light irradiation step of irradiating the curable composition for imprinting with light to form a cured product, and a mold separating step of separating the cured product from the mold. Manufacturing method. A method for manufacturing a circuit board, which comprises a step of obtaining a cured product pattern by the manufacturing method according to claim 25 .

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