WO2019189556A1 - Fluorinated monomer, fluorinated polymer, curable composition, and production method for pattern - Google Patents

Abstract

The present invention provides a curable composition that is suitable for performing imprinting and has a high filling rate into a micro-mold in imprinting technology. The curable composition according to the present invention contains a polymerization initiator and a fluorinated monomer represented by formula (1) (R¹ and R² each independently represent a hydrogen atom or a methyl group). The fluorinated monomer represented by formula (1) can be used to form a homopolymer, or can be mixed with another polymerizable monomer to form a copolymer. Therefore, as the polymerizable monomer contained in the curable composition, the fluorinated monomer may be used alone, or a mixture of various polymerizable monomers can also be used.

Description

Fluorine-containing monomer, fluorine-containing polymer, curable composition, and pattern production method

The present invention relates to a novel fluorine-containing monomer, a fluorine-containing polymer polymerized or copolymerized using the fluorine-containing monomer, and a curable composition containing a polymerization initiator and the fluorine-containing monomer. About. In particular, the present invention relates to an imprint that forms a pattern using the curable composition.

Imprinting is one of the fine processing methods required for manufacturing semiconductor integrated circuits. Imprint is a state in which a mold having a fine concavo-convex pattern is pressed against a curable composition applied to a substrate, the curable composition is cured by light, heat, etc. This is a method for producing “a member in which a cured film having a fine concavo-convex pattern shape is arranged on a substrate” by transferring to the curable composition. Currently, active research is being conducted on curable compositions used in imprinting.

In imprinting, the formation of a nano-sized (1 nm or more and 100 nm or less) uneven pattern is particularly called nanoimprinting.

For example, Patent Document 1 discloses a photocurable composition suitable for optical nanoimprint technology and a pattern forming method using the same. That is, it is stated that when a specific compound among monomers having a plurality of acryloyl groups is used as the polymerizable compound constituting the photocurable composition, an excellent fine pattern can be formed by nanoimprinting. Specifically, among radically polymerizable compounds having a plurality of acryloyl groups in the molecule, for example, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,10-decanediol diacrylate, trimethylolpropane triacrylate. It is said that acrylate can be suitably used as one component of the polymerizable compound for the application. When they are in contact with the mold, they can be polymerized to form a cured film having a high strength by irradiation with ultraviolet light, and have good mold release properties in the subsequent mold release process. It is disclosed that an excellent fine pattern can be formed through an etching process.

Patent Document 2 specifies the number of particles having a particle size of 0.07 μm or more that are present in a liquid material for nanoimprinting (typically, the curable composition for pattern formation disclosed in Patent Document 1). It is disclosed that, when the number is less than the number, damage and defects of the pattern are significantly suppressed in nanoimprinting, and a decrease in the yield of the nanoimprinting process can be significantly suppressed.

On the other hand, Non-Patent Document 1 describes nano-imprint technology in general, and in particular, in nano-imprint, the filling rate of a curable composition into a mold in a mold contact process (cured in a fine uneven portion of the mold). It is described that there is a strong demand for an improvement in the rate at which the composition is filled.

Japanese Unexamined Patent Publication No. 2016-162862 JP 2016-164977 A

The “curable composition containing a radically polymerizable compound having a plurality of acryloyl groups (acrylic sites) in one molecule” disclosed in Patent Documents 1 and 2 is excellent as a nanoimprint material. By using it, in a nanoimprint, a fine uneven | corrugated pattern can be produced, suppressing a defect.

On the other hand, in the nanoimprint technology, “the filling speed of the curable composition into the mold” is also an important factor. In other words, in order to successfully transfer the uneven pattern of the mold onto the film of the curable composition, it is necessary to perform curing after the curable composition is filled in the fine uneven portions of the mold without any gaps. In addition, the time required for filling can greatly affect the working efficiency during nanoimprinting.

In that respect, in the above-mentioned Patent Document 1, it is pointed out that “viscosity of the photocurable composition excluding the solvent” is related to the filling speed of the uneven portion of the mold, and the “photocurable composition excluding the solvent” It is stated that optical nanoimprinting can be carried out with high productivity by setting the “viscosity of the product” to 100 mPa · s or less.

In Patent Document 1 and Patent Document 2, neopentyl glycol diacrylate shown below is particularly preferably used.

However, the “viscosity of the cured composition” is only one of the factors that determine the “filling rate into the mold”. Specifically, in nanoimprint, it is known that the filling speed is proportional to the reciprocal of the number of capillaries (Ca) (Non-patent Document 1).

An object of the present invention is to provide an imprint material having a small capillary number (Ca).

Regarding neopentyl glycol diacrylate, which is particularly preferably used in Patent Document 1 and Patent Document 2, when the present inventors measured the number of capillaries (Ca), the result was 1.57 V [L / h ₀ ] ^2. Although it is an excellent material, it has been found that there is still room for improvement in terms of filling speed into the mold (see Comparative Example 1 in this specification).
The number of capillaries (Ca) is derived from the following formula (i).

(Ca: number of capillaries, γ: surface tension, θ ₁ : mold contact angle, θ ₂ : substrate contact angle, μ: viscosity, V: mold lowering speed, L and h ₀ : apparatus constants depending on the imprint apparatus. )

As equation (i) shows, the capillary number (Ca) is proportional to the viscosity (μ) and inversely proportional to the surface tension (γ). Mold contact angle (θ ₁ ) and substrate contact angle (θ ₂ ) are also important factors. As the number of capillaries (Ca) decreases, the filling rate increases.

In view of the above circumstances, the inventors have conducted intensive studies. As a result, it has been found that the above problem can be solved by a curable composition containing a fluorine-containing monomer represented by the formula (1) and a polymerization initiator.

(R ¹ and R ² are each independently a hydrogen atom or a methyl group.)

As shown in Example 1 of the present specification, the fluorine-containing monomer has the same basic skeleton as that of the neopentyl glycol diacrylate, and a trifluoromethyl group (— The main difference is that two CF ₃ ) are introduced. The number of capillaries (Ca) of the fluorine-containing monomer represented by the formula (1) was found to be significantly smaller than that of neopentyl diacrylate, and the filling rate of the mold irregularities was significantly high.

The reason for this is not necessarily clear, but in the comparative material neopentyl glycol diacrylate, there are two methyl group side chains in the center of the molecular skeleton, but the fluorine-containing monomer of the present invention is near the center of the molecular skeleton. Since two trifluoromethyl group (—CF ₃ ) side chains are introduced, it is presumed to be based on the specific action of the fluorine atom of the trifluoromethyl group.

Since the value of the number of capillaries (Ca) varies depending on the composition, if a monomer other than the fluorine-containing monomer of formula (1) is mixed as the curable composition for imprint, It is possible to finely adjust the “Ca value of the entire composition”.

In addition, the fluorine-containing monomer represented by the formula (1) can be efficiently obtained by using a diol represented by the formula (2) which is easily available as a starting material and subjecting it to (meth) acrylation. Can be manufactured (described later).

Furthermore, the present inventor uses a curable composition containing the fluorine-containing monomer as a component, and a method for producing a “member having a cured film having a pattern shape on a substrate” (hereinafter referred to as a pattern forming method). Found).

That is, the present invention includes the following inventions.

[Invention 1]
A fluorine-containing monomer represented by the following formula (1).

(R ¹ and R ² are each independently a hydrogen atom or a methyl group.)

[Invention 2]
A curable composition comprising the fluorine-containing monomer of Invention 1 and a polymerization initiator.

[Invention 3]
The curable composition according to Invention 2, wherein the polymerization initiator is a photopolymerization initiator.

[Invention 4]
The manufacturing method of the member with a pattern which arranged the cured film which has a pattern shape on a board | substrate including the following each process.
Arrangement step: a step of arranging the curable composition of Invention 2 or Invention 3 on a substrate.
Mold contact step: a step of bringing a mold having a pattern shape into contact with the curable composition disposed on the substrate.
Curing step: a step of curing the curable composition in contact with the mold with light or heat to form a cured film.
Mold release step: a step of separating the mold from the cured film to obtain the patterned member.

[Invention 5]
The manufacturing method of the member with a pattern of the invention 4 with which the said type | mold contact process is performed in the gas atmosphere containing a condensable gas.

[Invention 6]
The condensable gas in the mold contact step is 1,1,1,3,3-pentafluoropropane (HFC-245fa), trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E) ), Cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), or cis The method for producing a patterned member according to invention 5, comprising at least one of -1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)).

[Invention 7]
The fluorine-containing monomer of Invention 1 is homopolymerized, or one or more kinds of single monomers selected from the group consisting of the fluorine-containing monomer and acrylic acid ester, methacrylic acid ester, styrene compound, and olefin. A fluorine-containing polymer obtained by copolymerizing a monomer.

[Invention 8]
A step of homopolymerizing the fluorine-containing monomer of the invention 1, or
Including the step of copolymerizing the fluorine-containing monomer and one or more monomers selected from the group consisting of acrylic acid esters, methacrylic acid esters, styrene compounds, and olefins. A method for producing a fluoropolymer.

According to the present invention, a fluorine-containing monomer of the formula (1) is provided. Moreover, according to the present invention, it is possible to provide a curable composition containing the fluorine-containing monomer of the formula (1) having a small capillary number (Ca) as a constituent component. This curable composition is presumed to have a high filling rate into the mold in imprinting. Furthermore, the present invention provides a pattern forming method in imprinting (“manufacturing method of a member with a pattern in which a cured film having a pattern shape is arranged on a substrate”) using the curable composition.

The present invention will be described in detail. The present invention is not limited to the embodiments described below. Based on the ordinary knowledge of those skilled in the art, the present invention includes those in which the embodiments described below are appropriately modified and improved without departing from the spirit of the present invention.

In this specification, description will be given in the following order.
1. 1. Regarding the fluorine-containing monomer represented by the formula (1) 2. Method for producing the fluorine-containing monomer 3. Curable composition containing the fluorine-containing monomer as a constituent component About pattern formation method

In addition, in this specification, (meth) acryl means acrylic and methacryl. (Meth) acrylate means acrylate and methacrylate. (Meth) acryloyl means acryloyl and methacryloyl. EO represents ethylene oxide, and the EO-modified compound means having at least one ethyleneoxy group. PO represents propylene oxide, and the PO-modified compound means having at least one propyleneoxy group.

1. About the fluorine-containing monomer represented by Formula (1) One aspect of the present invention is a fluorine-containing monomer represented by Formula (1).

R ¹ and R ² are each independently a hydrogen atom or a methyl group. The fluorine-containing monomer is one of the following three types.
"Fluorine-containing monomer in which R ¹ and R ² are both hydrogen atoms"
"Fluorine-containing monomer in which R ¹ and R ² are both methyl groups"
"Fluorine-containing monomer in which either R ¹ or R ² is a hydrogen atom and the other is a methyl group"

In the present invention, any of these three types of fluorine-containing monomers can be preferably used. Of these, the object of the present invention can be achieved by using only one type, but two or more of these three types of fluorine-containing monomers may be used in combination as a mixture.

2. About the manufacturing method of the said fluorine-containing monomer The fluorine-containing monomer represented by Formula (1) is a novel compound. The synthesis method is shown below. Preferred synthesis methods include a “first method” and a “second method”, both of which use a diol represented by the formula (2) (which is an easily available fluorine-containing compound) as a raw material. It is subjected to (meth) acrylation reaction.

2-1. First Method The first method is represented by the formula (4) by first reacting the diol represented by the formula (2) with a (meth) acrylic anhydride represented by the formula (3). A first step of synthesizing (meth) acrylic acid ester, and then reacting the (meth) acrylic acid ester with a (meth) acrylic acid halide represented by formula (6) And a second step of obtaining the object to be expressed (see the following formula).

When the anhydride represented by the formula (3) is used as the (meth) acrylate for the diol represented by the formula (2), the mono (meth) acrylic acid represented by the formula (4) The reaction tends to stop when the ester is formed, and the second (meth) acrylic moiety is difficult to be introduced (first step). After obtaining the mono (meth) acrylic acid ester of the formula (4) with high selectivity in this way, the (meth) acrylic acid halide represented by the formula (6) is reacted as the second step. A second meta (acrylic) moiety is introduced and the target of formula (1) is obtained with high selectivity.

In the “first method”, for the above reasons, among the three compounds of the formula (1), either one of R ¹ and R ² is a hydrogen atom and the other is a methyl group. It is particularly suitable for synthesizing a “fluorinated monomer”.

On the other hand, R ¹ and R ² are the same type of group “fluorinated monomer in which R ¹ and R ² are both hydrogen atoms”, “fluorinated monomer in which both R ¹ and R ² are methyl groups. The `` mer '' can be synthesized by the first method, but it is advantageous because the following second method can be synthesized in a single reaction step rather than synthesize through a two-step reaction. There are many cases.

2-2. Second Method In the second method, the diol represented by the formula (2) is reacted with the (meth) acrylic acid halide represented by the formula (6) and the formula (7) to obtain the formula (1). Comprising a reaction (third step) for synthesizing the desired product (see formula below).

As described in the first method, the second method is a method in which only one kind of (meth) acrylic acid halide is reacted with a diol of the formula (2) to obtain R as an object of the formula (1). Synthesis of “fluorinated monomer in which R ¹ and R ² are both hydrogen atoms” and “fluorinated monomer in which both R ¹ and R ² are methyl groups”, wherein ¹ and R ² are the same type of group It is suitable for doing. (While the first method requires two reaction steps, the second method allows the target product to be synthesized in a single reaction step). If R ² is equal to R ¹ , the reaction of the second method can also be expressed as:

In the second method, even when the compounds of the formulas (6) and (7) are different (that is, one is an acrylic acid halide and the other is a methacrylic acid halide), the implementation is not hindered. . in this case,
“The compounds of formula (6) and formula (7) are mixed at a molar ratio of 1: 1, for example, and reacted simultaneously with the compound of formula (2)”, “After first subjecting the acrylate halide to the reaction, Next, subject the methacrylic acid halide to the reaction ",
“First, methacrylic acid halide is subjected to reaction, and then acrylic acid halide is subjected to reaction”,
Any of these methods can be adopted. However, when this method is adopted, it is difficult to obtain a single product, and usually “ ^one of R ¹ and R ² is a hydrogen atom and the other is a methyl group”, “R ^A “fluorinated monomer in which both ¹ and R ² are hydrogen atoms” and a “fluorinated monomer in which both R ¹ and R ² are methyl groups” are obtained in the form of a mixture. As described above, since it is also within the scope of the present invention to use such a mixture of a plurality of chemical species as the object of the formula (1), when the object is to be obtained as the mixture, the “second method” Can also be implemented in such a manner. The compound mixing procedure and the like at that time may be optimized based on the knowledge of those skilled in the art.

The following is a more specific explanation for each process.

[First step]
In the first step, the diol represented by the formula (2) and the (meth) acrylic anhydride represented by the formula (3) are reacted to produce the (meth) acrylic ester represented by the formula (4). It is a process. The method for producing the diol represented by the formula (2) and the first step are disclosed in Japanese Patent No. 4667035. For example, 1,1,1-trifluoro-2- (trifluoromethyl) pent-4-en-2-ol is reacted with concentrated sulfuric acid and then contacted with water to hydrolyze 1,1 -Bis (trifluoromethyl) butane-1,3-diol (diol represented by the formula (2)) is obtained.

The amount of (meth) acrylic anhydride represented by formula (3) is usually 0.5 mol or more and 5.0 mol or less with respect to 1.0 mol of diol represented by formula (2), 0.7 mol or more and 3.0 mol or less are preferable, and 1.0 mol or more and 2.0 mol or less are more preferable. If the amount of (meth) acrylic anhydride is less than 0.5 mol with respect to 1.0 mol of diol, the conversion rate of the reaction and the yield of the target product are not sufficient, and if it exceeds 5.0 mol, the reaction is involved. Not (meth) acrylic anhydride increases, which is not economically preferable from the time of disposal.

In the first step, additives can be added to accelerate the reaction. Additives used can include organic sulfonic acids or Lewis acids. Examples of the organic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and trifluoromethanesulfonic acid. Examples of the Lewis acid include BF ₃ , BCl ₂ and anhydrous hydrogen fluoride. Preferred are methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and trifluoromethanesulfonic acid. The amount of the additive used in this reaction is 0.01 mol or more and 2.0 mol or less with respect to 1.0 mol of the diol represented by the formula (2) of the substrate. The amount is preferably 8 mol or less, more preferably 0.05 mol or more and 1.5 mol or less. If the amount of the additive is less than 0.01 mol with respect to 1.0 mol of the diol, the conversion rate of the reaction and the yield of the target product are both decreased, and if it exceeds 2.0 mol, the amount of the additive not involved in the reaction is decreased. Since it increases, it is not economically preferable.

When this reaction is performed, the reaction temperature is usually 80 ° C. or higher and 200 ° C. or lower, preferably 100 ° C. or higher and 180 ° C. or lower, more preferably 120 ° C. or higher and 160 ° C. or lower when no additive is added. To do. In this case, if it is less than 80 ° C., the reaction rate is extremely slow, and if it exceeds 200 ° C., the raw acid anhydride or product ester may be polymerized, which is not preferable. When adding an additive, it is 0 degreeC or more and 80 degrees C or less normally, Preferably it is 10 degreeC or more and 70 degrees C or less, More preferably, it implements at 20 degrees C or more and 60 degrees C or less. In this case, if it is less than 0 ° C., the reaction rate is slow and it is not a practical production method. Moreover, when it exceeds 80 degreeC, a side reaction will advance easily and since the selectivity of ester which is a target object may fall, it is unpreferable. In this reaction, it is preferable to add an additive because sufficient reactivity can be obtained at a low temperature and the selectivity is improved. In other words, additives such as methane sulfonic acid, ethane sulfonic acid, p-toluene sulfonic acid, benzene sulfonic acid, trifluoromethane sulfonic acid are coexisted in the system, and the reaction is carried out in a temperature range of 20 ° C. or higher and 60 ° C. or lower. This is a particularly preferred embodiment of this step.

This reaction proceeds even without solvent, but it is preferable to use a solvent in consideration of the uniformity of the reaction and the operability after the reaction. Although there is no special restriction | limiting in the kind of solvent which can be used, An aromatic compound, an ether solvent, and a halogen-type solvent can be mentioned.
Examples of the aromatic compound include benzene, toluene, xylene, or mesitylene. Examples of ether solvents include diethyl ether, methyl-t-butyl ether, diisopropyl ether, and tetrahydrofuran. Examples of the halogen solvent include methylene chloride, chloroform, and carbon tetrachloride. These may be used alone or in combination.

The amount of the solvent used in this reaction is usually from 0.1 g to 100 g, preferably from 0.5 g to 50 g, preferably from 1.0 g to 20 g, based on 1 g of the diol represented by the formula (2). Is more preferable. If the amount of the solvent is less than 0.1 g with respect to 1 g of the diol, the merit of using the solvent cannot be sufficiently extracted. If it exceeds 100 g, it is not economically preferable from the viewpoint of productivity.

[Second step]
In the second step, the (meth) acrylic acid ester represented by the formula (4) is reacted with the (meth) acrylic acid halide represented by the formula (6), and the fluorine-containing single monomer represented by the formula (1) It is a process of manufacturing a body. In addition, as halogen (X) of the (meth) acrylic acid halide represented by (6), F, Cl, Br, and I can be mentioned independently, and Cl is particularly preferable. The amount of the (meth) acrylic acid halide represented by the formula (6) to be reacted with the ester represented by the formula (4) is not particularly limited, but 1 mol of the ester represented by the formula (4) Is preferably 0.1 mol or more and 50 mol or less, more preferably 0.5 mol or more and 10 mol or less, and particularly preferably 0.8 mol or more and 1.5 mol or less.

The reaction proceeds without the use of a solvent, but it is easier to control the use. The solvent that can be used is only required to dissolve the reaction reagent, and examples thereof include tetrahydrofuran, diethyl ether, diisopropyl ether, dichloroethane, and toluene. These solvents may be used alone or in combination of two or more.

The reaction temperature is not particularly limited and is preferably −78 ° C. or higher and 100 ° C. or lower, more preferably −20 ° C. or higher and 50 ° C. or lower, and further preferably −10 ° C. or higher and 30 ° C. or lower. The reaction is preferably carried out with stirring.

Although the reaction time depends on the reaction temperature, it is preferably 1 minute or more and 100 hours or less, more preferably 30 minutes or more and 50 hours or less, and particularly preferably 1 hour or more and 24 hours or less. Using an analytical instrument such as gas chromatography (GC), the end point of the reaction is preferably the time when the (meth) acrylic acid ester represented by the formula (4) as the raw material is consumed.

In this reaction, it is preferable to use a base. Examples of the base that can be used include pyridine, triethylamine, and diisopropylethylamine. The amount of these bases to be used is not particularly limited, but is preferably 0.1 mol or more and 50 mol or less with respect to 1 mol of the (meth) acrylic acid ester represented by the formula (4). Preferably they are 0.5 mol or more and 10 mol or less, Especially preferably, they are 0.8 mol or more and 1.5 mol or less.

After completion of the reaction, the fluorine-containing monomer represented by the formula (1) can be obtained by extraction, washing, distillation or column chromatography. Further, the obtained fluorine-containing monomer can be purified by precision distillation or the like.

[Third step]
In the third step, the diol represented by the formula (2) and the (meth) acrylic acid halide represented by the formula (6) or (7) are reacted, and the fluorine-containing single monomer represented by the formula (1) It is a process of manufacturing a body. Examples of the halogen (X) of the (meth) acrylic acid halide include F, Cl, Br, and I, and Cl is particularly preferable. The amount of (meth) acrylic acid halide used is not particularly limited, but is preferably 0.1 mol or more and 50 mol or less, and more preferably, with respect to 1 mol of the diol represented by the formula (2). Is 1.5 mol or more and 10 mol or less, and particularly preferably 1.8 mol or more and 3 mol or less.

The reaction proceeds without the use of a solvent, but it is easier to control the use. Examples of the solvent that can be used include tetrahydrofuran, diethyl ether, diisopropyl ether, dichloroethane, and toluene. These solvents may be used alone or in combination of two or more.

The reaction temperature is not particularly limited and is preferably −78 ° C. or higher and 100 ° C. or lower, more preferably −20 ° C. or higher and 50 ° C. or lower, and particularly preferably −10 ° C. or higher and 30 ° C. or lower. The reaction is preferably carried out with stirring.

Although the reaction time depends on the reaction temperature, it is preferably 1 minute or more and 100 hours or less, more preferably 30 minutes or more and 50 hours or less, and particularly preferably 1 hour or more and 24 hours or less. It is preferable to use an analytical instrument such as gas chromatography (GC) and set the end point of the reaction to the time when the diol represented by the formula (2) as the raw material is consumed.

In this reaction, it is preferable to use a base. Examples of the base that can be used include pyridine, triethylamine, and diisopropylethylamine. The amount of these bases to be used is not particularly limited, but is preferably 0.1 mol or more and 50 mol or less, more preferably 1.5 mol, with respect to 1 mol of the diol represented by the formula (2). The amount is from 1 mol to 10 mol, particularly preferably from 1.8 mol to 3 mol.

After completion of the reaction, the fluorine-containing monomer represented by the formula (1) can be obtained by extraction, washing, distillation or column chromatography. Moreover, it can refine | purify by the precision distillation etc. which were obtained as needed.

In any of the first step, the second step, and the third step, the polymerization may be carried out in the presence of a polymerization inhibitor for the purpose of preventing the reaction product or product from being polymerized, and it is usually preferable. Specific examples of polymerization inhibitors to be used include hydroquinone, methoquinone, 2,5-di-t-butylhydroquinone, 1,2,4-trihydroxybenzene, 2,5-bistetramethylbutylhydroquinone, leucoquinizarin, phenothiazine, Tetraethylthiuram disulfide, 1,1-diphenyl-2-picrylhydrazyl, or 1,1-diphenyl-2-picrylhydrazine, manufactured by Seiko Chemical Co., Ltd., trade names, Nonflex F, Nonflex H, Nonflex DCD Non-flex MBP, Ozonon 35, Fuji Film Wako Pure Chemical Industries, Ltd., Q-1300, Q-1301 can be exemplified. The above polymerization inhibitors are commercially available and can be easily obtained.

3. About the curable composition containing the said fluorine-containing monomer as a structural component Another aspect of this invention is a curable composition containing the fluorine-containing monomer represented by Formula (1), and a polymerization initiator. It is. The curable composition further comprises, as an optional component, a polymerizable compound other than the fluorine-containing monomer represented by the above formula (1) (sometimes referred to as “other polymerizable compound” in this specification), an increase Sensitizers, surfactants, solvents, and various additives can be included.

Hereinafter, each component will be described. For convenience of explanation, “the fluorine-containing monomer represented by the formula (1)” and “other polymerizable compound” are collectively described as “polymerizable compound”. Other optional components will be described as “other additive components”.

3-1. Polymerizable Compound The polymerizable compound is a generic term for “the fluorine-containing monomer represented by the formula (1)” and “other polymerizable compounds” as described above. The polymerizable compound is the main component of the curable composition for imprints. The content of the polymerizable compound in the curable composition is usually 50% by mass or more, and typically 80% by mass or more. When a curable composition contains a solvent, it is not prevented that there is little content of a polymeric compound from this. However, since the fluorine-containing monomer represented by the formula (1) exhibits sufficient fluidity even without a solvent and can sufficiently fill the uneven portion of the mold, the solvent is not an essential component. If it does so, it is one of the especially preferable aspects that the content of the polymeric compound which occupies for the whole curable composition is 90 mass% or more.

As the polymerizable compound, a fluorine-containing monomer represented by the formula (1) may be used alone (see Example 1 in this specification). However, “other polymerizable compounds” can be used in combination with the fluorine-containing monomer represented by the formula (1), and in that case, a cured film having even higher mechanical strength may be obtained. The “other polymerizable compounds” are not particularly limited as long as they are radically polymerizable compounds, but are preferably compounds having one or more acryloyl groups or methacryloyl groups, that is, (meth) acrylic compounds. “(Fluorine-containing monomer of formula (1)” and “(meth) acrylic in other polymerizable compounds relative to the total mass of“ fluorine-containing monomer of formula (1) ”and“ other polymerizable compound ” The proportion of the “compound” mass is preferably 90% or more.
In "other polymerizable compounds", the monofunctional monomer that is a compound having one acryloyl group or methacryloyl group in its structure acts only for polymerization, and is a polyfunctional monomer that is a compound having two or more. Performs cross-linking. The physical properties such as hardness of the cured product obtained can be adjusted by the ratio of these monomers. In order to obtain hardness in the cured film, it is preferable to perform crosslinking with a polyfunctional monomer.

There is no particular lower limit of the proportion of the fluorine-containing monomer of the formula (1) to the total mass of the polymerizable compound, but the proportion of the fluorine-containing monomer of the formula (1) is usually 10% or more, 30 % Or more is preferable. When emphasizing the excellent filling property (filling speed) of the fluorine-containing monomer of the formula (1), it is particularly preferable to make the ratio 60% or more (including 100%). On the other hand, even if the content of the fluorine-containing monomer represented by the formula (1) is smaller than these, the filling property of the curable composition is improved by the contribution. Therefore, even when a smaller amount of the fluorine-containing monomer represented by the formula (1) is contained, it is not excluded from the scope of the present invention.

Among the “other polymerizable compounds”, monofunctional (meth) acrylic compounds having one acryloyl group or methacryloyl group include, for example, phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxy Ethoxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2 -Hydroxypropyl (meth) acrylate, (meth) acrylate of EO-modified p-cumylphenol, 2-bromophenoxyethyl (meth) acrylate, 2,4-dibromophenoxyethyl (meth) acrylate, 2,4,6-tri Lomophenoxyethyl (meth) acrylate, EO-modified phenoxy (meth) acrylate, PO-modified phenoxy (meth) acrylate, polyoxyethylene nonylphenyl ether (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2 -Methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydro Cypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodeci (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) ) Acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, Diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (me ) Acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide , Or N, N-dimethylaminopropyl (meth) acrylamide, but is not limited thereto.

Commercial products corresponding to these monofunctional (meth) acrylic compounds include trade names, Aronix M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (above, Toagosei Co., Ltd.) Manufactured), MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscoat # 150, # 155, # 158, # 190, # 192, # 193, # 220, # 2000, # 2100, # 2150 (above Osaka Organic Chemical Co., Ltd.), light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO -A, P-200A, NP 4EA, NP-8EA, epoxy ester M-600A (above, Kyoeisha Chemical Co., Ltd.), KAYARADＡＲTC110S, R-564, R-128H (above, Nippon Kayaku Co., Ltd.), NK ester AMP-10G, AMP- 20G (above, Shin-Nakamura Chemical Co., Ltd.), FA-511A, 512A, 513A (above, Hitachi Chemical Co., Ltd.), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), VP (made by BASF Japan Ltd.), ACMO, DMAA, DMAPAA (above, manufactured by Kojin Co., Ltd.) can be exemplified, but are not limited thereto. It is not something.

Among the “other polymerizable compounds”, polyfunctional (meth) acrylic compounds having two or more acryloyl groups or methacryloyl groups include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and EO modification. Trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris ( Acryloyloxy) isocyanurate, bis (hydroxymethyl) tricyclodecane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO modified 2,2-bis (4-(( Meth) acryloxy) phenyl) propane, PO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane, or EO, PO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane Can be illustrated , But it is not limited thereto.

Commercially available products corresponding to polyfunctional (meth) acrylic compounds include trade names, Iupimer UV SA1002, SA2007 (above, manufactured by Mitsubishi Chemical Corporation), Biscoat # 195, # 230, # 215, # 260, # 335HP, # 295, # 300, # 360, # 700, GPT, 3PA (above, manufactured by Osaka Organic Chemical Co., Ltd.), Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP- 4PA, TMP-A, PE-3A, PE-4A, DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (Nippon Kayaku Co., Ltd.), Aronix M208, M210 M215, M220, M240, M305, M309, M310, M315, M325, M400 (above, manufactured by Toagosei Co., Ltd.), Lipoxy VR-77, VR-60, VR-90 (above, manufactured by Showa Denko KK) Although it can illustrate, it is not limited to these.

The “other polymerizable compounds” exemplified above may be used alone or in combination of two or more.

3-2. Polymerization initiator The polymerization initiator includes a photopolymerization initiator and a thermal polymerization initiator.

[Photopolymerization initiator]
The photopolymerization initiator is a substance that generates reactive species that cause a polymerization reaction of the polymerizable compound by light stimulation. Specific examples include a photo radical generator that generates radicals by light stimulation.

Photoradical generators are polymerization initiators that generate radicals by light (infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, charged particle beams such as X-rays, electron beams, etc., radiation). Used for radically polymerizable compounds.

Examples of the photoradical generator include 2,4,5-triarylimidazole dimer which may have a substituent, benzophenone derivative, aromatic ketone derivative, quinones, benzoin ether derivative, benzyl derivative, acridine derivative, N -Phenylglycine derivatives, acetophenone derivatives, benzoin derivatives, thioxanthone derivatives, other photoradical generators, and commercial products thereof. Each is illustrated below. The following photo radical generators may be used alone or in combination of two or more.
<2,4,5-triarylimidazole dimer optionally having substituent>
2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4 , 5-diphenylimidazole dimer, or 2- (o- or p-methoxyphenyl) -4,5-diphenylimidazole dimer <benzophenone derivative>
Benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 4- chlorobenzophenone 4,4′-dimethoxybenzophenone or 4,4′-diaminobenzophenone <Aromatic ketone derivative>
2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one <Quinones>
2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, or 2,3-dimethylanthraquinone <benzoin ether derivative>
Benzoin methyl ether, benzoin ethyl ether, or benzoin phenyl ether <benzoin derivative>
Benzoin, methylbenzoin, ethylbenzoin, or propylbenzoin <Benzyl derivatives>
Benzyldimethyl ketal <acridine derivative>
9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane <N-phenylglycine derivative>
N-phenylglycine <acetophenone derivative>
Acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, or 2,2-dimethoxy-2-phenylacetophenone <thioxanthone derivative>
Thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, or 2-chlorothioxanthone <Other photoradical generator>
Xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide <commercially available product>
Product name, Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173 (above, manufactured by Ciba Japan Co., Ltd.), Lucirin TPO , LR8883, LR8970 (above, manufactured by BASF Japan Ltd.), Ubekrill P36 (UCB Japan Ltd.), and the like, but are not limited thereto.

[Thermal polymerization initiator]
The thermal polymerization initiator is a substance that generates reactive species that cause a polymerization reaction of the polymerizable compound by thermal stimulation. Specific examples include thermal radical generators that generate radicals upon thermal stimulation.

Examples of the thermal radical generator include azo compounds and organic peroxides.
<Azo compound>
Azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrile), 2,2′-azobis-2-methylbutyronitrile, Examples include 1,1′-azobis (1-cyclohexanecarbonitrile), 2,2′-azobis (methylisobutyrate), or 2,2′-azobis (2-amidinopropane) dihydrochloride.
<Organic peroxide>
Dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or di An example is -t-butyl peroxide.

In the curable composition of the present invention, one polymerization initiator may be used alone, or two or more polymerization initiators may be used in combination. Here, in the case where the step of curing the curable composition is based on light, a photopolymerization initiator is used as the initiator, and in the case where it is based on heat, a thermal polymerization initiator is used as the initiator. Among these initiators, it is preferable to use a photopolymerization initiator when manufacturing a film to be a microstructure such as a semiconductor integrated circuit. This is because when a photopolymerization initiator is used, a heat process such as heating or cooling is not required in the process for producing a cured film, and productivity is excellent.

Although there is no restriction | limiting in particular in content of the polymerization initiator contained in the curable composition of this invention, Preferably, 0.01 mass% or more and 10 mass with respect to the mass (total mass) of a curable composition % Or less. More preferably, they are 0.1 mass% or more and 7 mass% or less, Especially preferably, they are 1 mass% or more and 5 mass% or less. Within this range, both the curing rate of the curable composition and the strength (resin strength) of the film (cured film) are excellent.

3-3. Other Additive Components The curable composition of the present invention may contain additional additive components in addition to the above-described components within a range not impairing the effects of the invention according to various purposes. Examples of such additive components include surfactants, sensitizers, hydrogen donors, antioxidants, solvents, and polymer components. In particular, the photocurable composition preferably contains a sensitizer. This will be described below.

[Sensitizer]
By including a sensitizer, there is a tendency that the polymerization reaction is accelerated and the reaction conversion rate is improved. Examples of the sensitizer include a hydrogen donor or a sensitizing dye.

When the curable composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 10% by mass or less with respect to the mass of the polymerizable compound. More preferably, it is 0.1 mass% or more and 5 mass% or less. Here, when the content of the sensitizer is 0.1% by mass or more, the polymerization promoting effect can be expressed more effectively. Moreover, when content of a sensitizer is 10 mass% or less, there exists a tendency for solubility and storage stability to be excellent.

[Hydrogen donor]
A hydrogen donor is a compound in which hydrogen is donated to an initiation radical generated from a polymerization initiator or a radical at a polymerization growth terminal, and the hydrogen donor itself generates a radical. If the polymerization initiator is a photoradical generator, the polymerization rate may be improved.

Examples of the hydrogen donor include amine compounds and mercapto compounds. Examples of these compounds acting as hydrogen donors are shown below, but are not limited thereto.
<Amine compound>
N-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiouronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate, triethylenetetramine, 4,4'-bis (Dialkylamino) benzophenone, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethanolamine, or N-phenylglycine Specific examples of 4,4′-bis (dialkylamino) benzophenone include 4,4′-bis (diethylamino) benzophenone.
<Mercapto compound>
Examples thereof include 2-mercapto-N-phenylbenzimidazole and mercaptopropionic acid ester.

[Sensitizing dye]
A sensitizing dye is a compound that is excited by absorbing light of a specific wavelength and acts on a photopolymerization initiator. The action here means energy transfer or electron transfer from the excited state sensitizing dye to the photopolymerization initiator. If the photopolymerization initiator is a photoradical generator, the addition of a sensitizer may improve the polymerization rate.

Sensitizing dyes include anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, thiopyrylium salt dyes, merocyanine Dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, or pyrylium salt dyes. It is not limited to.

The sensitizing dyes may be used alone or in combination of two or more.

[Polymer component]
The curable composition of the present invention may contain a polymer component. Examples of the polymer component used herein include the above 3-1. The (meth) acrylic polymer (for example, polymethyl methacrylate) and the vinyl polymer (for example, polystyrene) which contain the repeating unit derived from the polymeric compound as described in the paragraph of (5) as a structural unit are contained. The polymer component may be a copolymer.

3-4. Preparation of curable composition [Temperature when compounding curable composition]
When preparing a curable composition by mixing and dissolving a polymerization initiator and a polymerizable compound, it is carried out under a predetermined temperature condition. From workability etc., Preferably, they are 0 degreeC or more and 100 degrees C or less, More preferably, they are 10 degreeC or more and 50 degrees C or less.

[Impurities such as particles mixed in the curable composition]
The curable composition of the present invention removes impurities such as particles as much as possible in order to prevent inadvertent irregularities in the photocured product due to particles mixed in the curable composition and pattern defects. It is preferable. Specifically, after mixing each component contained in the curable composition, it is preferable to filter with a filter having a pore size of 0.001 μm or more and 5.0 μm or less, for example. When performing filtration using a filter, it is more preferable to carry out in multiple stages or repeat many times. Moreover, you may filter the filtered liquid again. As a filter used for filtration, filters made of polyethylene resin, polypropylene resin, fluororesin, nylon resin, etc. can be used, but are not particularly limited.

When the curable composition of the present invention is used for manufacturing a semiconductor integrated circuit, it is preferable to avoid metal impurities from being mixed into the composition as much as possible so as not to hinder the operation of the product. . For this reason, in the curable composition of the present invention, the concentration of metal impurities contained in the composition is preferably 10 ppm or less, and more preferably 100 ppb or less.

4). About Pattern Forming Method Still another aspect of the present invention is a method for producing a “patterned member in which a cured film having a pattern shape is arranged on a substrate” (D) by imprinting using the above-described curable composition (hereinafter referred to as “patterned member”). , Simply referred to as the pattern forming method of the present invention), and includes the following steps.
Arrangement step: A step of arranging the above-mentioned curable composition on a substrate to obtain “a member in which the curable composition is arranged on the substrate” (A).
Mold contact step: A mold having a pattern shape is brought into contact with the curable composition in (A), and “a substrate / pattern composition having a curable composition / mold joined in this order” (B ).
Curing step: The curable composition in (B) is cured by light or heat to form a cured film, and “a member in which a substrate / patterned cured film / mold is joined in this order” (C) Obtaining step.
Mold release step: a step of separating the mold from (C) to obtain the patterned member (D).

In the pattern forming method of the present invention, the imprint includes a light imprint that is cured by light and a heat imprint that is cured by heat.

In this specification, the imprint is a method for producing “a member in which a cured film having a concavo-convex pattern shape of preferably 1 nm or more and 100 μm or less is arranged on a substrate”. Among them, nanoimprint is a method for producing “a member provided with a cured film having a concavo-convex pattern shape of 1 nm or more and 100 nm or less”. The pattern formation method of this invention can be used suitably for nanoimprint.
The “pattern forming method” is referred to here as “a member in which a cured film having a pattern shape is arranged on a substrate” described in [Invention 4] in imprinting (D). And includes the four steps of “arrangement step”, “die contact step”, “curing step”, and “mold release step” as essential.

In the following description, for the sake of convenience, the “arrangement process”, “mold contact process”, “curing process”, and “release process” are also referred to as processes [1] to [4], respectively.

FIG. 1 is a schematic cross-sectional view showing an example of an embodiment in the pattern forming method of the present invention. The pattern forming method shown in FIG. 1 includes the following steps.
[1] Step of arranging a curable composition on a substrate (arrangement step, FIG. 1 (a))
[2] A step of bringing the mold into contact with the curable composition (mold contact step, FIGS. 1 (b1) and (b2))
[3] Step of producing a cured film by curing the curable composition with light or heat (curing step, FIG. 1 (c))
[4] Step of separating the mold from the cured film (mold release step, FIG. 1 (d))
Through the steps shown in [1] to [4] above, the cured product 5 and the electronic component (electronic device) or optical component having the cured product 5 can be obtained from the curable composition 1.

Hereinafter, each step [1] to [4] will be described.

4-1. Step [1] (arrangement step; FIG. 1A)
First, the curable composition 1 is placed (applied) on the substrate 2 to form a coating film (FIG. 1A). The curable composition here is the curable composition of the present invention.

As the substrate to be processed corresponding to the substrate 2, a silicon wafer is usually used, but is not limited thereto. In addition to silicon wafers, semiconductor device substrates such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, or silicon nitride can be used. The substrate to be used (substrate to be processed) is a substrate that has improved adhesion to the curable composition by surface treatment such as silane coupling treatment, silazane treatment, or organic thin film formation. It may be used as

Examples of a method for disposing the curable composition of the present invention on a substrate to be processed include, for example, an inkjet method, a dip coating method, an air knife coating method, a curtain coating method, a wire barcode method, a gravure coating method, and an extrusion coating method. , Spin coating method, slit scanning method and the like. In addition, although the film thickness of a to-be-shaped transfer layer (coating film) changes with uses to be used, it is 0.01 micrometer or more and 100 micrometers or less, for example.

4-2. Step [2] (die contact step; FIG. 1 (b1), (b2))
Next, the process (a mold contact process, FIG. 1 (b1), (b2)) which makes a mold contact the coating film which consists of the curable composition 1 formed at the front process (arrangement | positioning process) is performed. Since the mold 3 can be regarded as a seal, this process is also called a stamping process. In this step, when the mold 3 is brought into contact with the curable composition 1 (shaped transfer layer) (FIG. 1 (b1)), a coating film (part) 4 is formed on the uneven portion of the fine pattern formed on the mold 3. Is filled (FIG. 1 (b2)).

The mold 3 used in the mold contact process is made of a light transmissive material when the next process (curing process) is a photocuring process using light. Specific examples of the constituent material of the mold 3 include optically transparent resins such as glass, quartz, PMMA, and polycarbonate resins, transparent metal vapor-deposited films, flexible films such as polydimethylsiloxane, photocured films, and metal films. Can do. However, when a light transparent resin is used as a constituent material of the mold 3, a resin that does not dissolve in the photocurable composition 1 is selected. Quartz is particularly preferred because of its low thermal expansion coefficient. On the other hand, when the curing step is a thermosetting step, there is no limitation on the transparency of the material, and the above-described materials can be used as the constituent material of the mold 3.

The mold 3 may be subjected to a surface treatment before this step (die contact step) in order to improve the peelability between the cured product 5 and the surface of the mold 3. Examples of the surface treatment method include a method of forming a release agent layer by applying a release agent to the surface of the mold. Here, as a mold release agent applied to the mold surface, a silicon mold release agent, a fluorine mold release agent, a polyethylene mold release agent, a polypropylene mold release agent, a paraffin mold release agent, a montan mold release agent Or carnauba release agents. For example, a commercially available coating mold release agent such as trade name OPTOOL DSX manufactured by Daikin Industries, Ltd. can also be used. In addition, a mold release agent may be used individually by 1 type, and may be used in combination of 2 or more types. Among these, a fluorine-type mold release agent is particularly preferable.

In the mold contact step, as shown in FIG. 1 (b1), when the mold 3 is brought into contact with the curable composition 1, the pressure applied to the curable composition 1 is not particularly limited, but is usually 0.1 MPa or more. , 100 MPa or less. Among them, it is preferably 0.1 MPa or more and 50 MPa or less, more preferably 0.1 MPa or more and 30 MPa or less, and further preferably 0.1 MPa or more and 20 MPa or less.

Further, the time for bringing the mold 3 into contact with the photocurable composition 1 in this step is not particularly limited, but is usually 0.1 seconds or more and 600 seconds or less, and is 0.1 seconds or more and 300 seconds or less. It is preferably 0.1 seconds or more and 180 seconds or less, and particularly preferably 0.1 seconds or more and 120 seconds or less.

The environment in which this step is performed includes an air atmosphere, a reduced pressure atmosphere, and an inert gas atmosphere. Here, when performing this process, there is no restriction | limiting in particular about the pressure of atmosphere, For example, it can set suitably in the range of 1.0133 * 10 < ^-5 > MPa or more and 1.0133MPa or less.

[Inert gas]
When this step is performed in an inert gas atmosphere, specific examples of the inert gas used include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbons, and mixed gases thereof. When used for nanoimprinting, helium is preferred.

When helium is used as the inert gas, when the uneven portion of the fine pattern formed on the mold 3 in this step is filled with the inert gas in the atmosphere together with a part of the coating film 4, The inert gas can escape through the mold. For this reason, it is excellent in the filling property of the curable composition 1 to the uneven part of the mold 3.

[Condensable gas]
Moreover, you may perform this process in the gas atmosphere containing a condensable gas. In the present invention, the condensable gas refers to a gas that satisfies the following requirements (i) and (ii).
(I) Gas existing in the atmosphere as a gas at the stage before the curable composition 1 (shaped transfer layer) and the mold 3 are in contact with each other in this step (FIG. 1 (b1)) (ii) curable composition 1 And the mold 3 are in contact with each other, and the gas in the atmosphere is filled together with the coating film (part) 4 into the recesses of the fine pattern formed on the mold 3 and the gap between the mold and the substrate. The gas that is condensed and liquefied by the capillary pressure generated by the pressure at the time of filling. Here, when the mold contact process is performed in a condensable gas atmosphere, the gas filled in the concave portions of the fine pattern of the mold 3 is liquefied. Since bubbles are less likely to be generated, the filling property is excellent. The condensable gas (at least a part thereof) may be dissolved in the curable composition.

The boiling point of the condensable gas is not particularly limited as long as it is equal to or lower than the environmental temperature of this step, but a gas having a low boiling point in the range of 5 ° C. or higher and 50 ° C. or lower from the environmental temperature is preferable. If it exists in this range, the filling property of the curable composition 1 to the fine pattern uneven | corrugated | grooved part of the mold 3 will be further excellent.

In this step, the vapor pressure of the gas containing the condensable gas is not particularly limited as long as it is equal to or lower than the mold pressure at the time of imprinting in this step, but is preferably 0.1 MPa or more and 0.4 MPa or less. If it exists in this range, the filling property of the curable composition 1 to the fine pattern uneven | corrugated | grooved part of the mold 3 will be further excellent. Here, when the vapor pressure at the ambient temperature is larger than 0.4 MPa, there is a tendency that the effect of eliminating the bubbles cannot be sufficiently obtained. On the other hand, if the vapor pressure at ambient temperature is less than 0.1 MPa, pressure reduction is required, and the apparatus tends to be complicated.

The environmental temperature during this step is not particularly limited, but is preferably 20 ° C or higher and 50 ° C or lower.

Examples of condensable gases include chlorofluorocarbons (CFC), fluorocarbons (FC), hydrochlorofluoroolefins (HCFO), hydrofluoroolefins (HFO), hydrofluoroethers (HFE), and other fluorocarbons. To do.
<Chlorofluorocarbon (CFC)>
Chlorofluoromethane <Fluorocarbon (FC)>
<Hydrochlorofluoroolefin (HCFO)>
Trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)), cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)), trans- 1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (E)), cis-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)), 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za), 1,1,2-trichloro-3,3,3-trifluoropropene (HCFO-1213xa), trans-1-chloro- 1,3,3,3-tetrafluoropropene (HCFO-1224zb (E)), cis-1-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224zb (Z))
<Hydrofluoroolefin (HFO)>
Trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz (E)), cis-1,1,1,4,4,4-hexafluoro-2-butene ( HFO-1336mzz (Z)), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis-1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)) )
<Hydrofluorocarbon (HFC)>
1,1,1,3,3-pentafluoropropane (CHF ₂ CH ₂ CF ₃ , HFC-245fa, PFP)
<Hydrofluoroether (HFE)>
Pentafluoroethyl methyl ether (CF ₃ CF ₂ OCH ₃ , HFE-245mc), 1,1,1,3,3,3-hexafluoro-2-methoxypropane (HFE-356 mmz)

Among these condensable gases, when the environmental temperature in the mold contact step is about room temperature (20 ° C. to 25 ° C.), the filling property of the curable composition 1 to the fine pattern irregularities of the mold 3 is excellent. It is preferable to use the compounds exemplified in.
・ 1,1,1,3,3-pentafluoropropane (vapor pressure at 23 ° C: 0.14 MPa, boiling point: 15 ° C)
・ Trichlorofluoromethane (vapor pressure 0.1056 MPa at 23 ° C., boiling point 24 ° C.)
・ Trans-1-chloro-3,3,3-trifluoropropene (boiling point 18 ° C)
・ Cis-1-chloro-3,3,3-trifluoropropene (boiling point 39 ° C.)
・ Trans-1,3,3,3-tetrafluoropropene (boiling point -19 ℃)
・ Pentafluoroethyl methyl ether Among these, 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene, cis-1 -Chloro-3,3,3-trifluoropropene, trans-1,3,3,3-tetrafluoropropene are particularly preferred.

Condensable gas may be used alone or in combination of two or more. These condensable gases may be used by mixing with non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon. As the non-condensable gas mixed with the condensable gas, helium is preferable from the viewpoint of filling properties. When helium is used, even if it is used as a mixed gas formed by mixing a condensable gas and a non-condensable gas (helium), the filling property is excellent because helium penetrates the mold.

Among these atmospheres, regardless of whether the curing process is a photocuring process or a thermal curing process, the influence on the curing reaction by oxygen or moisture can be prevented, so that a reduced pressure atmosphere, an inert gas atmosphere or a condensable gas atmosphere preferable.

4-3. Step [3] (Curing step; FIG. 1 (c))
Next, the coating film is cured. Specifically, the coating film 4 is irradiated with light through the mold 3 (FIG. 1C), or the coating film 4 is heated. In the curing step, the cured film 5 is formed by curing the coating film 4 with light or heat.

[Photocuring]
When the coating film 4 is cured by light, the light applied to the curable composition 1 constituting the coating film 4 is selected according to the sensitivity wavelength of the curable composition 1, and specifically, 150 nm to It is preferable to select and use ultraviolet light having a wavelength of about 400 nm, X-rays, electron beams or the like as appropriate. Here, many commercially available photopolymerization initiators are sensitive to ultraviolet light. For this reason, the light (irradiation light 6) applied to the curable composition 1 is particularly preferably ultraviolet light. Examples of the light source that emits ultraviolet light include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a deep-UV lamp, a carbon arc lamp, a chemical lamp, a metal halide lamp, a xenon lamp, a KrF excimer laser, an ArF excimer laser, or F. ₂ excimer laser and the like, and an ultrahigh pressure mercury lamp is particularly preferable. The number of light sources used may be one or plural. Moreover, when performing light irradiation, you may carry out to the whole surface of the curable composition 1, and may carry out only to a one part area | region. Moreover, when using together a photoinitiator and a thermal-polymerization initiator, in addition to light irradiation, you may further heat-harden. The order of photocuring and thermal curing is not limited, and includes cases where thermal curing is performed after photocuring, photocuring is performed after thermal curing, and photocuring and thermal curing are performed simultaneously.

[Heat curing]
In the case of curing by heat, the heating atmosphere and the heating temperature are not particularly limited. For example, the curable composition 1 can be heated in the range of 40 ° C. or higher and 200 ° C. or lower under an inert atmosphere or under reduced pressure. Moreover, when heating the to-be-shaped transfer layer (coating film 4), a hot plate, oven, furnace, etc. can be used.

4-4. Step [4] (Release step; FIG. 1 (d))
Next, the mold 3 is separated from the cured film 5, and a process of forming a cured film having a predetermined pattern shape on the substrate 2 (mold release process, FIG. 1D) is performed. This step is a step of peeling the mold 3 from the cured film 5, and a reverse pattern of the fine pattern formed on the mold 3 in the previous step (curing step) is obtained as the pattern of the cured film 5.

The method of separating the cured film 5 and the mold 3 is not particularly limited as long as a part of the cured film 5 is not physically damaged when being separated, and various conditions are not particularly limited. For example, the substrate 2 (substrate to be processed) may be fixed and the mold 3 may be moved away from the substrate 2 to be separated, or the mold 3 may be fixed and the substrate 2 moved away from the mold to be separated. Alternatively, both of them may be peeled by pulling in the opposite direction.

In addition, when the mold contact process is performed in a condensable gas atmosphere, when the cured film and the mold are separated in the mold release process, condensation occurs as the pressure at the interface between the cured film and the mold decreases. When the property gas is vaporized, the release force reducing effect tends to be exhibited.

A cured film having a desired concavo-convex pattern shape (inverted pattern shape of the concavo-convex shape of the mold 3) can be obtained by a series of steps (manufacturing process) from the steps [1] to [4] described above. The obtained cured film can also be used, for example, as an optical member (including a case where it is used as one member of an optical member) such as a Fresnel lens or a diffraction grating. In such a case, it can be set as the optical member which has the board | substrate 2 and the cured film 5 which has the pattern shape arrange | positioned on this board | substrate 2 at least.

The curable composition of the present invention has a high filling rate and is therefore highly productive and is excellent for imprinting. In particular, it is excellent for nanoimprinting for forming a nano-sized (1 nm or more, 100 nm or less) pattern.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

[Example 1]
[Synthesis of fluorinated monomer] (Synthesis of diacrylate (1))
In a 50 ml reactor, 6 g of diisopropyl ether, 2.2 g (0.022 mol, 2.5 equivalents) of triethylamine, 1,1-bis (trifluoromethyl) butane-1,3-diol 2 represented by the following formula (2) 0.0 g (0.009 mol, 1.0 equivalent, the synthesis method is described in Journal of Fluorine Chemistry, 128 (8), 902-909; 2007) was added and bathed in ice. Thereto, 2.0 g (0.022 mol, 2.5 equivalents) of acrylic acid chloride was slowly added dropwise, and the mixture was stirred at room temperature for 3 hours. After filtration of the reaction solution, the obtained organic layer was washed twice with 10 g of a saturated ammonium chloride aqueous solution, the solvent was distilled off, and the desired fluorine-containing solution was obtained by distillation under reduced pressure (0.3 kPa, bath 100 ° C.). 1.5 g (4.49 mmol) of a monomer (hereinafter sometimes referred to as diacrylate (1)) was obtained. The purity of diacrylate 1 was 99.7%, and the yield based on 1,1-bis (trifluoromethyl) butane-1,3-diol was 50%.

The analysis results obtained by NMR are shown below.
¹ H NMR (measurement solvent: deuterated chloroform, reference material: tetramethylsilane); δ = 6.48 (dd, 1H), 6.35 (dd, 1H), 6.11 (dd, 1H), 6.04 -5.94 (m, 2H), 5.79 (dd, 1H), 5.24 (m, 1H), 3.05 (dd, 1H), 2.63 (dd, 1H), 1.31 ( d, 3H).
¹⁹ F NMR (measurement solvent: deuterated chloroform, reference material: perfluorobenzene); δ = −73.1 (t, 3F), −73.2 (t, 3F).

[Physical property measurement]
About the obtained diacrylate (1), each physical property was measured by the method demonstrated below.

(1) Surface tension The surface tension of the diacrylate (1) was measured by the hanging drop method. The measurement was performed 10 times using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model DMs-601), and the average value of the 10 measured values was defined as the surface tension.

(2) Viscosity The viscosity of diacrylate (1) at 30 ° C. was measured using a Canon-Fenske viscometer (manufactured by Shibata Kagaku Co., Ltd., model SO-5X18).

(3) Contact angle The contact angle between the diacrylate (1) and the substrate was measured using the automatic contact angle meter. Each measurement was performed five times, and the average value of the five measurements was taken as the contact angle.
The substrates used in this measurement are as follows. In the following description, the mold contact angle is the contact angle between the mold and diacrylate (1), and the substrate contact angle is the contact angle between the substrate on which diacrylate (1) is applied and diacrylate (1). It is.
(3-1) Mold Contact Angle Measurement Substrate A quartz substrate having a release layer formed on the surface with a release agent (product name: OPTOOL HD-1100, manufactured by Daikin Industries, Ltd.) was used.
(3-2) Substrate Contact Angle Measurement Substrate A silicon wafer having an adhesion layer formed on the surface with a primer (manufactured by Microresist Technology, Germany, product name mr-APS1) was used.

In the above measurement for diacrylate (1), the surface tension is 25.5 mN / m, the viscosity is 2.7 mPa · s, the mold contact angle is 51.6 °, and the substrate contact angle is 11.5 °. Met.

[Comparative Example 1 (Neopentyl glycol diacrylate)]
The physical properties of neopentyl glycol diacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were measured in the same manner as in the case of diacrylate (1) in Example 1. As a result, the surface tension was 30.5 mN / m, the viscosity was 5.1 mPa · s, the mold contact angle was 73.5 °, and the substrate contact angle was 7.9 °.

[Capillary number (Ca)]
For the diacrylate (1) of Example 1, Ca was calculated. As a result, Ca was 0.79 V (L / h ₀ ) ² . V, L, and h ₀ are constants related to the apparatus or measurement conditions, and are constant in the examples and comparative examples.
Similarly to Example 1, Ca was calculated for the monomer of Comparative Example 1. As a result, Ca was 1.57 V (L / h ₀ ) ² .

The above results are shown in Table 1 below.

From Table 1, the fluorine-containing monomer represented by the formula (1) of the present invention described in Example 1 has a small capillary number (Ca).

[Example 2]
[Preparation of curable composition]
45 parts by mass of diacrylate (1), 10 parts by mass of isobornyl acrylate, 40 parts by mass of benzyl acrylate, 4 parts by mass of diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 4,4′-bis 1 part by mass of (diethylamino) benzophenone was mixed to prepare a curable composition.

[Comparative Example 2]
[Preparation of curable composition]
A curable composition was prepared in the same manner as in Example 2 except that diacrylate (1) was replaced with neopentyl glycol diacrylate.

[Measurement of physical properties of curable composition]
The physical properties of the curable compositions obtained in Example 2 and Comparative Example 2 were measured by the same method as in Example 1. The results are shown in Table 2.

From Table 2, also in Example 2 in which the content of diacrylate (1) in the curable composition is a small amount (45 parts by weight) compared to Example 1, the number of capillaries (Ca) is higher than that in Comparative Example 2. Is significantly smaller.

[Example 3]
[Synthesis of Fluoropolymer-1]
A 20 ml eggplant-shaped flask was charged with 1.5 g of the diacrylate (1) obtained in [Example 1] and 0.1 g of dimethyl 2,2′-azobis (2-methylpropionate) as a polymerization initiator. Dissolved in 7.5 g. While stirring in a nitrogen atmosphere, the mixture was heated to 80 ° C. and polymerized for 5 hours. The resulting polymerization solution was cooled to room temperature, 22.1 g of n-heptane was added, and the precipitated white powder was collected by filtration.
22.1 g of n-heptane was added to the collected white powder to form a slurry, followed by filtration, and then drying with an evaporator to obtain 1.0 g of a white powder of polymer. When ¹ H-NMR of the obtained fluoropolymer- ¹ was measured, no residual monomer was detected, and fluoropolymer-1 was synthesized.

[Example 4]
[Synthesis of fluorinated copolymer-2]
In a 20 ml eggplant-shaped flask, 2.0 g of the diacrylate (1) obtained in [Example 1], 0.6 g of styrene, and dimethyl 2,2′-azobis (2-methylpropionate) 0. 3 g was charged and dissolved in 7.8 g of tetrahydrofuran. While stirring in a nitrogen atmosphere, the mixture was heated to 80 ° C. and polymerized for 5 hours. The obtained polymerization solution was cooled to room temperature, 25.4 g of n-heptane was added, and the precipitated white powder was collected by filtration.
16.9 g of n-heptane was added to the collected white powder to form a slurry, followed by filtration and then drying with an evaporator to obtain 2.2 g of a polymer white powder. The obtained polymer was immersed in deuterated chloroform and allowed to stand at room temperature for 24 hours. When the obtained extract was measured by ¹ H-NMR, each residual monomer was not detected, and fluorinated copolymer-2 was synthesized. When the ¹³ C-NMR of the copolymer was measured, the content ratio of the repeating unit derived from diacrylate (1) and the repeating unit derived from styrene was 47:53 expressed in mol%.

[Example 5]
[Synthesis of fluorinated copolymer-3]
Except for changing the monomer from 0.6 g of styrene to 0.6 g of methyl methacrylate, a polymerization reaction and a post-treatment were performed in the same manner as in [Example 4] to obtain 2.5 g of a white powder of polymer. Also in the obtained polymer, each residual monomer was not detected, and fluorinated copolymer-3 was synthesized. When the ¹³ C-NMR of the copolymer was measured, the content ratio of the repeating unit derived from diacrylate (1) to the repeating unit derived from methyl methacrylate was 40:60 expressed in mol%.

FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a method for manufacturing a member with a pattern (pattern forming method) according to the present invention.

1: Curable composition 2: Substrate 3: Mold 4: Coating film 5: Cured film 6: Irradiation light

The fluorine-containing monomer represented by the general formula (1) obtained by the present invention, a fluorine-containing polymer polymerized or copolymerized using the same, and a curability containing a polymerization initiator and the fluorine-containing monomer Since the composition has a property of high filling speed, it can be used as a sealing material for semiconductors, an underfill material, a sealing material for organic EL elements or organic EL displays, and a bank material.

Claims (8)

1. A fluorine-containing monomer represented by the formula (1).
   

   

   (R ¹ and R ² are each independently a hydrogen atom or a methyl group.)
2. A curable composition comprising the fluorine-containing monomer according to claim 1 and a polymerization initiator.
3. The curable composition according to claim 2, wherein the polymerization initiator is a photopolymerization initiator.
4. The manufacturing method of the member with a pattern which arranged the cured film which has a pattern shape on a board | substrate including the following each process.
   Arranging step: A step of arranging the curable composition according to claim 2 or 3 on a substrate.
   Mold contact step: a step of bringing a mold having a pattern shape into contact with the curable composition disposed on the substrate.
   Curing step: a step of curing the curable composition in contact with the mold with light or heat to form a cured film.
   Mold release step: a step of separating the mold from the cured film to obtain the patterned member.
5. The method for producing a member with a pattern according to claim 4, wherein the mold contact step is performed in a gas atmosphere containing a condensable gas.
6. The condensable gas in the mold contact step is 1,1,1,3,3-pentafluoropropane (HFC-245fa), trans-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E) ), Cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)), trans-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), cis- The method for producing a patterned member according to claim 5, comprising at least one of 1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)).
7. The fluorine-containing monomer according to claim 1 is homopolymerized, or one kind selected from the group consisting of the fluorine-containing monomer and an acrylic ester, a methacrylic ester, a styrene compound, and an olefin. A fluorine-containing polymer obtained by copolymerizing the above monomers.
8. A step of homopolymerizing the fluorine-containing monomer according to claim 1, or
   And a step of copolymerizing the fluorine-containing monomer and one or more monomers selected from the group consisting of acrylic acid esters, methacrylic acid esters, styrene compounds, and olefins. A method for producing the fluorine-containing polymer as described.

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