WO2019189556A1 - Monomère fluoré, polymère fluoré, composition durcissable et procédé de production de motif - Google Patents

Monomère fluoré, polymère fluoré, composition durcissable et procédé de production de motif Download PDF

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WO2019189556A1
WO2019189556A1 PCT/JP2019/013542 JP2019013542W WO2019189556A1 WO 2019189556 A1 WO2019189556 A1 WO 2019189556A1 JP 2019013542 W JP2019013542 W JP 2019013542W WO 2019189556 A1 WO2019189556 A1 WO 2019189556A1
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curable composition
mold
meth
fluorine
acrylate
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PCT/JP2019/013542
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Japanese (ja)
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増渕　毅
実恵子 菊池
宮澤　覚
毅 小川
佑介 田中
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セントラル硝子株式会社
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Priority to JP2020509310A priority Critical patent/JP7277797B2/ja
Publication of WO2019189556A1 publication Critical patent/WO2019189556A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals

Definitions

  • 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.
  • 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.
  • active research is being conducted on curable compositions used in imprinting.
  • nanoimprinting the formation of a nano-sized (1 nm or more and 100 nm or less) uneven pattern is particularly called nanoimprinting.
  • 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.
  • acrylate can be suitably used as one component of the polymerizable compound for the application.
  • they 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 ⁇ m 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.
  • 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.
  • 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
  • the filling speed of the curable composition into the mold is also an important factor.
  • the time required for filling can greatly affect the working efficiency during nanoimprinting.
  • Patent Document 1 neopentyl glycol diacrylate shown below is particularly preferably used.
  • 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).
  • the number of capillaries (Ca) is derived from the following formula (i). (Ca: number of capillaries, ⁇ : surface tension, ⁇ 1 : mold contact angle, ⁇ 2 : substrate contact angle, ⁇ : viscosity, V: mold lowering speed, L and h 0 : apparatus constants depending on the imprint apparatus. )
  • the capillary number (Ca) is proportional to the viscosity ( ⁇ ) and inversely proportional to the surface tension ( ⁇ ). Mold contact angle ( ⁇ 1 ) and substrate contact angle ( ⁇ 2 ) are also important factors. As the number of capillaries (Ca) decreases, the filling rate increases.
  • 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 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).
  • 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).
  • the present invention includes the following inventions.
  • invention 2 A curable composition comprising the fluorine-containing monomer of Invention 1 and a polymerization 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
  • 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.
  • 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)).
  • 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.
  • 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.
  • 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.
  • (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.
  • 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"
  • any of these three types of fluorine-containing monomers can be preferably used.
  • 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.
  • 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.
  • 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 second step of obtaining the object to be expressed see the following formula.
  • 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).
  • 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.
  • 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”.
  • 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.
  • 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).
  • 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).
  • 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:
  • the implementation is not hindered.
  • “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.
  • 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.
  • additives can be added to accelerate the reaction.
  • Additives used can include organic sulfonic acids or Lewis acids.
  • the organic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and trifluoromethanesulfonic acid.
  • 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.
  • 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.
  • 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.
  • 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.
  • a solvent in consideration of the uniformity of the reaction and the operability after the reaction.
  • An aromatic compound, an ether solvent, and a halogen-type solvent can be mentioned.
  • the aromatic compound include benzene, toluene, xylene, or mesitylene.
  • ether solvents include diethyl ether, methyl-t-butyl ether, diisopropyl ether, and tetrahydrofuran.
  • 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.
  • 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.
  • 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.
  • 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.
  • a base examples 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.
  • 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.
  • 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.
  • 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.
  • the solvent examples 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.
  • 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.
  • GC gas chromatography
  • a base examples 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.
  • the fluorine-containing monomer represented by the formula (1) can be obtained by extraction, washing, distillation or column chromatography. Moreover, it can refine
  • 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.
  • 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.
  • curable composition containing the said fluorine-containing monomer as a structural component 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.
  • 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.
  • a curable composition contains a solvent, it is not prevented that there is little content of a polymeric compound from this.
  • 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.
  • a fluorine-containing monomer represented by the formula (1) may be used alone (see Example 1 in this specification).
  • “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.
  • the proportion of the “compound” mass is preferably 90% or more.
  • 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.
  • the proportion of the fluorine-containing monomer of the formula (1) is usually 10% or more, 30 % Or more is preferable.
  • the proportion of the fluorine-containing monomer of the formula (1) is usually 10% or more, 30 % Or more is preferable.
  • 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.
  • 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) acryl
  • acrylic compounds 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, Ky
  • 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.
  • the polymerization initiator includes a photopolymerization initiator and a thermal polymerization 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.
  • photoradical generator examples 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′-diamino
  • 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.
  • thermal radical generator examples include azo compounds and organic peroxides.
  • one polymerization initiator may be used alone, or two or more polymerization initiators may be used in combination.
  • a photopolymerization initiator is used as the initiator
  • a thermal polymerization initiator is used as the initiator.
  • 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.
  • 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.
  • additional additive components include surfactants, sensitizers, hydrogen donors, antioxidants, solvents, and polymer components.
  • 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.
  • the sensitizer include a hydrogen donor or a sensitizing dye.
  • 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.
  • the content of the sensitizer is 0.1% by mass or more, the polymerization promoting effect can be expressed more effectively.
  • content of a sensitizer is 10 mass% or less, there exists a tendency for solubility and storage stability to be excellent.
  • 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.
  • 4,4′-bis (dialkylamino) benzophenone include 4,4′-bis (diethylamino
  • 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.
  • the curable composition of the present invention may contain a polymer component.
  • 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.
  • curable composition Temporarily when compounding curable composition
  • 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.
  • 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 ⁇ m or more and 5.0 ⁇ m 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.
  • the concentration of metal impurities contained in the composition is preferably 10 ppm or less, and more preferably 100 ppb or less.
  • Pattern Forming Method 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”).
  • patterned member 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”).
  • 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).
  • the imprint includes a light imprint that is cured by light and a heat imprint that is cured by heat.
  • 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 ⁇ m or less is arranged on a substrate”.
  • 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.
  • 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.
  • 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.
  • a silicon wafer is usually used, but is not limited thereto.
  • 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 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.
  • 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.
  • Step [2] die contact step; FIG. 1 (b1), (b2)
  • 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
  • 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.
  • 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.
  • a light transparent resin is used as a constituent material of the mold 3
  • Quartz is particularly preferred because of its low thermal expansion coefficient.
  • 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.
  • the surface treatment method include a method of forming a release agent layer by applying a release agent to the surface of the mold.
  • 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.
  • a commercially available coating mold release agent such as trade name OPTOOL DSX manufactured by Daikin Industries, Ltd. can also be used.
  • a mold release agent may be used individually by 1 type, and may be used in combination of 2 or more types.
  • a fluorine-type mold release agent is particularly preferable.
  • 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.
  • 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.
  • an air atmosphere a reduced pressure atmosphere
  • an inert gas atmosphere there is no restriction
  • 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.
  • the condensable gas refers to a gas that satisfies the following requirements (i) and (ii).
  • the gas that is condensed and liquefied by the capillary pressure generated by the pressure at the time of filling 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
  • 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
  • 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.
  • 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.
  • condensable gases include chlorofluorocarbons (CFC), fluorocarbons (FC), hydrochlorofluoroolefins (HCFO), hydrofluoroolefins (HFO), hydrofluoroethers (HFE), and other fluorocarbons. To do.
  • Chlorofluorocarbon Chlorofluoromethane
  • FC Fluorocarbon
  • HCFO Hydrochlorofluoroolefin
  • 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
  • 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.
  • 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.
  • non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon.
  • 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.
  • Step [3] (Curing step; FIG. 1 (c))
  • 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.
  • 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.
  • 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.
  • 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.
  • the heating atmosphere and the heating temperature are not particularly limited.
  • 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.
  • a hot plate, oven, furnace, etc. can be used.
  • 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.
  • the substrate 2 substrate to be processed
  • 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.
  • both of them may be peeled by pulling in the opposite direction.
  • 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
  • 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.
  • 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.
  • 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).
  • 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.
  • the surface tension is 25.5 mN / m
  • the viscosity is 2.7 mPa ⁇ s
  • the mold contact angle is 51.6 °
  • the substrate contact angle is 11.5 °. Met.
  • 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 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.
  • 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.
  • 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.

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Abstract

La présente invention concerne une composition durcissable qui est appropriée pour réaliser une impression et qui offre un taux de remplissage élevé dans un micro-moule dans une technologie d'impression. La composition durcissable de la présente invention contient un initiateur de polymérisation ainsi qu'un monomère fluoré représenté par la formule (1) (R1 et R2 représentent chacun indépendamment un atome d'hydrogène ou un groupe méthyle). Le monomère fluoré représenté par la formule (1) peut être utilisé pour former un homopolymère ou peut être mélangé avec un autre monomère polymérisable pour former un copolymère. Par conséquent, en tant que monomère polymérisable contenu dans la composition durcissable, il est possible d'utiliser le monomère fluoré seul ou d'utiliser un mélange de divers monomères polymérisables.
PCT/JP2019/013542 2018-03-30 2019-03-28 Monomère fluoré, polymère fluoré, composition durcissable et procédé de production de motif WO2019189556A1 (fr)

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JP7442138B2 (ja) 2020-06-15 2024-03-04 パナソニックＩｐマネジメント株式会社 電子部品の実装方法

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JP2003040840A (ja) * 2001-07-24 2003-02-13 Central Glass Co Ltd 含フッ素重合性単量体およびそれを用いた高分子化合物
JP2009029974A (ja) * 2007-07-30 2009-02-12 Shin Etsu Chem Co Ltd 含フッ素単量体、含フッ素高分子化合物、レジスト材料及びパターン形成方法
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JP7442138B2 (ja) 2020-06-15 2024-03-04 パナソニックＩｐマネジメント株式会社 電子部品の実装方法
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