JP2013049841A - Curing resin composition for resin mold, resin mold, and replica mold fabricated using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing resin composition for a resin mold, and a resin mold, which allow transfer of a fine pattern of nano order, and are excellent in peelability.SOLUTION: Providing the curing resin composition for a resin mold, which contains a composite resin (A) having a polysiloxane segment (a1) and a vinylic polymer segment (a2), can provide the resin mold, which allows transfer of a fine pattern of nano order, and is excellent in peelability. There are also provided: a replica mold fabricated using the same; and a method for manufacturing the replica mold.

Description

  The present invention relates to a curable resin composition for a resin mold, a resin mold, and a replica mold produced using the same.

  As a technique for producing a resin molded body on which a fine concavo-convex pattern is formed, a technique is known in which a mold is cured while pressed against a resin. In particular, when the size of a fine pattern is nano-order, it is known as nanoimprint. Thus, the method of forming a pattern using a mold is characterized in that it can be manufactured at a lower cost and in a shorter time than using lithography or a direct drawing method.

  Generally, an initial mold called a master mold is prepared, and a resin molded product is directly created from the master mold, or a resin molded product can be prepared after transferring the master mold to a metal mold.

However, the master mold used as the first mold is made of quartz or silicon and is produced by an electron beam drawing method or the like, but it is known that the production is very expensive. In particular, in the case of a master mold for nanoimprinting in which a nano-order fine pattern is formed, not only is it expensive, but it takes a very long time to form a fine pattern.
Moreover, when producing a metal replica mold from a master mold, when taking out a replica mold after metal plating, it was necessary to destroy a master mold, and it was a problem from the surface of cost. In addition, when a resin molded body is created as a replica mold, the peelability from the master mold is insufficient, so the fine pattern of the master mold is lost or deformed, and there is a problem in the subsequent transferability. there were.

  Therefore, Patent Document 1 discloses that a resin mold is produced from a master mold and a metal mold is produced from the resin mold, and that the resin mold is produced from a vinyl monomer having an epoxy group. Yes. By removing the resin mold, a replica mold can be produced without damaging the master mold. However, because the resin mold has poor releasability, operations such as heating above the glass transition point or immersion in a solvent are required. The problem of being is not solved.

JP 2011-25877 A

    The problem to be solved by the present invention is to provide a curable resin composition for a resin mold, which can transfer a nano-order fine pattern and has excellent peelability, and a resin mold.

  As a result of intensive studies, the present inventors have found that a curable resin composition for resin molds containing a specific siloxane resin solves the above problems.

  That is, the present invention relates to a polysiloxane segment (a1) having a structural unit represented by general formula (1) and / or general formula (2), a silanol group and / or a hydrolyzable silyl group, Provided is a curable resin composition for a resin mold, which comprises a composite resin (A) in which a coalesced segment (a2) is bonded by a bond represented by the general formula (3).

（１）

(1)

（２）

(2)

(In the general formulas (1) and (2), R ¹ , R ² and R ³ are each independently -R ⁴ -CH = CH ₂ , -R ⁴ -C (CH ₃ ) = CH ₂ ,- A group having one polymerizable double bond selected from the group consisting of R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ and —R ⁴ —O—CO—CH═CH ₂ (where R ⁴ is A single bond, an aryl group, or an alkylene group having 1 to 6 carbon atoms.), An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or a carbon atom A aralkyl group having a number of 7 to 12 or a group in which part or all of the hydrogen atoms of the alkyl group, cycloalkyl group, aryl group or aralkyl group are substituted with fluorine atoms)

（３）
（一般式（３）中、炭素原子は前記ビニル系重合体セグメント（ａ２）の一部分を構成し、酸素原子のみに結合したケイ素原子は、前記ポリシロキサンセグメント（ａ１）の一部分を構成するものとする。

(3)
(In the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). To do.

  Moreover, this invention provides the resin mold formed by hardening | curing the said curable resin composition for resin molds.

  Moreover, this invention provides the manufacturing method of the replica mold produced from the said resin mold, and a replica mold.

  According to the present invention, it is possible to obtain a curable resin composition for a resin mold that can be transferred even with a nano-order size pattern and has excellent releasability from a master mold and a replica mold.

(Composite resin (A))
The composite resin (A) used in the present invention is a polysiloxane having a structural unit represented by the general formula (1) and / or the general formula (2), and a silanol group and / or a hydrolyzable silyl group. A composite resin (A) in which a segment (a1) (hereinafter simply referred to as a polysiloxane segment (a1)) and a vinyl polymer segment (a2) are bonded by a bond represented by the general formula (3) is there. The bond represented by the general formula (3) can withstand repeated use as a mold because the resulting resin mold is excellent in scratch resistance and releasability, and can transfer patterns in the nano-order size. It is preferable because it is excellent in releasability from the master mold.

（３）

(3)

The silanol group and / or hydrolyzable silyl group possessed by the polysiloxane segment (a1) described later and the silanol group and / or hydrolyzable silyl group possessed by the vinyl polymer segment (a2) described below undergo a dehydration condensation reaction. Thus, the bond represented by the general formula (3) is generated. Accordingly, in the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). And
The form of the composite resin (A) is, for example, a composite resin having a graft structure in which the polysiloxane segment (a1) is chemically bonded as a side chain of the polymer segment (a2), or the polymer segment (a2). And a composite resin having a block structure in which the polysiloxane segment (a1) is chemically bonded.

(Polysiloxane segment (a1))
The polysiloxane segment (a1) in the present invention is a segment having a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group.
Further, the structural unit represented by the general formula (1) and / or the general formula (2) may have a group having a polymerizable double bond.
Moreover, the polysiloxane segment (a1) in the present invention may further have an epoxy group.

(Structural unit represented by general formula (1) and / or general formula (2))
The structural unit represented by the general formula (1) and / or the general formula (2) may have a group having a polymerizable double bond.
Specifically, R ¹ , R ² and R ³ in the general formulas (1) and (2) are each independently —R ⁴ —CH═CH ₂ , —R ⁴ —C (CH ₃ ) = A group having one polymerizable double bond selected from the group consisting of CH ₂ , —R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ , and —R ⁴ —O—CO—CH═CH ₂ ( R ⁴ represents a single bond, an aryl group, or an alkylene group having 1 to 6 carbon atoms), an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, Alternatively, it represents an aralkyl group having 7 to 12 carbon atoms, or a group in which some or all of the hydrogen atoms of the alkyl group, cycloalkyl group, aryl group, or aralkyl group are substituted with fluorine atoms.

Examples of the alkylene group having 1 to 6 carbon atoms in R ⁴ include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, Pentylene group, isopentylene group, neopentylene group, tert-pentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohesylene group, 1-methylpentylene Len group, 2-methylpentylene group, 3-methylpentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1 , 2-trimethylpropylene group, 1,2,2-trimethylpropylene group, 1-ethyl-2 -A methylpropylene group, 1-ethyl-1-methylpropylene group, etc. are mentioned. Among these, R ⁴ is preferably a single bond, an aryl group, or an alkylene group having 2 to 4 carbon atoms because of easy availability of raw materials.

Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and isopentyl. Group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl Group, 3-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2 , 2-trimethylpropyl group, 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group, and the like.
Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.
The group in which some or all of the hydrogen atoms of the alkyl group, cycloalkyl group, aryl group, and aralkyl group are substituted with fluorine atoms is specifically a fluoroalkyl group having 1 to 6 carbon atoms. , Polyfluoroalkyl group, perfluoroalkyl group; or fluorocycloalkyl group having 3 to 8 carbon atoms, polyfluorocycloalkyl group, perfluorocycloalkyl group; or fluoroaryl group, polyfluoroaryl group, perfluoroaryl A group; or a fluoroaralkyl group having 7 to 12 carbon atoms, a polyfluoroaralkyl group, a perfluoroaralkyl group;
Examples include a fluoroalkyl group, a difluoroalkyl group, a trifluoroalkyl group, a polyfluoroalkyl group, and the like, and a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and the like. It is done.

Further, at least one of R ¹ , R ² and R ³ is preferably a group having the polymerizable double bond. Specifically, the polysiloxane segment (a1) is represented by the general formula (1). R ¹ is a group having a polymerizable double bond in the case where it has only a structural unit, and R ^{2 in the} case where the polysiloxane segment (a1) has only a structural unit represented by the general formula (2). And / or R ³ is a group having the polymerizable double bond, and the polysiloxane segment (a1) has both of the structural units represented by the general formula (1) and the general formula (2), It is preferable that at least one of R ¹ , R ² and R ³ is a group having a polymerizable double bond.

The polysiloxane segment (a1) of the present invention preferably has an epoxy group, and at least one of R ¹ , R ² and R ³ is preferably a group having an epoxy group.

In the present invention, it is preferable that two or more polymerizable double bonds exist in the polysiloxane segment (a1), more preferably 3 to 200, and more preferably 3 to 50. Preferably, a resin mold having excellent scratch resistance can be obtained. Specifically, if the content of the polymerizable double bond in the polysiloxane segment (a1) is 3 to 20% by weight, desired scratch resistance can be obtained.
Here, the calculation of the content of the polymerizable double bond is as follows. The molecular weight is 27 for a group having —CH═CH _2, and the molecular weight is 41 for a group having —C (CH ₃ ) ═CH _2. Calculated.

  The structural unit represented by the general formula (1) and / or the general formula (2) is a three-dimensional network polysiloxane structural unit in which two or three of the silicon bonds are involved in crosslinking. Since a dense network structure is not formed while a three-dimensional network structure is formed, gelation or the like does not occur during production, and the long-term storage stability of the resulting composite resin is improved.

(Silanol group and / or hydrolyzable silyl group)
In the present invention, the silanol group is a silicon-containing group having a hydroxyl group directly bonded to a silicon atom. Specifically, the silanol group is a silanol group formed by combining an oxygen atom having a bond with a hydrogen atom in the structural unit represented by the general formula (1) and / or the general formula (2). Preferably there is.

  In the present invention, the hydrolyzable silyl group is a silicon-containing group having a hydrolyzable group directly bonded to a silicon atom, and specifically includes, for example, a group represented by the general formula (4). .

（４）

(4)

(In the general formula (4), R ⁵ is a monovalent organic group such as an alkyl group, an aryl group or an aralkyl group, and R ⁶ is a halogen atom, an alkoxy group, an acyloxy group, a phenoxy group, an aryloxy group, a mercapto group, (It is a hydrolyzable group selected from the group consisting of an amino group, an amide group, an aminooxy group, an iminooxy group and an alkenyloxy group, and b is an integer of 0 to 2.)

Examples of the alkyl group in R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a tert group. -Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl Group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group 1-ethyl-2-methylpropyl group, 1-ethyl-1-methylpropyl group, and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, and a 3-isopropylphenyl group.
Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

In R ⁶ , examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Including a fluorine atom is particularly preferable because the obtained resin mold is excellent in releasability.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group, and a third butoxy group.
Examples of the acyloxy group include formyloxy, acetoxy, propanoyloxy, butanoyloxy, pivaloyloxy, pentanoyloxy, phenylacetoxy, acetoacetoxy, benzoyloxy, naphthoyloxy and the like.
Examples of the aryloxy group include phenyloxy and naphthyloxy.
Examples of the alkenyloxy group include a vinyloxy group, allyloxy group, 1-propenyloxy group, isopropenyloxy group, 2-butenyloxy group, 3-butenyloxy group, 2-petenyloxy group, 3-methyl-3-butenyloxy group, 2 -A hexenyloxy group etc. are mentioned.

By hydrolyzing the hydrolyzable group represented by R ⁶ , the hydrolyzable silyl group represented by the general formula (4) becomes a silanol group. Among these, a methoxy group and an ethoxy group are preferable because of excellent hydrolyzability.
The hydrolyzable silyl group specifically includes an oxygen atom having a bond in the structural unit represented by the general formula (1) and / or the general formula (2) bonded to the hydrolyzable group. Or it is preferable that it is the hydrolyzable silyl group substituted.

The silanol group or the hydrolyzable silyl group is formed between the hydroxyl group in the silanol group or the hydrolyzable group in the hydrolyzable silyl group in parallel with the ultraviolet curing reaction when the coating film is formed by ultraviolet curing. Since the hydrolysis condensation reaction proceeds, the crosslink density of the polysiloxane structure of the obtained resin mold is increased, and a resin mold having excellent solvent resistance can be formed.
Further, the polysiloxane segment (a1) containing the silanol group or the hydrolyzable silyl group and the vinyl polymer segment (a2) having an acid group described later are bonded to each other by the general formula (3). Used when connecting via

The polysiloxane segment (a1) is not particularly limited except that it has a structural unit represented by the general formula (1) and / or the general formula (2), and a silanol group and / or a hydrolyzable silyl group. Other groups may be included. For example,
A structural unit R ¹ is a group having a polymerizable double bond in the formula (1), R ¹ in the general formula (1) fluoroalkyl such as an alkyl group and / or perfluoro-methyl, such as methyl It may be a polysiloxane segment (a1) in which a structural unit as a group coexists,
A structural unit R ¹ is a group having a polymerizable double bond in the formula (1), alkyl groups and / or perfluoro-fluoro methyl, etc. R ¹ and methyl groups in the general formula (1) A polysiloxane segment in which a structural unit that is an alkyl group and a structural unit in which R ² and R ³ in the general formula (2) are an alkyl group such as a methyl group and / or a fluoroalkyl group such as perfluoromethyl coexist ( a1), or
A structural unit in which R ¹ in the general formula (1) is a group having a polymerizable double bond, and R ² and R ³ in the general formula (2) are alkyl groups such as a methyl group and / or perfluoromethyl. The polysiloxane segment (a1) coexisting with a structural unit which is a fluoroalkyl group such as the like may be used, and there is no particular limitation.
In addition to the above, a structure containing a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, contained in the polysiloxane segment (a1) By substituting a part of hydrogen of the units R1, R2, R3, R4, R5, and R6 with fluorine, it is possible to improve the releasability of the transferred material when used as a molding resin. The amount of fluorine component in the polysiloxane segment (a1) can be appropriately selected depending on the relationship with the amount of fluorine component in the vinyl polymer segment (a2) described later. The fluorine component not only increases the releasability of the transferred material by lowering the surface energy of the resin mold, but also the fluorine component contained in the polysiloxane segment (a1) decreases the surface energy of the segment portion (a1). (A1) The segment portion is promoted to be exposed on the mold surface. The polysiloxane segment that appears on the surface can be easily treated with a release agent such as a fluorine-based or silicone-based silane coupling agent, and the modification effect can be maintained over a long period of time. Order size pattern transfer is possible and preferable. As the fluorine-based release agent, OPTOOL DSX, OPTOOL HD1100, OPTOOL HD2100, and the like are preferable.

  Specifically, examples of the polysiloxane segment (a1) include those having the following structures.

  In the present invention, the polysiloxane segment (a1) is preferably contained in an amount of 10 to 90% by weight based on the total solid content of the composite resin (A), and it is possible to achieve both high scratch resistance and moldability. It becomes. Among these, it is preferable to contain 10 to 60% by weight.

(Composite resin (A) vinyl polymer segment (a2))
The vinyl polymer segment (a2) in the present invention is a vinyl polymer segment such as an acrylic polymer, a fluoroolefin polymer, a vinyl ester polymer, an aromatic vinyl polymer, and a polyolefin polymer. . These are preferably selected appropriately depending on the application.

  For example, the acrylic polymer is obtained by polymerizing or copolymerizing a general-purpose (meth) acrylic monomer. The (meth) acrylic monomer is not particularly limited, and vinyl monomers can also be copolymerized. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) Alkyl (meth) acrylates having an alkyl group having 1 to 22 carbon atoms such as acrylate and lauryl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate Cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; ω-alkoxyalkyl such as 2-methoxyethyl (meth) acrylate and 4-methoxybutyl (meth) acrylate ( ) Acrylates; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and other carboxylic acid vinyl esters; methyl crotonate, alkyl crotonate and other alkyl esters; dimethyl malate, di-n -Dialkyl esters of unsaturated dibasic acids such as butyl malate, dimethyl fumarate and dimethyl itaconate; α-olefins such as ethylene and propylene; vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene and the like Fluoroolefins; alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether and cyclohexyl vinyl ether; N, N-dimethyl (meth) Acrylamide, N- (meth) acryloyl morpholine, N- (meth) acryloyl pyrrolidine, tertiary amide group-containing monomers such as N- vinylpyrrolidone and the like.

(Fluorine-containing monomer)
In the composite resin (A), a fluorine-containing monomer can be copolymerized. The presence of fluorine is preferable because the mold release property of the resin mold is more excellent.
When the fluorine-containing monomer is copolymerized with the vinyl polymer segment (a2), it is preferable to use a radical polymerizable unsaturated monomer containing a fluorinated alkyl group.

(Radically polymerizable unsaturated monomer having a fluorinated alkyl group)
Fluorinated alkyl group (functional group in which 1 or 2 or more carbon atoms to which 1 to 3 fluorine atoms are bonded are connected, carbon atom in the fluorinated alkyl group is an unsaturated bond, fluorinated alkyl Examples of the radical polymerizable unsaturated monomer having a carbon atom in the group linked by an ether bond with an oxygen atom include monomers represented by the following general formula (1).

(In the general formula (1), R represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a benzyl group, or -CnH2n-Rf '(n represents an integer of 1 to 8, and Rf' represents the following formula) (Rf-1) to (Rf-7) represents one group), and R ′ represents any one of the following formulas (R′-1) to (R′-10). Rf represents any one group of the following formulas (Rf-1) to (Rf-7).

(N in the above formulas (R′-1), (R′-3), (R′-5), (R′-6) and (R′-7) represents an integer of 1 to 8.) M in the formulas (R′-8), (R′-9) and (R′-10) represents an integer of 1 to 8, and n represents an integer of 0 to 8. The above formula (R′-6) ) And (R′-7
) In R) represents any one of the following formulas (Rf-1) to (Rf-7). )

(In the formulas (Rf-1) and (Rf-2), n represents an integer of 1 to 6. The formula (Rf-3
N in) represents an integer of 2-6. N in the above formula (Rf-4) represents an integer of 4 to 6. M in the said formula (Rf-5) is an integer of 1-5, n is an integer of 0-4, and the sum total of m and n is 1-5. M in the formula (Rf-6) is an integer of 0 to 4, n is an integer of 1 to 4, p is an integer of 0 to 4, and the sum of m, n, and p is 1 to 4. 5. )

Among the monomers represented by the general formula (1), the fluorinated alkyl group has 4 to 6 carbon atoms.
Is preferable from the viewpoint of excellent liquid repellency. More specific examples of the preferred monomer (f1) include the following monomers (f1-1) to (f1-15).

(The above formulas (f1-6), (f1-7), (f1-13), (f1-14) and (f1-
N in 13) represents 3 or 5. )

  Further, a compound having a poly (perfluoroalkylene ether) chain and a structural portion having a radical polymerizable group at both ends thereof may be used.

  Those represented by the structural formulas F-1 to F-10 can be given. In the above structural formulas, “—PFPE—” represents a poly (perfluoroalkylene ether) chain.

  There are no particular limitations on the polymerization method, solvent, or polymerization initiator for copolymerizing the monomers, and the vinyl polymer segment (a2) can be obtained by a known method. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-) can be obtained by various polymerization methods such as bulk radical polymerization, solution radical polymerization, and non-aqueous dispersion radical polymerization. Dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), tert-butylperoxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di- The vinyl polymer segment (a2) can be obtained by using a polymerization initiator such as tert-butyl peroxide, cumene hydroperoxide, diisopropyl peroxycarbonate or the like.

(Vinyl polymer segment (a2) having an acid group)
The resin mold in the present invention does not require alkali cleaning because of its excellent releasability, but may be subjected to alkali cleaning when developing a very complicated shape such as nanoimprint. For alkali cleaning, the resin mold and replica mold may be immersed in an alkaline solution together to dissolve the resin mold. May be washed away.

  The vinyl polymer segment (a2) in the present invention is made of an acrylic polymer having an acid group, a fluoroolefin polymer, a vinyl ester polymer, and an aromatic vinyl in order to make the resin mold alkali soluble so that it can be washed with alkali. A vinyl polymer segment such as a polymer and a polyolefin polymer is preferred. Among these, an acrylic polymer segment obtained by copolymerizing a (meth) acrylic monomer having an acid group is preferable from the viewpoint of excellent transparency of the resulting coating film.

  Examples of (meth) acrylic monomers containing an acid group include various unsaturated carboxylic acids such as (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid or fumaric acid; Various kinds of saturated dicarboxylic acids and saturated monohydric alcohols such as monomethyl acid, mono-n-butyl itaconate, monomethyl maleate, mono-n-butyl maleate, monomethyl fumarate and mono-n-butyl fumarate Monoesters (half esters); monovinyl esters of various saturated dicarboxylic acids such as monovinyl adipate or monovinyl succinate; various types such as succinic anhydride, glutaric anhydride, phthalic anhydride or trimellitic anhydride And anhydrides of saturated polycarboxylic acids. Of these, (meth) acrylic acid is preferable because it is easy to react.

  The content of the acid group described above is preferably contained so as to be in the range of 30 to 400 KOHmg / g in terms of the acid value of the composite resin (A). If it is 30 KOHmg / g or more, the alkali solubility is excellent, and if it is 400 KOHmg / g or less, gelation at the time of synthesis is suppressed, which is preferable. In particular, it is particularly preferably 300 KOH mg / g or less because both alkali solubility and resin mold releasability can be achieved.

  The number average molecular weight of the vinyl polymer segment (a2) is preferably in the range of 500 to 200,000 in terms of number average molecular weight (hereinafter abbreviated as Mn), and the composite resin (A) is produced. It is possible to prevent thickening and gelation during the process and to have excellent durability. Among these, Mn is more preferably in the range of 700 to 100,000, and the range of 1,000 to 50,000 is still more preferable for the reason that a good cured film can be formed when a layer is formed on the substrate.

  In addition, the vinyl polymer segment (a2) is a vinyl polymer segment (A) in order to form a composite resin (A) bonded by the bond represented by the general formula (3) with the polysiloxane segment (a1). It has a silanol group and / or a hydrolyzable silyl group directly bonded to the carbon atom in a2). Since these silanol groups and / or hydrolyzable silyl groups become bonds represented by the general formula (3) in the production of the composite resin (A) described later, the composite resin (A ) In the vinyl polymer segment (a2). However, there is no problem even if silanol groups and / or hydrolyzable silyl groups remain in the vinyl polymer segment (a2), and when the coating film is formed by the curing reaction of the group having a polymerizable double bond. In parallel with the curing reaction, a hydrolytic condensation reaction proceeds between the hydroxyl group in the silanol group or the hydrolyzable group in the hydrolyzable silyl group, so that the crosslink density of the polysiloxane structure of the resulting cured product And a cured product excellent in solvent resistance can be formed.

Specifically, the vinyl polymer segment (a2) having a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom includes the general-purpose monomer, the silanol group directly bonded to the carbon bond, and / or It is obtained by copolymerizing a vinyl monomer containing a hydrolyzable silyl group.
Examples of vinyl monomers containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon atom include vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinyltri (2-methoxyethoxy) silane. , Vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyl Examples include methyldimethoxysilane and 3- (meth) acryloyloxypropyltrichlorosilane. Among these, vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane are preferable because the hydrolysis reaction can easily proceed and by-products after the reaction can be easily removed.

Moreover, when containing reactive compounds, such as polyisocyanate (B) mentioned later, it is preferable that the said vinyl-type polymer segment (a2) has reactive functional groups, such as alcoholic hydroxyl group. For example, the vinyl polymer segment (a2) having an alcoholic hydroxyl group can be obtained by copolymerizing a (meth) acrylic monomer having an alcohol hydroxyl group. Specific examples of the (meth) acrylic monomer having an alcohol hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) ) Acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl mono Various α such as butyl fumarate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, “Placcel FM or Plaxel FA” [Caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.] Hydroxyalkyl esters of β- ethylenically unsaturated carboxylic acid or an adduct thereof with ε- caprolactone, and the like.
Of these, 2-hydroxyethyl (meth) acrylate is preferable because it is easy to react.

  It is preferable that the amount of the alcoholic hydroxyl group is appropriately determined by calculating from the amount of polyisocyanate to be described later.

(Production method of composite resin (A))
Specifically, the composite resin (A) used in the present invention is produced by the methods shown in the following (Method 1) to (Method 3).

(Method 1) (meth) acrylic monomer having acid group, general-purpose (meth) acrylic monomer, etc., and vinyl monomer containing silanol group and / or hydrolyzable silyl group directly bonded to carbon bond To obtain a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond. A silane compound having both a silanol group and / or a hydrolyzable silyl group and a polymerizable double bond, and, if necessary, a general-purpose silane compound are mixed and subjected to a hydrolysis condensation reaction.
In this method, a silanol group and / or hydrolyzable silyl group and a silanol group or hydrolyzable silyl group of a silane compound having both a polymerizable double bond and a silanol group and / or hydrolyzed directly bonded to a carbon bond. The silanol group and / or hydrolyzable silyl group of the vinyl polymer segment (a2) containing a functional silyl group undergoes a hydrolytic condensation reaction to form the polysiloxane segment (a1), and the polysiloxane The composite resin (A) in which the segment (a1) and the vinyl polymer segment (a2) having an alcoholic hydroxyl group are combined by the bond represented by the general formula (3) is obtained.

(Method 2) In the same manner as in Method 1, a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond is obtained.
On the other hand, a polysiloxane segment (a1) is obtained by subjecting a silane compound having both a silanol group and / or a hydrolyzable silyl group and a polymerizable double bond and, if necessary, a general-purpose silane compound to a hydrolysis condensation reaction. Then, the silanol group and / or hydrolyzable silyl group of the vinyl polymer segment (a2) and the silanol group and / or hydrolyzable silyl group of the polysiloxane segment (a1) are hydrolyzed and condensed. Let

  (Method 3) Similarly to Method 1, a vinyl polymer segment (a2) containing a silanol group and / or a hydrolyzable silyl group directly bonded to a carbon bond is obtained. On the other hand, the polysiloxane segment (a1) is obtained in the same manner as in Method 2. Furthermore, a silane compound containing a silane compound having a polymerizable double bond and a general-purpose silane compound as necessary are mixed and subjected to a hydrolysis condensation reaction.

  Specific examples of the silane compound having both a silanol group and / or a hydrolyzable silyl group and a polymerizable double bond used in the (Method 1) to (Method 3) include, for example, vinyltrimethoxysilane, Vinyltriethoxysilane, vinylmethyldimethoxysilane, vinyltri (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinyltrichlorosilane, 2-trimethoxysilylethyl vinyl ether, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (Meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrichlorosilane and the like. Among these, vinyltrimethoxysilane and 3- (meth) acryloyloxypropyltrimethoxysilane are preferable because the hydrolysis reaction can easily proceed and by-products after the reaction can be easily removed.

  Examples of the general-purpose silane compound used in the (Method 1) to (Method 3) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, and n-propyl. Various organotrialkoxysilanes such as trimethoxysilane, iso-butyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane Various diorganodialkoxysilanes such as diethyldimethoxysilane, diphenyldimethoxysilane, methylcyclohexyldimethoxysilane, and methylphenyldimethoxysilane; Chill trichlorosilane, phenyl trichlorosilane, vinyl trichlorosilane, dimethyl dichlorosilane, chlorosilane such as diethyl dichlorosilane or diphenyl dichlorosilane and the like. Of these, organotrialkoxysilanes and diorganodialkoxysilanes that can easily undergo a hydrolysis reaction and easily remove by-products after the reaction are preferable.

Further, when the polysiloxane segment (a1) has an epoxy group, an epoxy group-containing silane compound may be used.
Epoxy group-containing silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltriacetoxysilane, γ-glycidoxypropyldimethoxymethylsilane, γ-glycidoxypropyldiethoxymethylsilane, γ-glycidoxypropyldimethoxyethoxymethylsilane, γ-glycidoxypropyldiacetoxy Methylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethoxymethylsilane, β -(3,4-epoxycyclohexyl) ethyldiacetoxymethylsilane, γ-glycidoxypropyldimethoxyethylsilane, γ-glycidoxypropyldiethoxyethylsilane, γ-glycidoxypropyldimethoxyethoxyethylsilane, γ-glycyl Sidoxypropyldiacetoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldimethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxyethylsilane, β- (3,4-epoxycyclohexyl) Tildimethoxyethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethyldiacetoxyethylsilane, γ-glycidoxypropyldimethoxyisopropylsilane, γ-glycidoxypropyldiethoxyisopropylsilane, γ-glycidoxypropyldimethoxy Ethoxyisopropylsilane, γ-glycidoxypropyldiacetoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldiethoxyisopropylsilane, β- ( 3,4-epoxycyclohexyl) ethyldimethoxyethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethyldiacetoxyisopropylsilane, γ-glycidoxypropylmethoxydi Methylsilane, γ-glycidoxypropylethoxydimethylsilane, γ-glycidoxypropylmethoxyethoxydimethylsilane, γ-glycidoxypropylacetoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxydimethylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxydimethylsilane, γ-glycidoxypropyl Methoxydiethylsilane, γ-glycidoxypropylethoxydiethylsilane, γ-glycidoxypropylmethoxyethoxydiethylsilane, γ-glycidoxypropylacetoxydiethylsilane, β- (3,4-epoxy Cyclohexyl) ethylmethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxydiethylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxy Diethylsilane, γ-glycidoxypropylmethoxydiisopropylsilane, γ-glycidoxypropylethoxydiisopropylsilane, γ-glycidoxypropylmethoxyethoxydiisopropylsilane, γ-glycidoxypropylacetoxydiisopropylsilane, β- (3,4) -Epoxycyclohexyl) ethylmethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) ethylethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) Tylmethoxyethoxydiisopropylsilane, β- (3,4-epoxycyclohexyl) ethylacetoxydiisopropylsilane, γ-glycidoxypropylmethoxyethoxymethylsilane, γ-glycidoxypropylacetoxymethoxymethylsilane, γ-glycidoxypropylacetoxy Ethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxymethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyacetoxymethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxyacetoxymethyl Silane, γ-glycidoxypropylmethoxyethoxyethylsilane, γ-glycidoxypropylacetoxymethoxyethylsilane, γ-glycidoxypropylacetoxyethoxyethylsila , Β- (3,4-epoxycyclohexyl) ethylmethoxyethoxyethylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyacetoxyethylsilane, β- (3,4-epoxycyclohexyl) ethylethoxyacetoxyethylsilane, γ -Glycidoxypropylmethoxyethoxyisopropylsilane, γ-glycidoxypropylacetoxymethoxyisopropylsilane, γ-glycidoxypropylacetoxyethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyethoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethylmethoxyacetoxyisopropylsilane, β- (3,4-epoxycyclohexyl) ethylethoxyacetoxyisopropylsilane, glycidoxymethyl Rutrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxymethyltrimethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxymethyltrimethoxy Silane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxy Silane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxy Silane, β-glycy Xylbutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxy Silane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltryptoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- ( 3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxy (Cyclohexyl) butyl Liethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxy Silane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropyl Methyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ Glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxy Examples thereof include silane, γ-glycidoxypropylvinyldimethoxysilane, and γ-glycidoxypropylvinyldiethoxysilane.

  Moreover, the silane coupling agent which has a fluorinated alkyl group can also be used, for example, trifluoropropyl trimethoxysilane etc. are mention | raise | lifted, and Shin-Etsu Chemical Co., Ltd. KBM-7013 etc. are mentioned as a commercial item. . When the composite resin (A) contains a fluorine atom, it is particularly preferable because the obtained resin mold is excellent in releasability.

    In addition, a tetrafunctional alkoxysilane compound such as tetramethoxysilane, tetraethoxysilane or tetra n-propoxysilane or a partial hydrolysis condensate of the tetrafunctional alkoxysilane compound may be used in combination as long as the effects of the present invention are not impaired. it can. When the tetrafunctional alkoxysilane compound or a partially hydrolyzed condensate thereof is used in combination, the silicon atoms of the tetrafunctional alkoxysilane compound are 20 with respect to the total silicon atoms constituting the polysiloxane segment (a1). It is preferable to use together so that it may become the range which does not exceed mol%.

    In addition, a metal alkoxide compound other than a silicon atom such as boron, titanium, zirconium or aluminum can be used in combination with the silane compound as long as the effects of the present invention are not impaired. For example, it is preferable to use the metal alkoxide compound in combination in a range not exceeding 25 mol% with respect to all silicon atoms constituting the polysiloxane segment (a1).

    In the hydrolysis condensation reaction in the (Method 1) to (Method 3), a part of the hydrolyzable group is hydrolyzed under the influence of water or the like to form a hydroxyl group, and then the hydroxyl groups or the hydroxyl group and the hydrolysis are hydrolyzed. This refers to a proceeding condensation reaction that proceeds with a functional group. The hydrolysis-condensation reaction can be performed by a known method, but a method in which the reaction is advanced by supplying water and a catalyst in the production process is simple and preferable.

  Examples of the catalyst used include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as p-toluenesulfonic acid, monoisopropyl phosphate and acetic acid; inorganic bases such as sodium hydroxide and potassium hydroxide; tetraisopropyl titanate , Titanates such as tetrabutyl titanate; 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1 Compounds containing various basic nitrogen atoms, such as 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine, dimethylbenzylamine, monoethanolamine, imidazole, 1-methylimidazole; Tetramethylammonium salt, tetrabutylammonium salt, dilauryldimethylammonium Quaternary ammonium salts having chloride, bromide, carboxylate or hydroxide as a counter anion; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetylacetate Examples thereof include tin carboxylates such as narate, tin octylate and tin stearate. A catalyst may be used independently and may be used together 2 or more types.

    The amount of the catalyst to be added is not particularly limited, but generally it is preferably used in the range of 0.0001 to 10% by weight with respect to the total amount of each compound having the silanol group or hydrolyzable silyl group. , More preferably in the range of 0.0005 to 3% by weight, and particularly preferably in the range of 0.001 to 1% by weight.

The amount of water to be supplied is preferably 0.05 mol or more with respect to 1 mol of the silanol group or hydrolyzable silyl group of each compound having the silanol group or hydrolyzable silyl group, The above is more preferable, and particularly preferably 0.5 mol or more.
These catalyst and water may be supplied collectively or sequentially, or may be supplied by previously mixing the catalyst and water.

    The reaction temperature for carrying out the hydrolytic condensation reaction in the above (Method 1) to (Method 3) is suitably in the range of 0 ° C to 150 ° C, and preferably in the range of 20 ° C to 100 ° C. The reaction can be carried out under any conditions of normal pressure, increased pressure, or reduced pressure. Moreover, you may remove the alcohol and water which are the by-products which can be produced | generated in the said hydrolysis-condensation reaction by methods, such as distillation, as needed.

  The charging ratio of each compound in the (Method 1) to (Method 3) is appropriately selected depending on the desired structure of the composite resin (A) used in the present invention. Especially, since the durability of the obtained coating film is excellent, it is preferable to obtain the composite resin (A) such that the content of the polysiloxane segment (a1) is 30 to 80% by weight, and 30 to 75% by weight. Further preferred.

  In the above (Method 1) to (Method 3), as a specific method for conjugating the polysiloxane segment and the vinyl polymer segment in a block form, the above-mentioned silanol group and Using a vinyl polymer segment having a structure having a hydrolyzable silyl group as an intermediate, for example, in the case of (Method 1), a silanol group and / or hydrolysis is added to the vinyl polymer segment. And a silane compound having both a polymerizable silyl group and a polymerizable double bond, and a general-purpose silane compound as required, followed by a hydrolysis condensation reaction.

  On the other hand, in the above (Method 1) to (Method 3), as a specific method of complexing the polysiloxane segment to the vinyl polymer segment in a graft form, the main chain of the vinyl polymer segment is The vinyl polymer segment having a structure in which silanol groups and / or hydrolyzable silyl groups are randomly distributed is used as an intermediate. For example, in the case of (Method 2), the vinyl polymer segment is Examples thereof include a method in which a hydrocondensation reaction is carried out between the silanol group and / or hydrolyzable silyl group possessed and the silanol group and / or hydrolyzable silyl group possessed by the polysiloxane segment.

(Curable resin composition for resin mold)
In the curable composition for resin molds of the present invention, the content of the polysiloxane segment (a1) in the total solid content of the curable composition for resin molds is not particularly limited, but is 10 to 90% by weight. preferable. If it is 10% or more, it is preferable because it is excellent in releasability due to curing of the contained silanol group and / or hydrolyzable silyl group.

The curable resin composition for a resin mold of the present invention preferably contains a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator according to the curing method.
What is necessary is just to use a well-known thing in a photocurable resin composition as a photoinitiator, For example, 1 or more types chosen from the group which consists of acetophenones, benzyl ketals, and benzophenones can be used preferably. Examples of the acetophenones include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4 -(2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and the like. Examples of the benzyl ketals include 1-hydroxycyclohexyl-phenyl ketone and benzyl dimethyl ketal. Examples of the benzophenones include benzophenone and methyl o-benzoylbenzoate. Examples of the benzoins include benzoin, benzoin methyl ether, and benzoin isopropyl ether. A photoinitiator may be used independently and may use 2 or more types together.

  Moreover, when the composite resin (A) has a photocationically polymerizable group such as a vinyl ether group or an epoxy group, a photocation initiator can be used in combination. Examples of the photocation initiator include a diazonium salt of a Lewis acid, an iodonium salt of a Lewis acid, a sulfonium salt of a Lewis acid, and the cation part is an aromatic diazonium, an aromatic iodonium, an aromatic sulfonium, and an anion. Preferably, the moiety is an onium salt composed of BF4-, PF6-, SbF6-, [BY4]-(wherein Y is a phenyl group substituted with at least two fluorine atoms or a trifluoromethyl group) and the like. Is a cationic polymerization initiator which is a phosphorus compound from the viewpoint of stability. Specifically, boron tetrafluoride phenyldiazonium salt, phosphorus hexafluoride diphenyliodonium salt, antimony hexafluoride diphenyliodonium salt, arsenic hexafluoride tri-4-methylphenylsulfonium salt, antimony tetrafluoride Examples include tri-4-methylphenylsulfonium salt, diphenyliodonium salt of tetrakis (pentafluorophenyl) boron, acetylacetone aluminum salt and orthonitrobenzylsilyl ether mixture, phenylthiopyridium salt, phosphorus hexafluoride allene-iron complex, etc. Can do.

Commercially available photopolymerization initiators include Irgacure 651, Irgacure 184, Irgacure 819, Irgacure 907, Irgacure 1870, Irgacure 500, Irgacure 369, Irgacure 1173, Irgacure 2959, Irgacure 4265, Irgacure 4263, Darocur OPO 01, Irgac・ Specialty Chemicals Co., Ltd.). Also, cationic photopolymerization of Irgacure 250 (Ciba Specialty Chemicals Co., Ltd.), CPI100P, CPI101A, CPI-200K, CPI210S (San Apro Co., Ltd.), Adekaoptomer SP300, SP150 (ADEKA Co., Ltd.), etc. Agents can also be used.

    The amount of the photopolymerization initiator used is preferably 1 to 15% by weight and more preferably 2 to 10% by weight with respect to 100% by weight of the composite resin (A).

  Further, by using a sensitizing dye in combination with the photopolymerization initiator, the photosensitivity can be greatly improved. Specific examples of the sensitizing dye include thioxanthene series, xanthene series, ketone series, thiopyrylium salt series, base styryl series, merocyanine series, 3-substituted coumarin series, cyanine series, acridine series, and thiazine series. It is done.

  As the thermal polymerization initiator, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile) can be used. ), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), azo compounds, benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t- And organic peroxides such as butylperoxy) cyclohexane, t-amylperoxy-2-ethylhexanoate, and t-hexylperoxy-2-ethylhexanoate. As a cationic thermal polymerization initiator, Sun Aid SI60L, 80L, 100L (manufactured by Sanshin Chemical Industry Co., Ltd.), Sun Apro TA90, TA100, TA120, TA160 (manufactured by San Apro Co., Ltd.) and the like can be used. Moreover, these polymerization initiators can be used alone or in combination of two or more.

(Reactive compounds)
The curable resin composition for resin molds in the present invention may contain a reactive compound in addition to the composite resin (A).
As the reactive compound, a polymer or monomer having a reactive group that directly contributes to the curing reaction with the composite resin (A) can be used. In particular, reactive diluents such as polyisocyanate (B) and active energy ray-curable monomers are particularly preferable.

  By introducing a reactive functional group into the composite resin (A), the composite resin (A) and the reactive diluent are three-dimensionally cross-linked, so that the curability generally increases and the pattern is maintained during mold transfer. A resin mold having excellent properties can be obtained.

  When polyisocyanate (B) is used as the reactive compound, the vinyl polymer segment (a2) in the composite resin (A) preferably has an alcoholic hydroxyl group. In that case, the polyisocyanate (B) is preferably contained in an amount of 5 to 50% by weight based on the total amount of the curable resin composition for a resin mold of the present invention.

  There is no limitation in particular as polyisocyanate (B) to be used, A well-known thing can be used. For example, aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane-4,4′-diisocyanate, and aralkyl diisocyanates such as meta-xylylene diisocyanate and α, α, α ′, α′-tetramethyl-meta-xylylene diisocyanate , Tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), 2,2,4- (or 2,4,4) 4-trimethyl-1,6-hexamethylene diisocyanate, lysine isocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,4-diisocyanate cyclohexane, 1,3-bis Diisocyanate methyl) cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, allophanate type polyisocyanate, biuret type polyisocyanate include adduct type polyisocyanate and isocyanurate type polyisocyanate.

  Reaction of polyisocyanate (B) with a hydroxyl group in the system (this is a hydroxyl group in the active energy ray-curable monomer having a hydroxyl group in the vinyl polymer segment (a2) or an alcoholic hydroxyl group described below). There is no particular need for heating or the like, and it reacts gradually when it is left at room temperature. If necessary, the reaction between the alcoholic hydroxyl group and the isocyanate may be promoted by heating at 80 ° C. for several minutes to several hours (20 minutes to 4 hours). In that case, you may use a well-known urethanation catalyst as needed. The urethanization catalyst is appropriately selected according to the desired reaction temperature.

Moreover, when making it ultraviolet-cure, it is preferable to contain polyfunctional (meth) acrylate as an active energy ray hardening monomer as needed.
As described above, the polyfunctional (meth) acrylate is preferably one having an alcoholic hydroxyl group because it is reacted with the polyisocyanate (B). For example, 1,2-ethanediol diacrylate, 1,2-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, Tripropylene glycol diacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, tris (2-acryloyloxy) isocyanurate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, di (trimethylolpropane) tetraacrylate, di (penta Erythritol) pentaacrylate, di (pentaerythritol) hexaacrylate, etc. have two or more polymerizable double bonds in one molecule That polyfunctional (meth) acrylate. Moreover, urethane acrylate, polyester acrylate, epoxy acrylate, etc. can be illustrated as polyfunctional acrylate. These may be used alone or in combination of two or more.
Especially, when making it react with polyisocyanate (B), the pentaerythritol triacrylate and dipentaerythritol pentaacrylate which have alcoholic hydroxyl group are preferable.

  In addition, a monofunctional (meth) acrylate can be used alone or in combination with the polyfunctional (meth) acrylate. For example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, “Plexel” manufactured by Daicel Chemical Industries), phthalic acid and propylene Mono (meth) acrylate of polyester diol obtained from glycol, mono (meth) acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, pentaerythritol Mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, (meth) acrylate of various epoxy esters Hydroxyl group-containing (meth) acrylic acid esters such as phosphoric acid adducts; carboxyl group-containing vinyl monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid; vinyl sulfonic acid, styrene sulfone Sulfonic acid group-containing vinyl monomers such as acid and sulfoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3- Examples thereof include acidic phosphate ester vinyl monomers such as chloro-propyl acid phosphate and 2-methacryloyloxyethylphenyl phosphoric acid; vinyl monomers having a methylol group such as N-methylol (meth) acrylamide. These can use 1 type (s) or 2 or more types. As the monomer, a (meth) acrylic acid ester having a hydroxyl group is particularly preferable.

In addition, from the viewpoint of improving scratch resistance and releasability for highly polar transferred materials, tricyclodecane dimethanol diacrylate, ethylene oxide-added bisphenol A diacrylate, propylene oxide-added bisphenol A diacrylate, 9, 9 bis A polyfunctional (meth) acrylate having a large number of aromatic rings or cyclic hydrocarbon groups such as diacrylate having a phenylfluorene skeleton and having two or more polymerizable double bonds in one molecule is preferably used. Similarly, the monofunctional (meth) acrylate is preferably a structure containing many aromatic rings or cyclic hydrocarbon groups such as phenylbenzyl acrylate.

Moreover, when using an active energy ray hardening monomer as said reactive compound, polyfunctional (meth) acrylate or monofunctional (meth) acrylate can be contained as needed.
As polyfunctional (meth) acrylate, 1,2-ethanediol di (meth) acrylate, 1,2-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, tris (2- (meth) acryloyloxy) isocyanurate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di (trimethylolpropane) tetra (meth) acrylate, (Pentaerythritol) penta (meth) acrylate, di (pentaerythritol) hexa (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di ( 2 or more per molecule such as (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, and 9,9-di (meth) acrylate having a bisphenylfluorene skeleton And a polyfunctional (meth) acrylate having a polymerizable double bond. In particular, from the viewpoint of improving dry etching resistance, a structure containing many aromatic rings or cyclic hydrocarbon groups is preferable. Tricyclodecane dimethanol di (meth) acrylate, ethylene oxide-added bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol Preferred are F di (meth) acrylate, propylene oxide-added bisphenol A di (meth) acrylate, propylene oxide-added bisphenol F di (meth) acrylate, and di (meth) acrylate having a 9,9-bisphenylfluorene skeleton.
Monofunctional (meth) acrylates include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, trade name “Placcel” manufactured by Daicel Chemical Industries, Ltd.) )), Mono (meth) acrylate of polyester diol obtained from phthalic acid and propylene glycol, mono (meth) acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (Meth) acrylate, pentaerythritol mono (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, various esters Hydroxyl group-containing (meth) acrylic acid esters such as (meth) acrylic acid adducts of xyesters; carboxyl group-containing vinyl monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid; Sulphonic acid group-containing vinyl monomers such as vinyl sulfonic acid, styrene sulfonic acid and sulfoethyl (meth) acrylate; 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meta ) Acid phosphate vinyl monomers such as acryloyloxy-3-chloro-propyl acid phosphate, 2-methacryloyloxyethylphenyl phosphate; vinyl monomers having a methylol group such as N-methylol (meth) acrylamide, Zyl acrylate Gills (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenol EO modified (meth) acrylate, o-phenylphenol EO modified (meth) acrylate, paracumylphenol EO modified (meth) acrylate, nonylphenol EO-modified (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (phenylthio) ethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, iso Examples include boronyl (meth) acrylate and adamantyl (meth) acrylate. These can use 1 type (s) or 2 or more types. In particular, from the viewpoint of improving dry etching resistance, a structure containing a large number of aromatic rings or cyclic hydrocarbon groups is preferred. Benzyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxybenzyl (meth) acrylate, phenol EO-modified (meth) Acrylate, o-phenylphenol EO modified (meth) acrylate, paracumylphenol EO modified (meth) acrylate, nonylphenol EO modified (meth) acrylate, monohydroxyethyl (meth) acrylate phthalate, 2-hydroxy-3-phenoxypropyl ( (Meth) acrylate, 2- (phenylthio) ethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate DOO, dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate.
Similarly, when an active energy ray-curable monomer is used, a polyfunctional or monofunctional epoxy resin can be contained as necessary. As the epoxy resin, bisphenol A type, bisphenol F type, cresol novolak type, phenol novolak type, epoxy polyol and the like can be used.

  The amount of the polyfunctional and monofunctional acrylate used is preferably 1 to 85% by weight, more preferably 5 to 80% by weight, based on the total solid content of the curable resin composition for resin molds of the present invention. . By using the polyfunctional acrylate and monofunctional within the above range, mold characteristics such as scratch resistance and hardness of the obtained resin mold and replica mold can be improved.

  When the curable resin composition for a resin mold of the present invention is cured, heat curing and photocuring are possible, but photocuring is preferable from the viewpoint of curing speed. In particular, active energy ray curing is preferable, and ultraviolet curing is particularly preferable.

  For example, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an argon laser, a helium / cadmium laser, or an ultraviolet light-emitting diode can be used as the light used for ultraviolet curing. Using these, it is possible to cure by irradiating the application surface of the curable resin composition with ultraviolet rays having a wavelength of about 180 to 400 nm. The irradiation amount of ultraviolet rays is appropriately selected depending on the type and amount of the photopolymerization initiator used.

On the other hand, when thermosetting the curable resin composition for resin molds used in the present invention, it is preferable to select each catalyst.
Moreover, it is also possible to use a thermosetting resin together. Examples of the thermosetting resin include vinyl resins, unsaturated polyester resins, polyurethane resins, epoxy resins, epoxy ester resins, acrylic resins, phenol resins, petroleum resins, ketone resins, silicon resins, and modified resins thereof.

  Moreover, in order to adjust the viscosity at the time of coating, you may contain the organic solvent. Examples of the organic solvent include aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane and cyclopentane; aromatic hydrocarbons such as toluene, xylene and ethylbenzene. Alcohols such as methanol, ethanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; ethyl acetate, butyl acetate, n-butyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl Esters such as ether acetate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone and cyclohexanone; diethylene glycol dimethyl ether, diethylene glycol dibuty Polyalkylene glycol dialkyl ethers such as ethers; ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane; N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate used alone or in combination of two or more Can be used.

(About mold release agent)
A release agent can be arbitrarily blended in the curable resin composition for a resin mold of the present invention for the purpose of neatly peeling the cured resin layer from the mold without roughening the surface. As the release agent, conventionally known release agents such as silicone release agents, fluorine release agents, paraffin waxes, amide waxes, solid waxes such as fluorine powder, fluorine type, phosphate ester type compounds, etc. Can be used, and one or more of these release agents may be used in combination. Moreover, these mold release agents can be adhered to the mold.
Among these, the silicone-based release agent and the fluorine-based release agent are preferable, and the releasability from the mold is particularly good when combined with the cured resin composition used in the present invention. Examples of the silicone release agent include unmodified or modified silicone oil, silicone acrylic resin, and the like. When these silicone release agent and fluorine release agent are silane coupling agents, polysiloxane segments are exposed on the surface of the mold made of the curable resin composition for resin molds of the present invention. Therefore, since the silane coupling agent and the polysiloxane segment can react efficiently, the release effect and the durability thereof are increased, which is preferable.

The modified silicone oil is obtained by modifying the side chain and / or terminal of polysiloxane, and is classified into a reactive silicone oil and a non-reactive silicone oil. Examples of the reactive silicone oil include amino modification, epoxy modification, carboxyl modification, carbinol modification, mercapto modification, phenol modification, one-terminal reactivity, and different functional group modification. Examples of the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, and fluorine modification.
Two or more modification methods as described above may be performed on one polysiloxane molecule.

  Especially when reactive silicone oil is used, it is fixed by chemical bonding in the cured film obtained by curing the curable resin composition of the present invention, thereby reducing problems such as adhesion inhibition, contamination and deterioration of the cured film. can do.

  When a release agent is added to the curable resin composition for resin molds of the present invention, it is preferably blended in a proportion of 0.001 to 10% by mass in the total amount of the composition, in a range of 0.01 to 5% by mass. More preferably, it is added at When the content of the release agent is in the range of 0.01 to 5% by mass, the effect of improving the peelability between the master mold and the resin mold is improved.

(About surfactant)
In order to ensure coating uniformity, the curable resin composition for resin molds of the present invention may contain a surfactant. The surfactant is contained in an amount of 0.001 to 5% by weight, more preferably 0.005 to 3% by weight, based on the solid content of the curable resin composition for a resin mold of the present invention.

  Surfactants include fluorine-based surfactants (for example, trade name Florard FC-430, FC-431 (manufactured by Sumitomo 3M Limited), trade names Unidyne DS-401, DS-403, DS-451 (all are Daikin). (Manufactured by Kogyo Co., Ltd.), trade names Megafuk 171, 172, 173, 178K, 178A (all manufactured by DIC Corporation), etc.), silicone surfactants (for example, MegaFac Paintad 31 (manufactured by DIC Corporation) ), KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like, and fluorine / silicone surfactants (for example, trade names X-70-090, X-70-091, X-70-092, X-70) -093 (all manufactured by Shin-Etsu Chemical Co., Ltd.), trade name Megafuk R-08, XRB-4 (all manufactured by DIC Corporation), etc.) Preferably includes both a fluorine surfactant and silicone surfactant or, more preferably comprising a fluorine-containing silicone-based surfactant, and most preferably comprises a fluorine-containing silicone-based surfactant.

  The curable resin composition for a resin mold of the present invention can greatly improve the coating uniformity by adding the surfactant, and is excellent regardless of the substrate size in coating using a spin coater or various coaters. Application suitability is obtained.

  In addition, the curable resin composition for resin molds used in the present invention includes an organic solvent, an inorganic pigment, an organic pigment, an extender pigment, a clay mineral, a wax, a surfactant, a stabilizer, a flow regulator, as necessary. Various additives such as dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, or plasticizers can also be used.

  In the curable resin composition for resin mold used in the present invention, the composite resin (A) to be contained has both the polysiloxane segment (a1) and the vinyl polymer segment (a2). The acrylic resin and the active energy ray curable monomer are relatively easily compatible with each other. Therefore, a composition having good compatibility can be obtained.

  The curable resin composition for resin molds of the present invention may contain other components as necessary within a range not impairing the effects of the present invention. For example, adhesive aids consisting of general-purpose silane coupling agents such as glycidoxyalkyltrimethoxysilane and (meth) acryloyloxyacryltrialkoxysilanesilane, talc, mica, clay, silica, alumina, sericite, white carbon , Gypsum, mica, inorganic fine particles such as barium sulfate, barium carbonate and magnesium carbonate, colored substances such as pigments and dyes, anti-fading agents, antioxidants, UV absorbers, paint additives such as plasticizers and lubricants, Can be mentioned.

(Master mold)
Quartz and silicon are well known as master mold materials. The master mold is produced by an electron beam drawing method or the like, and in particular, a nano-order fine pattern is formed on the master mold for nanoimprinting.

(Resin mold)
The resin mold of the present invention can be obtained by transferring a pattern from the master mold to the curable resin composition for a resin mold of the present invention.
When producing a resin mold, the master mold is pressed against the coating film of the curable resin composition applied to the resin mold substrate and cured, and then the cured resin mold is peeled off from the master mold. You can get it.
Alternatively, a resin mold may be produced by directly applying a curable resin composition for a resin mold to a master mold, and then curing the resin mold after adhering the substrate to the master mold.

[(1) Step of forming a coating film]
For the step of forming a coating film in which the curable resin composition for resin mold is in close contact with the substrate, a known and commonly used method may be used. For example, a liquid curable resin composition for resin mold is applied to the substrate surface. Can be obtained. When a curable resin composition for a resin mold is used as a liquid, the concentration of the total solid content in the curable resin composition for a resin mold is such that the coating property (for example, the film thickness after application and solvent removal is within a desired range). Etc., that the film thickness is uniform over the entire surface to be processed, and even if there are some irregularities on the surface to be processed, a coating film with a uniform thickness is formed following the irregularities, etc.) Is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.4% by mass or more and 5% by mass or less, and further preferably 0.7% by mass or more and 2% by mass or less. is there. Specifically, the film thickness of the coating film may be adjusted to be 10 nm to 50 μm, and more preferably 50 nm to 5 μm.
Since the curable resin composition for resin molds of the present invention can be finely patterned, the film thickness can be 1 μm or less.

  The solvent to be used may be any organic solvent used in known curable resin compositions. For example, aliphatic solvents such as n-hexane, n-heptane, n-octane, cyclohexane, cyclopentane, or alicyclic rings. Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; alcohols such as methanol, ethanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; ethyl acetate and n-butyl acetate , Esters such as isobutyl acetate, n-amyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, cyclohexanone; Polyalkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether and diethylene glycol dibutyl ether; ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane; N-methylpyrrolidone, dimethylformamide, dimethylacetamide or ethylene carbonate alone or 2 More than one species can be used in combination.

  The coating film of the curable resin composition for a resin mold of the present invention is formed by forming the curable resin composition for a resin mold of the present invention into a film by a known molding method such as extrusion molding, or on a temporary support film. It may be applied to the substrate and dried, and if necessary, the surface of the curable resin composition for a resin mold covered with a coating film may be thermocompression-bonded and laminated. As a temporary support film used at this time, conventionally well-known films, such as a polyethylene terephthalate film, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, are used, for example. In that case, when those films have solvent resistance, heat resistance, etc. necessary for the production of the resist film, the curable resin for resin mold of the present invention directly on the temporary support film. A coating film can be prepared by applying and drying the composition, and even if those films have low solvent resistance, heat resistance, etc., for example, polytetrafluoroethylene film, release film, etc. First, a curable resin composition for a resin mold of the present invention is formed on a film having a mold release property, and then a temporary support film having a low solvent resistance or heat resistance is laminated on the layer, and then the mold release is performed. A coating film of the curable resin composition for a resin mold can also be produced by peeling the film having moldability.

  Moreover, the coating film of the curable resin composition for resin molds of the present invention is formed by applying the curable resin composition for resin molds of the present invention on the surface to be treated and evaporating and removing the solvent. It may be a coating film. Examples of the coating method include a spray method, a spin coat method, a dip method, a roll coat method, a blade coat method, a doctor roll method, a doctor blade method, a curtain coat method, a slit coat method, and a screen printing method. The spin coating method is preferably used in terms of excellent productivity and easy control of the film thickness.

The resin mold substrate of the present invention is appropriately selected according to the purpose of the resin mold of the present invention.
For example, synthesis of quartz, sapphire, glass, optical film, ceramic material, deposited film, magnetic film, reflective film, metal substrate such as Al, Ni, Cu, Cr, Fe, stainless steel, screen mesh, paper, wood, silicon, etc. Resins, polymer substrates such as SOG (Spin On Glass), polyester film, polycarbonate film, polyimide film, TFT array substrates, light emitting diode (LED) substrates such as sapphire and GaN, glass and transparent plastic substrates, indium tin Examples thereof include conductive base materials such as oxide (ITO) and metal, insulating base materials, semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. These may be light transmissive or non-light transmissive.
Further, the shape of the substrate is not particularly limited, and may be any shape according to the purpose such as a flat plate, a sheet, or a three-dimensional shape having a curvature on the entire surface or a part thereof. There are no particular restrictions on the hardness and thickness of the substrate.

[(2) Step of forming resin mold]
Specifically, the step of pressing the master mold against the coating film of the curable resin composition for resin mold produced by the above method is to mold the curable resin composition layer for resin mold while pressing the master mold. Press into a fine shape. In that case, it can also press, heating and reducing a viscosity so that the said curable resin composition for resin molds may follow the fine shape of a mold more. Thereafter, the active mold is irradiated to cure the curable resin composition layer for resin mold, and then the master mold is separated so that the fine shape formed in the master mold is the curable resin composition for resin mold. A resin mold formed on the surface of the object can be obtained.

Specifically, the master mold is brought into contact with the curable composition layer for resin mold provided on the surface of the substrate so as to be held between them. The master mold is a method for efficiently producing a large-area molded body. The flat master up-down method, belt-shaped master bonding method, roll-shaped master roll transfer method, roll-belt shape, which are suitable for the roll process. A method of contacting by an original plate roll transfer method or the like is also preferable. Examples of the material of the master mold include quartz glass, ultraviolet transmissive glass, silicone materials such as sapphire, diamond, and polydimethylsiloxane, fluororesin, and other resin materials that transmit light. Further, if the base material to be used is a material that transmits light, the master mold may be a material that does not transmit light. Examples of the material that does not transmit light include metal, silicon, SiC, and mica.
As described above, the master mold can be selected in any form such as a flat form, a belt form, a roll form, and a roll belt form. For the purpose of preventing contamination of the original plate due to floating dust or the like, it is preferable to perform a conventionally known release treatment on the transfer surface.

  The curing method may be photocuring or thermal curing, but photocuring is preferred from the viewpoint of curing speed. In the case of photocuring, there is a method of irradiating light from the master mold side when the master mold is a material that transmits light, and a method of irradiating light from the substrate side when the substrate is a material that transmits light. When both the mold and the base material are light transmissive, light may be irradiated from both sides. The light used for the light irradiation may be light that reacts with the photopolymerization initiator. Among them, light with a wavelength of 450 nm or less is preferred because the photopolymerization initiator reacts easily and can be cured at a lower temperature. (Active energy rays such as ultraviolet rays, X-rays and γ rays) are preferred. In view of operability, light having a wavelength of 200 to 450 nm is particularly preferable. Specifically, the light used for the above-described ultraviolet curing can be used.

Further, if there is a defect in the followability of the coating film to the coating film with a concavo-convex structure, the film may be heated to a temperature at which sufficient fluidity can be obtained during light irradiation. The temperature for heating is preferably 300 ° C. or lower, more preferably 0 ° C. to 200 ° C., further preferably 0 ° C. to 150 ° C., and particularly preferably 25 ° C. to 80 ° C. In this temperature range, the precision of the fine pattern shape formed in the curable resin composition layer for resin mold is kept high.
In any of the above methods, as a method for efficiently producing a molded article having a large area, a method of curing by transporting the inside of the reactor so as to be compatible with the roll process is also preferable.

(Release process)
After the curing step, the resin mold is peeled off from the master mold, thereby obtaining a resin mold in which a concavo-convex pattern obtained by transferring the concavo-convex pattern of the master mold is formed on the surface of the cured product of the curable resin composition layer for a resin mold. . In terms of suppressing deformation such as warping of the base material and improving the accuracy of the uneven pattern, the temperature of the peeling process is a method performed after the temperature of the resist film is cooled to around room temperature (25 ° C.), or a resist Even when the film is peeled off when it is still heated, a method of cooling to around room temperature (25 ° C.) with a certain tension applied to the resist film is preferable.

(Replica mold)
A replica mold can be produced using the resin mold of the present invention as a mold. Examples of the replica mold include a metal mold such as nickel and a resin molded body made of a resin composition.

(Metal mold)
By producing the metal mold from the master mold through the resin mold, the metal mold can be produced without damaging the master mold. In addition, since a plurality of metal molds can be created from the same master mold, the same metal mold can be used at the same time, and it is possible to perform a molding process with further high throughput.

((3) Step of forming metal layer)
In order to create the metal mold of the present invention, a metal layer is formed on the surface of the resin mold, and the resin mold is peeled off from the obtained metal layer.
For the formation of the metal layer, a known and commonly used method may be used.
(3-1) Forming a conductive layer on the resin mold surface (3-2) A process of laminating a metal layer on the surface of the conductive layer by electroforming is often used.

(3-1) Forming conductive layer on resin mold surface Examples of methods for forming the conductive layer include physical vapor deposition and electroless plating. Examples of physical vapor deposition include sputtering, vacuum vapor deposition, and ion plating. In the electroless plating method, metal fine particles, colloids, organometallic complexes, and the like can be used as a catalyst, and salts such as nickel, copper, cobalt, gold, platinum, and silver can be used as an electroless plating solution.

(3-2) Laminating a metal layer on the surface of the conductive layer by electrocasting A resin mold having a conductive layer formed on the surface is immersed in an electrolytic plating solution and energized to deposit metal on the conductive layer, and the metal Form a layer. As a metal used for the metal layer, nickel, copper, chromium, aluminum, titanium, tungsten, molybdenum, platinum, and alloys thereof can be used.

((4) Step of peeling resin mold to obtain metal mold)
By peeling from the interface part of the resin mold and the conductive layer from the resin mold obtained by laminating the metal layer obtained in the above process, the metal layer can be separated into a metal mold.
Since the resin mold made of the curable resin composition for resin molds of the present invention is excellent in releasability, even when it is peeled off from the metal mold, it is difficult for the fine pattern to be lost or deformed. can do. Moreover, when a film is left on the replica mold due to the shape of the fine pattern or the type of metal, the acid value of the composite resin (A) contained in the curable resin composition for resin mold is set to 30 to 400 KOHmg / g. By doing so, alkali cleaning becomes possible.

  By using the metal mold in the present invention as a mold and further imprinting the resin composition, it is possible to obtain a resin molded product that is a tertiary molded product. The resin composition to be used may be a known and commonly used resin, and a thermosetting resin, a thermoplastic resin, a photocurable resin, etc., which will be described later, can be used.

(Resin molding)
The replica mold of the present invention may be a resin molded body.
With respect to the resin mold of the present invention, a second resin layer is formed, the second resin layer is cured, and then the resin mold is peeled off to obtain a resin molded body to which a fine pattern is transferred.
The obtained resin molded body may be used as the second resin mold or may be used as a product as it is.

The resin constituting the second resin layer can be appropriately selected from the curable resin composition for resin molds of the present invention, the thermosetting resin, the thermoplastic resin, the photocurable resin, and the like according to the purpose. .

Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, furan resin, alkyd resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicone resin, polyimide resin, polyurethane resin, guanamine resin, and the like. It is done.
Examples of the thermoplastic resin include polyolefin resins, polystyrene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyacrylonitrile resins, polyamide resins, polyether imides, polyamide imides, polyester resins, polycarbonate resins, Polyacetal resin, vinyl acetate resin, polyvinyl acetal, thermoplastic polyurethane elastomer, acrylic resin, polyphenylene resin, fluororesin, polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivative, phenol resin, urea resin, melamine resin, furan resin, alkyd resin , Unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicone resin, polyimide resin, polyurethane resin, guanamine resin and the like.

  As a photocurable resin, any of an ultraviolet curable resin and an electron beam curable resin may be sufficient, for example. Various known materials can be used as the ultraviolet curable resin or the electron beam curable resin, and examples thereof include acrylic resins, silicone resins, ester resins, and the like. Typical examples are UV curable resins having an acryloyl group in the molecule, epoxy acrylate, urethane acrylate, polyester acrylate, polyol acrylate oligomers, polymers and monofunctional, bifunctional, or polyfunctional. Polymerizable (meth) acrylic monomers such as tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tris Mixtures of monomers such as acrylate and pentaerythritol tetraacrylate, oligomers and polymers are used. In addition, you may mix | blend the photoinitiator etc. which are mix | blended normally with a photocurable resin.

  These resins may be used alone or in combination of two or more.

(5) Step of forming and curing second resin layer In order to form the second resin layer, the resin mold is pressed against the second resin layer applied on the second resin substrate and cured. It can be obtained by peeling the cured resin molded body from the resin mold.
Also, the resin for the second resin layer is directly applied to the resin mold, and the second resin layer is cured as it is, or the substrate is adhered to the second resin layer and then cured, and the resin mold is peeled off. Thus, a resin molded body may be produced.

(6) Step of removing resin mold and obtaining resin molded body In the above step (5), the second resin layer is cured while the resin mold is pressed against the second resin layer, or the second resin layer is formed on the resin mold. After the second resin layer is cured, the resin mold is peeled from the cured second resin layer to obtain a resin molded body that is a replica mold to which the fine structure of the resin mold is transferred. Can do. The resin molded body may be used as a product as it is or may be used as a mold.

  The resin for the second resin layer may be an organic solvent, inorganic pigment, organic pigment, extender pigment, clay mineral, wax, surfactant, stabilizer, flow regulator, dye, leveling agent, rheology control agent, ultraviolet ray as necessary. Various additives such as an absorbent, an antioxidant, or a plasticizer can also be used. Adhesive aid composed of silane coupling agent, talc, mica, clay, silica, alumina, sericite, white carbon, gypsum, mica, barium sulfate, inorganic fine particles such as barium carbonate and magnesium carbonate, pigments and dyes, etc. Such coloring materials, fading inhibitors, antioxidants, UV absorbers, paint additives such as plasticizers and lubricants may be blended.

Next, the present invention will be specifically described with reference to examples and comparative examples. Unless otherwise indicated, “parts” and “%” are weight standards.

(Synthesis Example 1 [Preparation Example of Polysiloxane (a1-1)])
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet is charged with 415 parts of methyltrimethoxysilane (MTMS) and 756 parts of 3-methacryloyloxypropyltrimethoxysilane (MPTS). The temperature was raised to 60 ° C. with stirring under aeration of gas. Next, a mixture of 0.1 part of “Phoslex A-3” (iso-propyl acid phosphate manufactured by Sakai Chemical Co., Ltd.) and 121 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C. and stirred for 4 hours to carry out a hydrolysis condensation reaction, thereby obtaining a reaction product.
By removing methanol and water contained in the obtained reaction product under conditions of 40 to 60 ° C. under reduced pressure of 1 to 30 kilopascals (kPa), the number average molecular weight is 1000 and the active ingredient is 75. 1000 parts of polysiloxane (a1-1) which is 0.0% was obtained.
The "active ingredient" is a value obtained by dividing the theoretical yield (parts by weight) when all the methoxy groups of the silane monomer used undergo hydrolysis condensation reaction by the actual yield (parts by weight) after hydrolysis condensation reaction, That is, it is calculated by the formula [theoretical yield when all methoxy groups of the silane monomer undergo hydrolysis condensation reaction (parts by weight) / actual yield after hydrolysis condensation reaction (parts by weight)].

(Synthesis example 2 (adjustment example of polysiloxane (a1-2)))
In a reaction vessel similar to that in Synthesis Example 1, 442 parts of MTMS and 760 parts of 3-acryloyloxypropyltrimethoxysilane (APTS) were charged, and the temperature was raised to 60 ° C. while stirring under aeration of nitrogen gas. Next, a mixture consisting of 0.1 part of “Phoslex A-3” and 129 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C. and stirred for 4 hours to carry out a hydrolysis condensation reaction, thereby obtaining a reaction product. By removing methanol and water contained in the obtained reaction product under conditions of 40 to 60 ° C. under reduced pressure of 1 to 30 kilopascals (kPa), the number average molecular weight is 1000 and the active ingredient is 75. 1000 parts of polysiloxane (a1-2) which is 0.0% was obtained.

(Synthesis Example 3 [Preparation Example of Vinyl Polymer (a2-1)])
In a reaction vessel similar to Synthesis Example 1, 20.1 parts of phenyltrimethoxysilane (PTMS), 24.4 parts of dimethyldimethoxysilane (DMDMS), and 107.7 parts of n-butyl acetate were charged under a nitrogen gas flow. The temperature was raised to 80 ° C. while stirring. Next, 15 parts of methyl methacrylate (MMA), 45 parts of n-butyl methacrylate (BMA), 39 parts of 2-ethylhexyl methacrylate (EHMA), 1.5 parts of acrylic acid (AA), 4.5 parts of MPTS, 2-hydroxyethyl A mixture containing 45 parts of methacrylate (HEMA), 15 parts of n-butyl acetate and 15 parts of tert-butylperoxy-2-ethylhexanoate (TBPEH) was stirred at the same temperature under a stream of nitrogen gas. And dropped into the reaction vessel in 4 hours. After further stirring for 2 hours at the same temperature, a mixture of 0.05 part of “Phoslex A-3” and 12.8 parts of deionized water was added dropwise to the reaction vessel over 5 minutes, and the mixture was kept at the same temperature for 4 hours. By stirring, the hydrolysis condensation reaction of PTMS, DMDMS, and MPTS was advanced. When the reaction product was analyzed by ¹ H-NMR, almost 100% of the trimethoxysilyl group of the silane monomer in the reaction vessel was hydrolyzed. Subsequently, the vinyl polymer (a2-1) which is a reaction product with a residual amount of TBPEH of 0.1% or less was obtained by stirring at the same temperature for 10 hours.

(Synthesis Example 4 [Preparation Example of Composite Resin (A-1)])
162.5 parts of the polysiloxane (a1-1) obtained in Synthesis Example 1 is added to 307 parts of the vinyl polymer (a2-1) obtained in Synthesis Example 23, and the mixture is stirred for 5 minutes. 27.5 parts of ionic water was added and the mixture was stirred at 80 ° C. for 4 hours to carry out a hydrolysis condensation reaction between the reaction product and polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa under conditions of 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 150 parts of methyl ethyl ketone (MEK), n-acetate -Butyl resin 27.3 parts, 600 parts of composite resin (A-1) having a polysiloxane segment (a1-1) and a vinyl polymer segment (a2-1) having a nonvolatile content of 50.0% Got.

(Synthesis Example 5 [Preparation Example of Composite Resin (A-2), Vinyl Polymer (a2- (2))])
In a reaction vessel similar to that of Synthesis Example 1, 20.1 parts of phenyltrimethoxysilane (PTMS), 24.4 parts of dimethyldimethoxysilane (DMDMS), and 106.4 parts of n-butyl acetate were charged under nitrogen gas. The temperature was raised to 95 ° C. while stirring. Subsequently, 105.8 parts of methyl methacrylate (MMA), 19.7 parts of n-butyl acrylate (BA), 19.3 parts of acrylic acid (AA), 4.5 parts of MPTS, 2-hydroxyethyl methacrylate (HEMA) 0. While stirring a mixture containing 8 parts, 15 parts of n-butyl acetate and 15 parts of tert-butylperoxy-2-ethylhexanoate (TBPEH) at the same temperature under aeration of nitrogen gas, the reaction vessel It was dripped in for 4 hours. After further stirring for 2 hours at the same temperature, a mixture of 0.05 part of “Phoslex A-3” and 12.8 parts of deionized water was dropped into the reaction vessel over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By stirring for a period of time, the hydrolysis condensation reaction of PTMS, DMDMS, and MPTS was advanced. When the reaction product was analyzed by ¹ H-NMR, almost 100% of the methoxysilyl group of the silane monomer in the reaction vessel was hydrolyzed. Next, by stirring at the same temperature for 10 hours, a reaction product (vinyl polymer a2- (2)) having a residual amount of TBPEH of 0.1% or less was obtained. The residual amount of TBPEH was measured by an iodometric titration method.

  Next, 162.5 parts of the polysiloxane (a1-1) obtained in Synthesis Example 1 was added to the reaction product (vinyl polymer a2- (2)), stirred for 5 minutes, and then deionized. 27.5 parts of water was added, and the mixture was stirred at 80 ° C. for 4 hours to carry out a hydrolysis condensation reaction between the reaction product and polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa under conditions of 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 150 parts of methyl ethyl ketone (MEK), n-acetate -28.6 parts of butyl were added, and 600 parts of composite resin (A-2) which consists of a polysiloxane segment and a vinyl polymer segment whose nonvolatile content is 50.0% were obtained.

  The acid value [number of milligrams (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the sample] of the obtained composite resin (A-2) is determined according to JIS K2501-2003, and phenol. It was measured by an indicator titration method using phthalein. The acid value of the solid content of the composite resin (A-2) was 50.2 KOHmg / g.

(Synthesis Example 6 (Preparation Example of Composite Resin (A-3), Vinyl Polymer (a2- (3))))
In a reaction vessel similar to Synthesis Example 1, 20.1 parts of PTMS, 24.4 parts of DMDMS, and 107.7 parts of n-butyl acetate were charged, and the temperature was raised to 95 ° C. while stirring under aeration of nitrogen gas. . Subsequently, a mixture containing 66.4 parts of MMA, 1.2 parts of BA, 77.1 parts of AA, 4.5 parts of MPTS, 0.8 part of HEMA, 15 parts of n-butyl acetate, and 15 parts of TBPEH was mixed at the same temperature. Then, the mixture was added dropwise to the reaction vessel in 4 hours while stirring under aeration of nitrogen gas. After further stirring for 2 hours at the same temperature, a mixture of 0.05 part of “Phoslex A-3” and 12.8 parts of deionized water was dropped into the reaction vessel over 5 minutes, and the mixture was stirred at the same temperature for 4 hours. By stirring for a period of time, the hydrolysis condensation reaction of PTMS, DMDMS, and MPTS was advanced. When the reaction product was analyzed by ¹ H-NMR, almost 100% of the methoxysilyl group of the silane monomer in the reaction vessel was hydrolyzed. Next, by stirring at the same temperature for 10 hours, a reaction product (vinyl polymer a2- (3)) having a residual amount of TBPEH of 0.1% or less was obtained. The residual amount of TBPEH was measured by an iodometric titration method.

  Next, 562.5 parts of the polysiloxane (a1-1) obtained in Synthesis Example 1 was added to the reaction product and stirred for 5 minutes, and then 80.0 parts of deionized water was added at 80 ° C. Stirring was carried out for 4 hours to carry out a hydrolysis condensation reaction between the reaction product and polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa under conditions of 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 128.6 parts of MEK, n-acetate 5.9 parts of butyl was added to obtain 857 parts of a composite resin (A-3) composed of a polysiloxane segment having a nonvolatile content of 70.0% and a vinyl polymer segment.

  The acid value of the obtained composite resin (A-3) was measured by an indicator titration method using phenolphthalein according to JIS K2501-2003. The acid value of the solid content of the composite resin (A-3) was 100.2 KOHmg / g.

(Synthesis example 7 (preparation example of composite resin (A-4), vinyl polymer (a2-4))
In a reaction vessel similar to Synthesis Example 1, 5.0 parts of PTMS, 6.1 parts of DMDMS, and 107.7 parts of n-butyl acetate were charged, and the temperature was raised to 95 ° C. with stirring under aeration of nitrogen gas. . Subsequently, a mixture containing 57.8 parts of MMA, 0.4 part of BA, 86.6 parts of AA, 4.5 parts of MPTS, 0.8 part of HEMA, 15 parts of n-butyl acetate, and 15 parts of TBPEH was mixed at the same temperature. Then, the mixture was added dropwise to the reaction vessel in 4 hours while stirring under aeration of nitrogen gas. After further stirring at the same temperature for 2 hours, a mixture of 0.05 part of “Phoslex A-3” and 3.2 parts of deionized water was dropped into the reaction vessel over a period of 5 minutes, and 4 parts at the same temperature. By stirring for a period of time, the hydrolysis condensation reaction of PTMS, DMDMS, and MPTS was advanced. When the reaction product was analyzed by ¹ H-NMR, almost 100% of the methoxysilyl group of the silane monomer in the reaction vessel was hydrolyzed. Subsequently, the reaction product (vinyl polymer (a2-4)) in which the remaining amount of TBPEH was 0.1% or less was obtained by stirring at the same temperature for 10 hours. The residual amount of TBPEH was measured by an iodometric titration method.

  Next, 40.6 parts of the polysiloxane (a1-2) obtained in Synthesis Example 2 was added to the reaction product and stirred for 5 minutes, and then 10.2 parts of deionized water was added at 80 ° C. Stirring was carried out for 4 hours to carry out a hydrolysis condensation reaction between the reaction product and polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa at 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 37.5 parts of MEK, n-acetate 27.3 parts of butyl was added to obtain 375.0 parts of a composite resin (A-4) composed of a polysiloxane segment having a nonvolatile content of 50.0% and a vinyl polymer segment.

The acid value of the obtained composite resin (A-4) was measured by an indicator titration method using phenolphthalein according to JIS K2501-2003. The acid value of the solid content of the composite resin (A-4) was 360.4 KOH mg / g.

(Synthesis Example 8 (Preparation Example of Composite Resin))
In a reaction vessel similar to Synthesis Example 1, 20.1 parts of PTMS, 24.4 parts of DMDMS, and 107.7 parts of n-butyl acetate were charged, and the temperature was raised to 95 ° C. while stirring under aeration of nitrogen gas. . Subsequently, a mixture containing 53.1 parts of MMA, 1.6 parts of BA, 90.0 parts of AA, 4.5 parts of MPTS, 0.8 part of HEMA, 15 parts of n-butyl acetate, and 15 parts of TBPEH was mixed at the same temperature. Then, the mixture was added dropwise to the reaction vessel in 4 hours while stirring under aeration of nitrogen gas. When the mixture was stirred at the same temperature for 1 hour, the viscosity of the reaction solution increased rapidly and gelled within a few minutes.

  From the content of AA, it is estimated that the acid value of the vinyl polymer segment of the resin solution that led to gelation was 467.5 KOHmg / g.

(Synthesis example 9 (adjustment example of polysiloxane (a1-3)))
In a reaction container similar to Synthesis Example 1, 379.9 parts of MTMS, 756 parts of 3-methacryloyloxypropyltrimethoxysilane (MPTS), tridecafluoro-1,1,2,2, -tetrahydrooctyltrimethoxysilane ( C8F13H4TS) was charged in 35 parts, and the temperature was raised to 60 ° C. with stirring under nitrogen gas. Next, a mixture consisting of 0.1 part of “Phoslex A-3” and 129 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C. and stirred for 4 hours to carry out a hydrolysis condensation reaction, thereby obtaining a reaction product. By removing methanol and water contained in the obtained reaction product under conditions of 40 to 60 ° C. under reduced pressure of 1 to 30 kilopascals (kPa), the number average molecular weight is 1000 and the active ingredient is 75. .0% "
1000 parts of polysiloxane (a1-3) was obtained.

(Synthesis Example 10 [Preparation Example of Vinyl Polymer (a2-5)])
In a reaction vessel similar to Synthesis Example 1, 20.1 parts of phenyltrimethoxysilane (PTMS), 24.4 parts of dimethyldimethoxysilane (DMDMS), and 107.7 parts of n-butyl acetate were charged under a nitrogen gas flow. The temperature was raised to 80 ° C. while stirring. Next, 10 parts of methyl methacrylate (MMA), 1 part of acrylic acid (AA), 1 part of n-butyl acrylate (BA), 3 parts of MPTS, 30 parts of 2-hydroxyethyl methacrylate (HEMA), perfluorohexyl ethyl methacrylate (C8F13H4MA) ) The above reaction was carried out while stirring a mixture containing 20 parts, 15 parts of n-butyl acetate and 15 parts of tert-butylperoxy-2-ethylhexanoate (TBPEH) at the same temperature under aeration of nitrogen gas. The solution was dropped into the container in 4 hours. After further stirring for 2 hours at the same temperature, a mixture of 0.05 part of “Phoslex A-3” and 12.8 parts of deionized water was added dropwise to the reaction vessel over 5 minutes, and the mixture was kept at the same temperature for 4 hours. By stirring, the hydrolysis condensation reaction of PTMS, DMDMS, and MPTS was advanced. When the reaction product was analyzed by ¹ H-NMR, almost 100% of the trimethoxysilyl group of the silane monomer in the reaction vessel was hydrolyzed. Subsequently, by stirring at the same temperature for 10 hours, a vinyl polymer (a2-5) which is a reaction product having a residual amount of TBPEH of 0.1% or less was obtained.

(Synthesis Example 11 [Preparation Example of Composite Resin (A-5)])
Synthesis Example After adding 162.5 parts of the polysiloxane (a1-3) obtained in Synthesis Example 9 to 307 parts of the vinyl polymer (a2-1) obtained in Synthesis Example 3, the mixture was stirred for 5 minutes. Then, 27.5 parts of deionized water was added, and the mixture was stirred at 80 ° C. for 4 hours to carry out hydrolysis condensation reaction between the reaction product and polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa at 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 150 parts of methyl ethyl ketone (MEK), n-acetate -Composite resin (A-5) having 29.3 parts of butyl and having a polysiloxane segment (a1-3) having a nonvolatile content of 50.0% and a vinyl polymer segment (a2-1) 600 parts Got.

(Synthesis Example 12 [Preparation Example of Composite Resin (A-6)])
162.5 parts of the polysiloxane (a1-1) obtained in Synthesis Example 1 is added to 307 parts of the vinyl polymer (a2-2) obtained in Synthesis Example 10 and stirred for 5 minutes. 27.5 parts of ionic water was added, and the mixture was stirred at 80 ° C. for 4 hours to carry out a hydrolysis condensation reaction between the reaction product and polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa under conditions of 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 150 parts of methyl ethyl ketone (MEK), n-acetate -Butyl resin 27.3 parts, 600 parts of composite resin (A-6) having a polysiloxane segment (a1-1) and a vinyl polymer segment (a2-1) having a nonvolatile content of 50.0% Got.

(Synthesis Example 13 [Preparation Example of Composite Resin (A-7)])
487.5 parts of the polysiloxane (a1-1) obtained in Synthesis Example 1 is added to 307 parts of the vinyl polymer (a2-2) obtained in Synthesis Example 10 and stirred for 5 minutes. 82.5 parts of ionic water was added and the mixture was stirred at 80 ° C. for 4 hours to carry out a hydrolysis condensation reaction between the reaction product and polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa under conditions of 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 150 parts of methyl ethyl ketone (MEK), n-acetate -27.3 parts of butyl are added, and the composite resin (A-7) having a polysiloxane segment (a1-1) and a vinyl polymer segment (a2-1) having a nonvolatile content of 50.0% is obtained. It was.

(Synthesis example 14 (adjustment example of polysiloxane (a1-4)))
In the same reaction vessel as in Synthesis Example 1, 379.9 parts of MTMS, 719 parts of γ-glycidoxypropyltrimethoxysilane (GPTS), tridecafluoro-1,1,2,2, -tetrahydrooctyltrimethoxysilane 35 parts of (C8F13H4TS) were charged, and the temperature was raised to 60 ° C. while stirring under aeration of nitrogen gas. Next, a mixture consisting of 0.1 part of “Phoslex A-3” and 129 parts of deionized water was added dropwise over 5 minutes. After completion of the dropwise addition, the reaction vessel was heated to 80 ° C. and stirred for 4 hours to carry out a hydrolysis condensation reaction, thereby obtaining a reaction product. By removing methanol and water contained in the obtained reaction product under conditions of 40 to 60 ° C. under reduced pressure of 1 to 30 kilopascals (kPa), the number average molecular weight is 1000 and the active ingredient is 75. 0.00% "of polysiloxane (a1-4) was obtained.

(Synthesis Example 15 [Preparation Example of Composite Resin (A-8)])
Synthesis Example After adding 162.5 parts of the polysiloxane (a1-4) obtained in Synthesis Example 14 to 307 parts of the vinyl polymer (a2-1) obtained in Synthesis Example 3, the mixture was stirred for 5 minutes. Then, 27.5 parts of deionized water was added, and the mixture was stirred at 80 ° C. for 4 hours to carry out hydrolysis condensation reaction between the reaction product and polysiloxane. The obtained reaction product was distilled under reduced pressure of 10 to 300 kPa at 40 to 60 ° C. for 2 hours to remove the produced methanol and water, and then 150 parts of methyl ethyl ketone (MEK), n-acetate -Composite resin (A-8) having 23.0 parts of butyl and having a polysiloxane segment (a1-4) and a vinyl polymer segment (a2-1) having a nonvolatile content of 50.0% 600 parts Got.

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, this invention is not limited to a following example.

Example 1
(Preparation example of resin mold composition-1)
40.0 parts of composite resin (A-4) obtained in Synthesis Example 7, 14.7 parts of dipentaerythritol hexaacrylate (DPHA), Irgacure 184 (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.) Resin mold composition-1 (Composition-1) was obtained by mixing 39 parts.

(Production example of resin mold)
The composition-1 is applied onto a silicon wafer substrate with a spin coater, heated on a hot plate at 80 ° C. for 1 minute, and then has a regular triangular lattice columnar structure with a diameter of 230 nm, a height of 200 nm, and a pitch of 460 nm on the surface. By pressing a flat master mold made of quartz glass, an LED light source having a peak wavelength of 375 nm ± 5 (manufactured by Immac Co., Ltd.), in this state, light irradiation with a light amount of 300 mJ / cm ² from the master mold side is cured, Thereafter, the master mold and the silicon wafer substrate were peeled off to obtain a resin mold-1 having a columnar pattern.

(Production example of metal mold by resin mold alkali soluble)
A nickel conductive layer is formed by sputtering on the cylindrical pattern surface of the obtained resin mold-1. Thereafter, the resin mold provided with the conductive layer is immersed in a nickel electroforming bath having the following composition to perform electroforming, and then immersed in a 1 wt% sodium carbonate aqueous solution at 30 ° C. for 120 seconds. The resin mold was dissolved to obtain a metal mold 1-1.

(Example of metal mold production by peeling resin mold)
A conductive layer is formed on the cylindrical pattern surface of the obtained resin mold 1 by sputtering. Thereafter, the resin mold provided with the conductive layer was immersed in a nickel electroforming bath having the following composition to perform electroforming, and then the nickel layer and the resin mold were peeled off to obtain a metal mold 1-2.

(Production example of resin molding from metal mold)
Composition-1 was coated on an optically easy-adhesive PET film substrate (A-4300 manufactured by Toyobo Co., Ltd .; 125 μm) with a bar coater, heated at 80 ° C. for 4 minutes, and then the surface had a diameter of 230 nm, a height of 200 nm, The metal mold 1-2 created above having a columnar structure of a regular triangular lattice with a pitch of 460 nm is pressed, and 300 mJ / cm from the coating film side in this state by an LED light source (manufactured by Immac Co., Ltd.) having a peak wavelength of 375 nm ± 5. ^The resin mold 1 having a columnar pattern was obtained by peeling off the metal mold 1-2 and the PET film substrate.

(Nickel electroforming bath composition and temperature)
Nickel sulfamate ... 450g / L
Nickel chloride ... 5g / L
Boric acid ... 40g / L
Pit inhibitor ... 3g / L
pH adjuster-appropriate amount PH = 4.0
Temperature = 50 ° C

(Example 2)
Based on the formulation shown in Table 1, a resin mold composition for preparing a metal mold (Composition-2) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, resin mold 2, resin mold alkali-soluble metal mold 2-1, metal mold 2-2 by resin mold peeling, and resin molded product 2 were obtained.

(Example 3)
Based on the formulation shown in Table 1, a resin mold composition (Composition-3) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, resin mold 3, resin mold alkali-soluble metal mold 3-1, metal mold 3-2 by resin mold peeling, and resin molded product 3 were obtained.

Example 4
A resin mold composition (Composition-4) was obtained in the same manner as in Example 1 based on the formulation shown in Table 1.
In the same manner as in Example 1, a resin mold 4, a metal mold 4-1 by alkali-solubility of the resin mold, a metal mold 4-2 by peeling off the resin mold, and a resin molded product 4 were obtained.

(Example 5)
Based on the composition shown in Table 1, a resin mold composition (Composition-5) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, a resin mold 5, a metal mold 5-1 by resin mold alkali-soluble, a metal mold 5-2 by peeling off the resin mold, and a resin molded product 5 were obtained.

(Example 6)
Based on the formulation shown in Table 1, a resin mold composition (Composition-6) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, a resin mold 6, a metal mold 6-1 by resin mold alkali-soluble, a metal mold 6-2 by peeling off the resin mold, and a resin molded product 6 were obtained.

(Example 7)
Based on the formulation shown in Table 1, a resin mold composition (Composition-7) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, a resin mold 7, a metal mold 7-1 by resin alkali-soluble, a metal mold 7-2 by peeling off the resin mold, and a resin molded product 7 were obtained.

(Example 8)
Based on the formulation shown in Table 1, a resin mold composition (Composition-8) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, a resin mold 8, a resin mold alkali-soluble metal mold 8-1, a metal mold 8-2 by peeling the resin mold, and a resin molded product 8 were obtained.

Example 9
Based on the composition shown in Table 2, a resin mold composition (Composition-9) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, a resin mold 9, a metal mold 9-2 by peeling off the resin mold, and a resin molded product 9 were obtained.

(Example 10)
Based on the composition shown in Table 2, a resin mold composition (Composition-10) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, a resin mold 10, a metal mold 10-2 by peeling off a resin mold, and a resin molded product 10 were obtained.

(Example 11)
A resin mold composition (Composition-11) was obtained in the same manner as in Example 1 based on the formulation shown in Table 2. Resin mold 11-1 was obtained in the same manner as Example 1. The resin mold 11-1 was immersed in a solution obtained by diluting Obtool DSX (manufactured by Daikin Industries, Ltd.), which is a fluorine-based surface treatment agent, to 0.1%, and rinsed to treat the mold surface (resin mold 11- 2).
In the same manner as in Example 1, a resin mold 11-2 was used to obtain a metal mold 11-2 and a resin molded product 11 by peeling the resin mold.

(Example 12)
Based on the formulation shown in Table 2, a resin mold composition (Composition-12) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, a resin mold 12, a metal mold 12-2 by peeling the resin mold, and a resin molded product 12 were obtained.

(Example 13)
The composition-1 was coated on an optically easy-adhesive PET film substrate (A-4300 manufactured by Toyobo Co., Ltd .; 125 μm) with a bar coater, heated at 80 ° C. for 4 minutes, and then resin mold 11 prepared in Example 11 -2 is pressed and cured with an LED light source having a peak wavelength of 375 nm ± 5 (manufactured by Immac Co., Ltd.) in this state by light irradiation with a light amount of 300 mJ / cm ² from the coating film side, and then the resin mold 11-2 The PET film substrate was peeled off to obtain a resin molded product 13 having a columnar pattern.
When the resin molded product 13 was evaluated based on the resin molded product pattern transferability evaluation described below, it was confirmed that the resin molded product 13 had no defects or deformation, and the mold pattern was satisfactorily transferred.

(Example 14)
A resin mold composition (Composition-14) was obtained in the same manner as in Example 1 based on the formulation shown in Table 2.
In the same manner as in Example 1, a resin mold 14, a metal mold 14-2 by peeling off the resin mold, and a resin molded product 14 were obtained.

(Comparative Example 1)
Based on the formulation shown in Table 2, a resin mold composition (specific composition-1) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, the comparative resin mold-1, the comparative metal mold 1-1 by resin mold alkali-soluble, the comparative metal mold 1-2 by peeling off the resin mold, and the comparative resin molding 1 were obtained.

(Comparative Example 2)
Based on the formulation shown in Table 2, a resin mold composition (specific composition-2) was obtained in the same manner as in Comparative Example 1. The composition surface was treated by immersing the specific composition-2 in a solution obtained by diluting Obtool DSX (manufactured by Daikin Industries, Ltd.), which is a fluorine-based surface treatment agent, to 0.1%, and rinsing.
In the same manner as in Example 1, comparative resin mold-2, comparative metal mold 2-1 based on resin mold alkali solubility, comparative metal mold 2-2 based on resin mold peeling, and comparative resin molded product 2 were obtained.

(Evaluation)
Evaluation of the resin mold, metal mold, and resin molded product obtained in Examples 1 to 14 and Comparative Examples 1 and 2 was performed as follows.

(Evaluation of resin mold alkali solubility)
The resin mold remaining on the metal mold release surface is 0% by weight, and the resin mold residual rate exceeds 0% by weight. evaluated.

(Evaluation of resin mold peelability)
The resin mold remaining rate remaining on the metal mold release surface is 0% by weight, and the resin mold remaining rate is more than 0% by weight and less than 1% by weight. The exfoliation property between the resin mold and the metal mold was evaluated with Δ for less than 5% by weight and x for 5% by weight or more.

(Metal mold pattern transferability evaluation)
The pattern transferability of the obtained metal mold was observed with a scanning microscope (manufactured by JEOL Ltd .: JSM-7500F) at a magnification of 100,000 times and evaluated as follows.
○: No defect or deformation in metal mold ×: Defect or deformation in metal mold

(Resin molded product pattern transferability evaluation)
The pattern transferability of the obtained resin molded product was observed at a magnification of 100,000 times with a scanning microscope (manufactured by JEOL Ltd .: JSM-7500F) and evaluated as follows.
○: No defect or deformation in resin molding ×: Defect or deformation in resin molding

Compositions of resin mold compositions of Examples 1 to 12, 14 and Comparative Examples 1 and 2, alkali solubility and peelability of the obtained metal mold and resin mold, metal mold pattern transferability, and obtained resin molding Tables 1 and 2 show the results of evaluating the object pattern transferability.

About abbreviations in Tables 1-2.
(A1) is an abbreviation for polysiloxane segment (a1).
(A2) is an abbreviation for vinyl polymer segment (a2).
* 1 Content (%) of the polysiloxane segment (a1) with respect to the total solid content of the resin mold composition.
PETA: Pentaerythritol triacrylate.
DPHA: dipentaerythritol hexaacrylate.
DN-902S: Burnock 902S [isocyanate compound manufactured by DIC Corporation].
17-806: Burnock 17-806 [made by urethane acrylate DIC Corporation].
I-184: Irgacure 184.
BY16-201: Release agent [bifunctional carbinol-modified silicone, manufactured by Toray Dow Corning Co., Ltd.].

As a result, the resin mold compositions for preparing metal molds (Composition-1) to (Composition-4) and (Composition-8) evaluated in Examples 1 to 4 and 8 were excellent in alkali solubility and obtained. The peelability from the obtained metal mold was good. Moreover, the resin mold compositions (Composition-2) to (Composition-3) and (Composition-5) to (Composition-7) evaluated in Examples 2-3, 5-7, 9-12, and 14 ), (Composition-9) to (Composition-12), and (Composition-14) were excellent in peelability from the metal mold and good in peelability between the resin molded product and the metal mold. .
Resin mold compositions for metal mold preparation evaluated in Comparative Examples 1 and 2 (Specific Compositions-1 and -2) are examples of urethane acrylate and surface modification, but alkali solubility, metal mold and resin The peelability from the molded product was inferior to the peelability.

  Resin moldings and resin moldings produced using the resin mold and replica mold of the present invention have various applications such as mold films, nano / micro optical elements, optical elements, display elements, electronic paper, storage, MEMS. It can also be used for PCB mounting materials, high-performance three-dimensional nano / micro channels, next-generation electronic devices, DNA chips, and the like for the purpose of trace biochemical analysis, trace chemical synthesis, and biotechnology.

Claims (11)

A polysiloxane segment (a1) having a structural unit represented by the general formula (1) and / or the general formula (2), a silanol group and / or a hydrolyzable silyl group, and a vinyl polymer segment (a2) Containing a composite resin (A) bonded by a bond represented by the general formula (3),
Curable resin composition for resin molds.

(1)

(2)
(In the general formulas (1) and (2), R ¹ , R ² and R ³ are each independently -R ⁴ -CH = CH ₂ , -R ⁴ -C (CH ₃ ) = CH ₂ ,- A group having one polymerizable double bond selected from the group consisting of R ⁴ —O—CO—C (CH ₃ ) ═CH ₂ and —R ⁴ —O—CO—CH═CH ₂ (provided that R ⁴ Represents a single bond, an aryl group or an alkylene group having 1 to 6 carbon atoms.), An alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group, or a carbon atom. A aralkyl group having a number of 7 to 12 or a group in which part or all of the hydrogen atoms of the alkyl group, cycloalkyl group, aryl group or aralkyl group are substituted with fluorine atoms)

(3)
(In the general formula (3), carbon atoms constitute a part of the vinyl polymer segment (a2), and silicon atoms bonded only to oxygen atoms constitute a part of the polysiloxane segment (a1). To do) The curable resin composition for a resin mold according to claim 1, wherein the polysiloxane segment (a1) further has an epoxy group. The curable resin composition for resin molds of Claim 1 or 2 whose acid value of the solid content of the said composite resin (A) is 30-400 KOHmg / g. The curable resin composition for resin molds according to any one of claims 1 to 3, wherein the composite resin (A) is obtained by copolymerizing a fluorine-containing monomer. The curable resin composition for resin molds according to any one of claims 1 to 4, comprising a release agent. A resin mold using the curable composition for a resin mold according to any one of claims 1 to 5. It produces using the resin mold of Claim 6, The replica mold characterized by the above-mentioned. The replica mold according to claim 7, which is a metal mold. The replica mold according to claim 7, which is a resin molded body. (1) The process of forming the coating film of the curable composition for resin molds in any one of Claims 1-5,
(2) a step of pressing a master mold against the coating film, irradiating and curing an active energy ray, and forming a resin mold;
(3) forming a metal layer on the resin mold;
(4) A method for producing a metal mold, comprising: removing a resin mold from the metal layer to obtain a metal mold. (1) The process of forming the coating film of the curable composition for resin molds in any one of Claims 1-5,
(5) a step of pressing a master mold against the coating film, irradiating and curing an active energy ray, and forming a resin mold;
(6) forming a second resin layer on the resin mold and curing the second resin layer;
(7) A method for producing a resin molded body, comprising a step of peeling a resin mold from the second resin layer to obtain a resin molded body.