JP2013051410A - Dry etching resist material, resist film, and pattern formed article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition for a dry etching resist, excellent in dry etching resistance.SOLUTION: There are provided: a curable resin composition for a dry etching resist, which is excellent in dry etching resistance and obtained by providing a dry etching resist material containing a composite resin (A) having a polysiloxane segment (a1) and a vinyl-based polymer segment (a2); and a resist film formed of the curable resin composition for a dry etching resist. In addition, there are also provided: a laminate formed by laminating the resist film; and a pattern formed article.

Description

  The present invention relates to a resist material and a resist film, and more particularly to a dry etching resist material and a resist film excellent in dry etching resistance suitable for manufacturing printed circuit boards, lead frames, semiconductor packages and the like.

  Conventionally, for printed circuit boards, liquid crystal display elements, plasma displays, large-scale integrated circuits, thin transistors, semiconductor packages, color filters, formation of conductor circuits and electrode processing substrates in organic electroluminescence, etc., or precision metal processing Is known to use a photosensitive composition and a dry film resist material using the same as a resist material such as a solder resist, an etching resist or a plating resist.

  For example, a coating solution of a photosensitive composition is applied on a temporary support film and dried to form a photosensitive composition layer, and a dry film resist material in which the surface of the photosensitive composition layer is covered with a coating film is coated A photosensitive image forming material prepared by peeling a film and laminating it on a substrate to be processed, or a photosensitive composition coating liquid directly applied on a substrate to be processed and dried to form a photosensitive composition layer Using a photosensitive image forming material prepared by covering the surface of the photosensitive composition layer with a protective layer as necessary, the circuit or electrode pattern is drawn on the photosensitive composition layer on the substrate to be processed. After the image exposure through the mask film, the temporary support film or the protective layer is peeled off, and development processing is performed using the difference in solubility in the developer between the exposed area and the unexposed area. Then, after processing the substrate to be processed using this resist image as a resist, etching, plating, soldering, etc., the resist image is removed, so that the circuit or electrode pattern drawn on the mask film is removed. A lithography method for forming on a substrate and a laser direct drawing method for directly forming an image from digital information such as a computer without using a mask film by using a laser beam as an exposure light source are known.

These resist materials include, in addition to alkali solubility when removing resist images, transparency, heat resistance and light resistance, and excellent water resistance, solvent resistance, acid resistance and alkali resistance. Performance is required. This is because during the manufacturing process of the soldered element, the display element is immersed in a solvent, acid or alkali solution, or the surface of the element is locally heated when the wiring electrode layer is formed by sputtering. Etching material or etching resist may be exposed to strong alkali or strong acid (eg cupric chloride, ferric chloride, copper ammonia complex solution, sulfuric acid / hydrogen peroxide solution, hydrofluoric acid, etc.) Derived from.
In recent years, as electronic devices used in personal computers and mobile phones are becoming lighter, thinner and smaller, packages such as printed wiring boards, lead frames, BGAs, and CSPs are required to have fine patterns. .

  It is known to use polysilane as a resin having excellent acid resistance, and as a resist material using this, a unit derived from a polysiloxane group-containing acrylic acid or methacrylic acid derivative, derived from an unsaturated monomer having a carboxyl group A copolymer obtained by copolymerizing a unit and a unit derived from an unsaturated monomer copolymerizable therewith, at least one polymerizable unsaturated group and one or more carboxyl groups in the molecule; A photosensitive resin composition for a solder resist comprising a prepolymer (B) having an acid content (see, for example, Patent Document 1), an acid group-containing resin, an unsaturated compound, a photoinitiator, an unsaturated group, or an epoxy group An ultraviolet curable resist composition for glass etching (for example, see Patent Document 2) containing an alkoxysilane compound and an inorganic fine powder is known.

  However, even with these resins, the present situation is that the dry etching resistance is not sufficiently compatible with the recent fine patterning.

JP 2000-298340 A JP 2007-128052 A

    The problem to be solved by the present invention is to provide a curable resin composition for dry etching resists excellent in dry etching resistance.

Another object of the present invention is to provide a resist film containing the curable resin composition for dry etching resist and a laminate formed by laminating the resist film.

  As a result of intensive studies, the present inventors have found that a curable resin composition for a dry etching resist 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 dry etching resist material containing a composite resin (A) in which a combined 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 This represents an aralkyl group having a number of 7 to 12.)

（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 resist film which consists of said curable resin composition for dry etching resists.

  Moreover, this invention provides the laminated body formed by laminating | stacking the said resist film on a board | substrate.

  The present invention also provides a pattern forming method characterized by patterning a resist film laminated on the laminate and dry etching the substrate using the resist film as a mask, and a pattern formed product obtained thereby.

  According to the present invention, it is possible to obtain a curable resin composition for a dry etching resist that has excellent dry etching resistance and good reproducibility of a fine pattern on a substrate by dry etching.

(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. The segment (a1) (hereinafter simply referred to as polysiloxane segment (a1)) and the vinyl polymer segment (a2) having acid groups (hereinafter simply referred to as vinyl polymer segment (a2)) are represented by the above general formula. It is the composite resin (A) bonded by the bond represented by (3). The bond represented by the general formula (3) is particularly excellent in the acid resistance of the resulting resist film, and is excellent in dry etching resistance and fine pattern reproducibility.

（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.
The structural unit represented by the general formula (1) and / or the general formula (2) preferably contains 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) has a group having a polymerizable double bond as an essential component.
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, or An aralkyl group having 7 to 12 carbon atoms is represented. 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.
In the molecular structure described above, a structure containing a large amount of an aromatic ring or a cyclic hydrocarbon group is preferable from the viewpoint of improving dry etching resistance.

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 the 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 resist film 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.
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.
Further, from the viewpoint of improving dry etching resistance, a structure containing a large amount of aromatic rings or cyclic hydrocarbon groups is preferable.

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 and the hydrolyzable silyl group are formed between the hydroxyl group in the silanol group and the hydrolyzable group in the hydrolyzable silyl group in parallel with the ultraviolet curing reaction when forming a resist film by ultraviolet curing. Since the hydrolysis condensation reaction proceeds, the cross-linking density of the polysiloxane structure of the resulting resist film is increased, and a resist film 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,
Polysiloxanes R ¹ in the general formula (1) is a structural unit is a group having a polymerizable double bond, R ¹ in the general formula (1) coexist and the structural unit is an alkyl group such as methyl It may be segment (a1)
A structural unit R ¹ is an alkyl group such as a methyl group and structural units R ¹ is a group having a polymerizable double bond in the formula (1), the formula in (1), the general formula It may be a polysiloxane segment (a1) in which R ² and R ³ in (2) coexist with a structural unit that is an alkyl group such as a methyl group,
A structural unit in which R ¹ in the general formula (1) is a group having the polymerizable double bond, and a structural unit in which R ² and R ³ in the general formula (2) are alkyl groups such as a methyl group. It may be a coexisting polysiloxane segment (a1),
The polysiloxane segment (a1) may have an epoxy group and is not particularly limited.
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 has high acid resistance, dry etching resistance, and fine pattern reproducibility. It is possible to achieve both the properties of adhesion to a substrate such as glass. Among these, it is preferable to contain 10 to 60% by weight. Further, from the viewpoint of improving dry etching resistance, a structure containing a large amount of aromatic rings or cyclic hydrocarbon groups is preferable.

(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 vinyl polymer segment (a2) 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 Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl ( ) Cycloalkyl (meth) acrylates such as acrylate; ω-alkoxyalkyl (meth) acrylates such as 2-methoxyethyl (meth) acrylate and 4-methoxybutyl (meth) acrylate; styrene, α-methylstyrene, o -Vinyl aromatics such as methyl styrene, m-methyl styrene, p-methyl styrene, 1,3-dimethyl styrene, vinyl naphthalene, vinyl anthracene; carboxyls such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate Acid vinyl esters; alkyl esters of crotonic acid such as methyl crotonic acid and ethyl crotonic acid; dialkyl esters of unsaturated dibasic acids such as dimethyl malate, di-n-butyl malate, dimethyl fumarate, dimethyl itaconate; Ethylene propylene Α-olefins such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene and the like; alkyl vinyl ethers such as ethyl vinyl ether and n-butyl vinyl ether; cyclopentyl vinyl ether, cyclohexyl vinyl ether and the like Alkyl vinyl ethers; tertiary amide group-containing monomers such as N, N-dimethyl (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine, N-vinylpyrrolidone, and the like.

  In addition, the vinyl polymer segment (a2) in the present invention is more preferably a (meth) acrylic repeating unit having an aromatic ring or a cyclic hydrocarbon group from the viewpoint of improving dry etching resistance. The (meth) acrylic repeating unit having an aromatic ring or cyclic hydrocarbon group is preferably a (meth) acrylate having an aromatic ring such as phenyl (meth) acrylate or benzyl (meth) acrylate; cyclohexyl (meth) acrylate, cyclopenta Nyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetracyclododecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, ethylene glycol di (meth) acrylate, isobornyl It has cyclic hydrocarbon groups such as acrylate, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, vinylanthracene ( Data) acrylate and vinyl monomers. Monomers used include ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, 1,4-cyclohexanedimethanol diacrylate, cyclodehydrate Candimethanol di (meth) acrylate, tricyclo [5.2.1.02,6] decandimethanol (meth) acrylate, dicyclopentenyl di (meth) acrylate, 1,4-benzenedimethanol di (meth) acrylate, Examples thereof include hydrogenated bisphenol A di (meth) acrylate and 1,3-adamantanediol di (meth) acrylate. These may be used alone or in combination of two or more.

  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.

  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 Methyldimethoxysilane, 3- (meth) acryloyloxypropyltrichlorosilane, styryltrimethoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, bi-adaman Le trimethoxysilane 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. From the viewpoint of improving dry etching resistance, a structure containing many aromatic rings or cyclic hydrocarbon groups is preferable, and styryltrimethoxysilane, adamantyltrimethoxysilane, adamantyltriethoxysilane, bi-adamantyltrimethoxysilane, and the like are preferable.

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.

  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.

(Dry etching resist material)
The dry etching resist material of the present invention preferably uses a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator according to the curing method.
As the photopolymerization initiator, a known resist material may be used. For example, one or more selected from the group consisting of acetophenones, benzyl ketals, and benzophenones can be preferably used. 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 dry etching resist material 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 generally the curability is increased and the pattern is maintained during dry etching. A resist film excellent in production 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 dry etching resist material 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 Polyisocyanates mainly composed of
Tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (hereinafter abbreviated as “HDI”), 2,2,4- (or 2,4,4-trimethyl-1,6-hexa Methylene 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 Examples include polyisocyanates, biuret type polyisocyanates, adduct type polyisocyanates and isocyanurate type polyisocyanates.

  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-harden, it is preferable to contain polyfunctional (meth) acrylate 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. Polyfunctional (meth) acrylate and the like to be. 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.
Among these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferable.

  In addition, a monofunctional (meth) acrylate can be used 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.

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.
When the polyfunctional and monofunctional acrylates are used, the amount used is preferably 1 to 85% by weight, more preferably 5 to 80% by weight, based on the total solid content of the dry etching resist material of the present invention. By using the polyfunctional acrylate within the above range, physical properties such as hardness of the resulting resist film can be improved.

  When the dry etching resist material of the present invention is cured, thermal curing and photocuring are possible, but photocuring is preferable from the viewpoint of curing speed. Active energy ray curing is particularly preferable, and ultraviolet curing is particularly preferable among them.

  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 the dry etching resist material used in the present invention is thermally cured, 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.

  Other dry etching resist materials used in the present invention include organic solvents, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow regulators, dyes, and leveling agents as necessary. Further, various additives such as a rheology control agent, an ultraviolet absorber, an antioxidant, or a plasticizer can be used.

  In the dry etching resist material used in the present invention, since the composite resin (A) contained has both the polysiloxane segment (a1) and the vinyl polymer segment (a2), the surface smoothness of the coating film is improved. A silicon resin that can be used, an acrylic resin, and an active energy ray-curable monomer are relatively compatible. Therefore, a composition having good compatibility can be obtained.

  The dry etching resist material 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.

(Resist film)
By laminating and curing the dry etching resist material of the present invention on a substrate, a laminate having a resist film and a resist film can be obtained.

As a method for forming the resist film, a known and commonly used method may be used. For example, the resist film can be obtained by applying a resist solution, which is a liquid dry etching resist material, on the surface of the substrate and then curing it. In the case of a liquid dry etching resist material, the concentration of the total solid content in the dry etching resist material is determined according to the coating property (for example, the film thickness after application and solvent removal is within a desired range, 0.1 mass considering the uniformity of the entire processed surface, and even if there are some irregularities on the surface to be processed, a uniform thickness coating film is formed following the irregularities, etc. % To 10% by mass, more preferably 0.4% to 5% by mass, and still more preferably 0.7% to 2% by mass. 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 dry etching resist material of the present invention allows fine pattern processing, the film thickness can be 1 μm or less.

  The solvent to be used may be any organic solvent used in known resist materials, for example, aliphatic or alicyclic systems such as n-hexane, n-heptane, n-octane, cyclohexane, and cyclopentane. Hydrocarbons; 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, n-butyl acetate and isobutyl acetate , Esters such as 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 lenglycol 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 resist film of the present invention is formed as necessary by forming the dry etching resist material of the present invention into a film by a known molding method such as extrusion molding, or applying and drying on a temporary support film. Alternatively, the surface of the photocurable composition layer covered with a coating film may be heat-pressed and laminated on the surface to be processed. 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. At that time, when those films have solvent resistance, heat resistance, etc. necessary for the production of the resist film, the resist material of the present invention is directly applied onto the temporary support film and dried. The resist film of the present invention can be produced, and even if those films have low solvent resistance, heat resistance, etc., for example, mold release such as polytetrafluoroethylene film or release film First, the resist material of the present invention is formed on a film having the property, and then a temporary support film having a low solvent resistance or heat resistance is laminated on the layer, and then the film having the releasability is peeled off. Thus, the resist film of the present invention can also be produced.

  The resist film of the present invention may be formed from a coating film formed by applying the dry etching resist material of the present invention on the surface to be treated and evaporating and removing the solvent. 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.

[Laminate]
The laminate of the present invention is a laminate formed by laminating the resist film of the present invention on a substrate. The substrate used varies depending on the purpose of the resist film of the present invention. For example, quartz, sapphire, glass, optical film, ceramic material, vapor deposition film, magnetic film, reflection film, Al, Ni, Cu, Cr, Fe, stainless steel, etc. Metal substrate, screen mesh, paper, wood, synthetic resin such as silicon, polymer substrate such as SOG (Spin On Glass), polyester film, polycarbonate film, polyimide film, TFT array substrate, light emitting diode such as sapphire and GaN (LED) base materials, glass and transparent plastic base materials, conductive base materials such as indium tin oxide (ITO) and metals, insulating base materials, semiconductors such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon Examples include base materials. 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.
Further, the substrate may already be laminated with a resist underlayer film made of a synthetic resin or the like, and can be used for a multi-layer resist.

[Pattern formation method]
The resist film in the present invention can form a pattern by various methods. For example, a photoresist method such as a photolithography method or a laser direct drawing method may be used, and a pattern-formed resist film is formed by curing in a state where a pattern-formed mold is pressed against a resist film before curing, and then a mold is formed. The pattern can also be formed by peeling off the film.

  As an example of the lithography method, for example, a resist film which is formed by the above method and is cured is laminated on a substrate to be processed, and then image exposure is performed with active light through a mask film. As the light used for the exposure, for example, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an ultraviolet light emitting diode, an argon laser, a helium / cadmium laser, or the like can be used. The amount of light irradiation is appropriately selected depending on the type and amount of the photopolymerization initiator used.

  On the other hand, as an example of the laser direct writing method, a film is formed by the above method and a resist film before curing is laminated, and then scanning exposure is performed with a laser beam having a wavelength of 350 to 430 nm. As the exposure light source, carbon arc lamp, mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp, and laser such as HeNe laser, argon ion laser, YAG laser, HeCd laser, semiconductor laser, ruby laser, etc. Although a light source is mentioned, the light source which generate | occur | produces the laser beam of a blue violet region with a wavelength range of 350-430 nm is especially preferable, and it is more preferable that the center wavelength is about 405 nm. Specific examples include an indium gallium nitride semiconductor laser that oscillates at 405 nm. The scanning exposure method using a laser light source is not particularly limited, and examples thereof include a plane scanning exposure method, an outer drum scanning exposure method, an inner drum scanning exposure method, and the like. The output light intensity is preferably 1 to 100 mW, more preferably 3 to 70 mW, the oscillation wavelength is preferably 390 to 430 nm, more preferably 400 to 420 nm, and the beam spot diameter is preferably 2 to 30 μm, more preferably 4 Scan exposure is performed at a scanning speed of ˜20 μm, a scanning speed of preferably 50 to 500 m / second, more preferably 100 to 400 m / second, and a scanning density of preferably 2,000 dpi or more, more preferably 4,000 dpi or more.

  Next, the uncured portion of the unexposed portion is developed and removed using an alkaline aqueous solution. An aqueous solution of sodium carbonate, potassium carbonate or the like is used as the alkaline aqueous solution. These alkaline aqueous solutions are selected according to the characteristics of the photosensitive resin layer, but generally 0.5 to 3% by mass of sodium carbonate aqueous solution is used.

In the case of pattern formation using a mold, the pattern formed on the resist film is obtained by contacting the film prepared by the above method for pressing the mold on which the pattern is formed and curing the dry etching resist material while holding the mold. Can be formed. The dry etching resist material of the present invention can be suitably used particularly for nanoimprint capable of forming a pattern of 100 nm or less.
Nanoimprinting is a technique in which a nanoimprint mold in which a predetermined fine concavo-convex pattern has been created in advance by electron beam lithography or the like is pressed against a resist-coated substrate, and the concavoconvex of the nanoimprint mold is transferred to a resist film on the substrate. For example, in a region of 1 inch 2 or more, the time required for one process is very short as compared with the laser direct writing method.

  Specifically, in the step of pressing the nanoimprint mold having the concavo-convex structure, the resist film made of the dry etching resist material is pressed into the fine shape of the mold while pressing the nanoimprint mold. At that time, the dry etching resist material can be pressed while being heated to lower the viscosity so that the dry etching resist material more closely follows the fine shape of the mold. Thereafter, the nanoimprint mold is separated by curing the resist film made of the dry etching resist material by irradiating ultraviolet rays, so that the fine shape formed in the nanoimprint mold becomes a resist film made of the dry etching resist material A pattern formed on the surface can be obtained.

Specifically, the nanoimprint mold is pressed and held on a resist film made of a dry etching resist material provided on the substrate surface. The nanoimprint mold is a method for efficiently producing a large-area molded product. An up / down method of a planar original plate suitable for a roll process, a bonding method of a belt original plate, a roll transfer method of a roll original plate, a roll belt A method of contacting by a method such as a roll transfer method of a plate precursor is also preferable. Examples of the material for the nanoimprint mold include quartz glass, ultraviolet transmissive glass, silicon materials such as sapphire, diamond, and polydimethylsiloxane, fluororesin, and other resin materials that transmit light. Further, if the base material used is a material that transmits light, the nanoimprint 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 nanoimprint mold can be selected in any form such as a planar shape, a belt shape, a roll shape, and a roll belt shape. 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.

(Curing process)
Examples of the curing method include a method of irradiating light from the mold side when the 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. 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 pattern to be formed, the pattern 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 on the resist film made of the dry etching resist material 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 molded body is peeled off from the mold, thereby obtaining a resist film in which a concave / convex pattern obtained by transferring the concave / convex pattern of the mold is formed on the surface of a cured resist film made of the dry etching resist material. 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.

[Dry etching resist]
By dry-etching a laminate having a resist film with a pattern formed by the above method, the pattern can be satisfactorily formed on the substrate, and a pattern-formed product with the pattern formed by dry etching can be obtained. it can.
Since the resist film made of the dry etching resist material of the present invention is excellent in dry etching resistance, the pattern or the like is not broken even during the etching, and a fine etching pattern can be provided. Thereby, since the pattern formed on the resist can be transferred to the substrate with high accuracy, the pattern formed product obtained can be a pattern formed product with excellent pattern reproducibility.

As a gas used for dry etching, a known and commonly used gas may be used, for example, oxygen atom-containing gas such as oxygen, carbon monoxide, carbon dioxide, helium, nitrogen, a certain robber inert gas, chlorine, boron chloride, etc. These chlorine-based gas, fluorine-based gas, hydrogen gas, ammonia gas, and the like can be used, and these gases may be used alone or mixed as appropriate.
By etching using these etching gases, a desired pattern can be formed on the substrate.

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 consisting of 0.1 part of “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 [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 at the same temperature for 2 hours, a mixture of 0.05 part of “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 3 [Preparation Example of Vinyl Polymer (a2-2)])
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, 14.5 parts of methyl methacrylate (MMA), 2 parts of n-butyl methacrylate (BMA), 105 parts of cyclohexyl methacrylate (CHMA), 7.5 parts of acrylic acid (AA), 4.5 parts of MPTS, 2-hydroxyethyl While stirring a mixture containing 15 parts of methacrylate (HEMA), 15 parts of n-butyl acetate and 6 parts of tert-butylperoxy-2-ethylhexanoate (TBPEH) at the same temperature under aeration of nitrogen gas And dropped into the reaction vessel in 4 hours. After further stirring at the same temperature for 2 hours, a mixture of 0.05 part of “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 for 10 hours at the same temperature, a vinyl polymer (a2-2) which was a reaction product having a residual amount of TBPEH of 0.1% or less was obtained.

(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 2 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-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)])
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 3 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 -600 parts of composite resin (A-2) having 23.3 parts of butyl and having a polysiloxane segment (a1-1) and a vinyl polymer segment (a2-2) having a nonvolatile content of 50.0% Got.

(Synthesis Example 6 [Preparation Example of Polysiloxane (a1-2)])
In a reaction vessel similar to Synthesis Example 1, 415 parts of methyltrimethoxysilane (MTMS) and 682 parts of styryltrimethoxysilane were charged, and the temperature was raised to 60 ° C. while stirring under nitrogen gas. Next, a mixture consisting of 0.1 part of “A-3” 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. % Polysiloxane (a1-2) 900 parts.

(Synthesis Example 7 [Preparation Example of Vinyl Polymer (a2-3)])
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, 75 parts of styrene (St), 63 parts of methyl methacrylate (MMA), 4.5 parts of MPTS, 7.5 parts of 2-hydroxyethyl methacrylate (HEMA), 15 parts of n-butyl acetate, tert-butyl peroxy-2 -A mixture containing 6 parts of ethylhexanoate (TBPEH) was dropped into the reaction vessel over 4 hours at the same temperature while stirring under a stream of nitrogen gas. After further stirring at the same temperature for 2 hours, a mixture of 0.05 part of “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 1H-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 (a2-3) which is a reaction product having a residual amount of TBPEH of 0.1% or less was obtained.

(Synthesis Example 8 [Preparation Example of Composite Resin (A-3)])
162.5 parts of the polysiloxane (a1-2) obtained in Synthesis Example 16 is added to 307 parts of the vinyl polymer (a2-3) obtained in Synthesis Example 7 and stirred for 5 minutes. 9.6 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 -600 parts of composite resin (A-3) comprising 27.3 parts of butyl and having a polysiloxane segment (a1-2) and a vinyl polymer segment (a2-3) having a nonvolatile content of 50.0% Got.

(Synthesis Example 9 [Preparation Example of Polysiloxane (a1-3)])
In a reaction vessel similar to Synthesis Example 1, 415 parts of methyltrimethoxysilane (MTMS) and 719 parts of γ-glycidoxypropyltrimethoxysilane (GPTS) were charged and stirred at 60 ° C. under aeration of nitrogen gas. The temperature was raised to. Next, a mixture consisting of 0.1 part of “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 (a1-3) which is 0.0% was obtained.

(Synthesis Example 10 [Preparation Example of Composite Resin (A-4)])
162.5 parts of the polysiloxane (a1-3) obtained in Synthesis Example 9 is added to 307 parts of the vinyl polymer (a2-2) obtained in Synthesis Example 3 and stirred for 5 minutes. 9.6 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 -600 parts of composite resin (A-4) comprising 27.3 parts of butyl and having a polysiloxane segment (a1-3) and a vinyl polymer segment (a2-2) having a nonvolatile content of 50.0% Got.

Example 1
(Preparation example of resist composition)
108.5 parts of composite resin (A-1) obtained in Synthesis Example 4, 20.2 parts of pentaerythritol triacrylate (PETA), Irgacure 184 [photopolymerization initiator manufactured by Ciba Japan Co., Ltd.] 3.2 parts, Tinuvin 123 [Hindered amine light stabilizer (HALS), manufactured by Ciba Japan Ltd.] 0.74 parts was mixed to obtain a resist composition (Composition-1).

(Example of uniform coated resist film)
Composition 1 was applied onto a silicon wafer substrate with a spin coater, heated on a hot plate at 80 ° C. for 1 minute, and then from an LED light source (manufactured by Immac Co., Ltd.) having a peak wavelength of 375 nm ± 5 from the resist composition side. The resist film was cured by light irradiation with a light amount of 1000 mJ / cm ² to obtain a resist film (1) having a uniform thickness of 0.5 μm on the substrate surface. By the same method, the uniformly coated resist film (2) was obtained on the white glass substrate, the uniformly coated resist film (3) was obtained on the quartz glass substrate, and the uniformly coated resist film (4) was obtained on the sapphire substrate surface.

(Method for producing pattern resist film)
The composition-1 is coated on a silicon wafer substrate with a spin coater, heated on a hot plate at 80 ° C. for 1 minute, and then a quartz glass having a line and space structure with a width of 200 nm, a pitch of 200 nm, and a height of 200 nm on the surface. A plate-shaped mold made by pressing is pressed and cured by light irradiation with a light amount of 1000 mJ / cm ² from the resist composition side in this state by an LED light source (manufactured by Immac Co., Ltd.) having a peak wavelength of 375 nm ± 5. The silicon wafer substrate was peeled off to obtain a resist film (5) having a line-and-space pattern. By a similar method, a pattern resist film (6) was obtained on a white glass substrate, a pattern resist film (7) was obtained on a quartz glass substrate, and a pattern resist film (8) was obtained on a sapphire substrate.

(Example 2)
A resist composition (Composition-2) 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, uniform coated resist films (9) to (12) and pattern resist films (13) to (16) were obtained.

(Comparative Example 1)
Based on the formulation shown in Table 2, a resist composition (specific composition-1) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, uniform coated resist films (H1) to (H4) and pattern resist films (H5) to (H8) were obtained.

(Example 3)
(Preparation example of resist composition)
Based on the formulation shown in Table 3, a resist composition (Composition-3) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, uniform coated resist films (17) to (20) and pattern resist films (21) to (24) were obtained.

Example 4
(Preparation example of resist composition)
A resist composition (Composition-4) was obtained in the same manner as in Example 1 based on the formulation shown in Table 3.
In the same manner as in Example 1, uniform coated resist films (25) to (28) and pattern resist films (29) to (32) were obtained.

(Example 5)
(Preparation example of resist composition)
Based on the formulation shown in Table 4, a resist composition (Composition-5) was obtained in the same manner as in Example 1.
In the same manner as in Example 1, uniform coated resist films (33) to (36) and pattern resist films (37) to (40) were obtained.

(Evaluation)
The resist films (1) to (40) and (H1) to (H8) obtained in Examples 1 to 5 and Comparative Example 1 were evaluated as follows.

(Dry etching resistance)
Resist films (1), (5), (9), (13), (17), (21), (25), (29), (33), (37) on the obtained silicon wafer substrate , (H1), and (H5), a mixed gas of CF4 / 02 is supplied at a flow rate of 40 sccm and 10 sccm, respectively, using a desktop series Plasma Etching manufactured by UTEC Co., Ltd., and for 1 minute under a vacuum of 0.8 Pa. After performing plasma dry etching, the remaining film thickness was measured, and the etching rate per minute was calculated.

  Resist films (2), (6), (10), (14), (18), (22), (26), (30), (34), (38) on the obtained white glass substrate , (H2), and (H6), an SF6 / C4F8 mixed gas is supplied at a flow rate of 20 sccm and 5 sccm, respectively, using EIS-700 manufactured by Elionix Co., Ltd. After etching, the remaining film thickness was measured and the etching rate per minute was calculated.

  Resist films (3), (7), (11), (15), (19), (23), (27), (31), (35), (39) on the obtained quartz glass substrate , (H3), and (H7), an SF6 / C4F8 mixed gas is supplied at a flow rate of 20 sccm and 5 sccm, respectively, using an EIS-700 manufactured by Elionix Co., Ltd. After etching, the remaining film thickness was measured and the etching rate per minute was calculated.

  Resist films (4), (8), (12), (16), (20), (24), (28), (32), (36), (40) on the obtained sapphire substrate A mixed system of BCl3 / Cl2 / Ar is supplied to (H4) and (H8) at a flow rate of 20 sccm, 15 sccm, and 20 sccm using RIE-101iPH manufactured by SAMCO Co., Ltd. for 1 minute under a vacuum of 0.7 Pa. After performing plasma etching, the remaining film thickness was measured, and the etching rate per minute was calculated.

The obtained etching rate was normalized so that the value of Comparative Example 1 was 1. The smaller the standard value, the better the dry etching resistance, and the evaluation was as follows.
A: Standardized etching rate is 0 or more and less than 0.3 ○: Standardized etching rate is 0.3 or more and less than 0.6 Δ: Standardized etching rate is 0.6 or more and less than 1 x: Standard Etching rate is 1 or more

(Evaluation of pattern reproducibility)
Pattern resist films (5) to (8), (13) to (16), (21) to (24), (29) to (32), (37) to (40), (H5) to (H8) The reproducibility of the accuracy of the pattern after transfer to the substrate after dry etching was evaluated as follows.
A: The pattern sidewall has a high verticality and a highly rectangular cross-sectional shape, and the line pattern has little edge disturbance ○: The pattern sidewall has a high verticality and a highly rectangular cross-sectional shape ×: The pattern sidewall Inferior verticality and inferior rectangularity

Tables 1 and 2 show the compositions of the resist compositions of Examples 1 and 2 and Comparative Example 1 and the evaluation results of the etching rates of the obtained resist films.

About abbreviations in Tables 1-4.
(A1) is an abbreviation for polysiloxane segment (a1).
* 1 Content (%) of the polysiloxane segment (a1) with respect to the total solid content of the curable resin composition.
* 2 Content of the polysiloxane segment (a1) relative to the total solid content of the composite resin (A).
PETA: Pentaerythritol triacrylate.
DN902S: Burnock 902S (isocyanate compound manufactured by DIC Corporation).
PBA: phenylbenzyl acrylate.
TCDDA: Tricyclodecane dimethanol diacrylate.
EPICLON840: Bisphenol A type epoxy resin (manufactured by DIC Corporation).
I-184: Irgacure 184 [manufactured by Ciba Japan Co., Ltd., a photopolymerization initiator].
Tinuvin 123: [hindered amine light stabilizer (HALS) manufactured by Ciba Japan Ltd.].

As a result, the resist films (1) to (44) using the resist compositions (Composition-1) to (Composition-5) evaluated in Examples 1 to 5 were all excellent in dry etching resistance. .
The resist film obtained in Comparative Example 1 is an example not containing the composite resins (A) and (B), but the dry etching resistance and pattern reproducibility evaluation were inferior.

  The resist film using the curable composition of the present invention can be applied to various applications such as mold films, nano / micro optical elements, optical elements, display elements, electronic paper, storage, MEMS / PCB mounting materials, microbiochemical analysis, It can also be used for highly functional three-dimensional nano / micro-channels, next-generation electronic devices, DNA chips, and the like for microchemical synthesis and bioapplications.

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),
Dry etching resist material.

(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. Represents an aralkyl group having a number of 7 to 12)

(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 dry etching resist material according to claim 1, wherein the vinyl polymer segment (a2) has an aromatic ring or a cyclic hydrocarbon group. The dry etching resist material according to claim 1 or 2, wherein the polysiloxane segment (a1) further has an epoxy group. The dry etching resist material according to any one of claims 1 to 3, wherein the vinyl polymer segment (a2) has an alcoholic hydroxyl group. The dry etching resist material according to claim 4, further comprising a polyisocyanate (B). A resist film obtained by curing the dry etching resist material according to claim 1. The resist film according to claim 6, wherein a pattern is formed. The resist film according to claim 7, wherein the pattern is formed by nanoimprinting. A laminate comprising the resist film according to any one of claims 6 to 8 laminated on a substrate. A pattern forming method comprising: forming a pattern on a substrate by dry etching the substrate using the pattern formed on the resist film laminated on the laminate according to claim 9 as a mask. A pattern formed article, wherein a pattern is formed on a substrate by the pattern forming method according to claim 10.