JP5503316B2 - Sheet for forming fine uneven patterns - Google Patents

Description

In order to form a fine concavo-convex pattern by pressing a mold by an imprint method to transfer the pattern onto a sheet for forming a fine concavo-convex pattern, and then curing by irradiating electromagnetic radiation in a state where the mold is removed from the sheet. The present invention relates to a semi-cured fine uneven pattern forming sheet.
Moreover, this invention relates to the composition for fine concavo-convex pattern formation used in order to form the said sheet | seat, and the fine concavo-convex pattern formation method using the composition.

  In recent years, a technique for faithfully transferring a fine pattern called an imprint method has been proposed as a method for forming a fine concavo-convex pattern (see Non-Patent Document 1). In the imprint method, a nanometer order is often referred to as a nanoimprint method, and a micrometer order is referred to as an imprint method. Here, all of them are referred to as an imprint method.

  In the imprint method, a mold formed on a metal, a quartz substrate, a silicon substrate, or the like called a mold on which a pattern corresponding to a negative / positive reversal image of a pattern to be finally transferred is formed is impressed on a resin. The pattern is transferred by curing the resin in the state. A thermal imprint method (see Non-Patent Document 1 and Non-Patent Document 2) in which a resin is cured by heat, an optical imprint method (see Patent Document 1) in which a resin is cured by ultraviolet rays, and the like have been proposed.

  As the thermal imprint method, for example, a (meth) acrylic resin or polycarbonate resin represented by polymethacrylic acid is used as a resin material, and a mold having a fine pattern heated to a temperature higher than the glass transition temperature of the resin is pressed on the resin surface. There is a method of transferring a fine pattern of a mold onto a molten resin surface (see Patent Document 2).

  As the optical imprinting method, for example, after applying a liquid photocurable resist at room temperature on the substrate, a light-transmitting mold is pressed against the resist and irradiated with light to cure the resist on the substrate. There is a method of forming. In the fine unevenness transfer pattern formed when the photocurable resist is cured, a base layer of the photocurable resist is formed in the concave portion. In order to transfer the fine concavo-convex pattern onto the substrate, the base layer is usually removed by dry etching or wet etching (see Patent Document 3).

  In any of these methods, a sheet (foil) having a semi-cured hard coat precursor layer on a substrate is used. However, these sheets cannot be stored for a long time in a semi-cured state because the semi-cured state is unstable. When a long sheet is wound around a roll or the like, adhesion between the sheets (blocking) is avoided. Therefore, there is a problem that it is necessary to sandwich a releasable resin film or the like.

  On the other hand, in the hard coat film, it is known to use an acrylate resin or the like as the UV curable resin. For example, Patent Document 4 discloses (meth) acrylic acid ester mixture (A), photopolymerization initiator (B), ethylenically unsaturated group-containing urethane oligomer (C), colloidal silica sol (D), and diluent (E). It is described that the hard coat film containing is good, and the obtained film has good pencil hardness, curl, and adhesion to the substrate.

  Patent Document 5 discloses (A) oxide particles of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, and cerium, and polymerizable unsaturated. A curable composition containing particles formed by bonding an organic compound containing a group, (B) a compound having a urethane bond and two or more polymerizable unsaturated groups in the molecule, and (C) a photopolymerization initiator. It has been described that it has excellent coating properties, and has high hardness and high refractive index on the surface of various base materials, as well as scratch resistance and adhesion between the base material and the low refractive index layer. It is described that an excellent film (layer) can be formed.

  Furthermore, Patent Document 6 discloses an ultraviolet ray comprising a mixture of a hydrolyzate of an organosilicon compound and metal oxide fine particles, (B) a polyfunctional acrylate or methacrylate, and (C) a photopolymerization initiator. The curable hard coat resin composition is described, and can bleed the surface of the antistatic agent, decrease in transparency, deterioration in moisture resistance, etc. within a practically acceptable range, and as a hard coat Satisfying the above functions (abrasion resistance, surface hardness, moisture resistance, solvent resistance, chemical resistance, etc.).

However, hard coat films using these acrylate resins and the like are inferior to inorganic films in terms of wear resistance, and therefore are improved by adding a metal oxide sol, so that the hardness is improved, There was a problem that transparency and flexibility were lowered.
In response to this problem, the present inventors have found that the thin film containing the polysiloxane-based composition and the ultraviolet curable compound has excellent scratch resistance because the surface is mineralized and has a very high hardness, and is attached to the thin film. It has been found that it has excellent adhesion to the body (Patent Document 7).

JP 2000-194142 A US Pat. No. 5,772,905 JP 2004-304097 A JP 2006-150949 A JP 2005-272702 A JP 2001-214092 A International Publication No. 2008/069217

S. Y. Chou et al. Appl. Phys. Lett., Vol. 67, 1995, P3314 "Thorough explanation of nanoimprint technology", Electric Journal, November 22, 2004, PP20-38

  An object of the present invention is a fine concavo-convex pattern forming sheet used in an imprint method, which is excellent in storage stability before use and has a fine concavo-convex pattern for forming a hard coat layer having high scratch resistance. It is to provide a forming sheet.

  As a result of earnestly researching the above problems, the inventors of the present invention obtained a polysiloxane-based composition, an ultraviolet curable compound, and an organic-inorganic composite containing a photosensitive compound (Patent Document 6), When applied to a sheet for forming a fine concavo-convex pattern by the imprint method, it has excellent storage stability before use and can form a fine concavo-convex pattern for having a certain degree of flexibility. After curing, the fine concavo-convex pattern was maintained. Since the surface is mineralized and has a very high hardness, it has been found that the surface is excellent in scratch resistance, and the present invention has been completed.

That is, the present invention
(1)
On the substrate
a) Formula (I)
R ¹ _n SiX _4-n (I)
(In the formula, n represents 1 or 2, and when n is 2, R ¹ may be the same or different, R ¹ is an organic group, and one or more of R ¹ contains a vinyl group) Represents a hydrocarbon group, X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other.
R ² _n SiX _4-n (II)
(In the formula, n represents 1 or 2, and when n is 2, R ² may be the same or different, and R ² is a vinyl group-containing hydrocarbon in which a carbon atom is directly bonded to Si in the formula. X represents an organic group other than the group, X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other), and a hydrolysis condensate thereof.
{[Compound of formula (I)] + [unit derived from compound of formula (I) in hydrolysis condensate]} / {[compound of formula (I)] + [compound of formula (II)] + [hydrolysis Unit derived from compound of formula (I) in decomposition condensate] + [unit derived from compound of formula (II) in hydrolysis condensate]} × 100 = 30 to 100 mol%, and
{[Compound of formula (II)] + [unit derived from compound of formula (II) in hydrolysis condensate]} / {[compound of formula (I)] + [compound of formula (II)] + [hydrolysis Unit derived from compound of formula (I) in decomposition condensate] + [unit derived from compound of formula (II) in hydrolysis condensate]} × 100 = 0 to 70 mol% of organosilicon compound b) electromagnetic It comprises a layer made of a semi-cured material containing a linear curable compound or a partially cured electromagnetic radiation curable compound, and c) one or more metal compounds selected from Ti, Sn, Al and Zr. Sheet for forming fine uneven patterns by imprinting,
(2)
{[Compound of formula (I)] + [unit derived from compound of formula (I) in hydrolysis condensate]} / {[compound of formula (I)] + [compound of formula (II)] + [hydrolysis Unit derived from compound of formula (I) in decomposition condensate] + [unit derived from compound of formula (II) in hydrolysis condensate]} × 100 = 30 to 95 mol%, and
{[Compound of formula (II)] + [unit derived from compound of formula (II) in hydrolysis condensate]} / {[compound of formula (I)] + [compound of formula (II)] + [hydrolysis Unit derived from compound of formula (I) in decomposition condensate] + [unit derived from compound of formula (II) in hydrolysis condensate]} × 100 = 5 to 70 mol%, The sheet for forming a fine uneven pattern according to the above (1),
(3) The electromagnetic radiation curable compound or the partially cured electromagnetic radiation curable compound is 80% by mass or less based on the total mass of the solid content of the composition, (1) or ( 2) The sheet for forming a fine uneven pattern according to 2), and
(4) The fine concavo-convex pattern forming sheet according to any one of (1) to (3) above, wherein the metal compound is a photosensitive compound.

The present invention also provides:
(5)
a) Formula (I)
R ¹ _n SiX _4-n (I)
(In the formula, n represents 1 or 2, and when n is 2, R ¹ may be the same or different, R ¹ is an organic group, and one or more of R ¹ are vinyl group-containing carbonized. Represents a hydrogen group, X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other.
Formula (II)
R ² _n SiX _4-n (II)
(In the formula, n represents 1 or 2, and when n is 2, R ² may be the same or different, and R ² is a vinyl group-containing hydrocarbon in which a carbon atom is directly bonded to Si in the formula. And X represents a hydroxyl group or a hydrolyzable group, which may be the same or different from each other), and if present, their hydrolytic condensation Made of things,
{[Compound of formula (I)] + [if present, unit derived from compound of formula (I) in hydrolysis condensate]} / {[compound of formula (I)] + [compound of formula (II) Compound] + [if present, a unit derived from the compound of formula (I) in the hydrolysis condensate] + [if present, a unit derived from the compound of formula (II) in the hydrolysis condensate]} × 100 = 30-100 mol%, and
{[Compound of formula (II)] + [unit from the compound of formula (II) in the hydrolysis condensate if present]} / {[compound of formula (I)] + [compound of formula (II) Compound] + [if present, a unit derived from the compound of formula (I) in the hydrolysis condensate] + [if present, a unit derived from the compound of formula (II) in the hydrolysis condensate]} × 100 = 0 to 70 mol%
An organosilicon compound b) an electromagnetic radiation curable compound, and c) one or more metal compounds selected from Ti, Sn, Al and Zr,
including,
A composition for forming a fine concavo-convex pattern by an imprint method,
(6)
{[Compound of formula (I)] + [unit from the compound of formula (I) in the hydrolysis condensate if present]} / {[compound of formula (I)] + [compound of formula (II) Compound] + [if present, a unit derived from the compound of formula (I) in the hydrolysis condensate] + [if present, a unit derived from the compound of formula (II) in the hydrolysis condensate]} × 100 = 30-95 mol%, and
{[Compound of formula (II)] + [unit from the compound of formula (II) in the hydrolysis condensate if present]} / {[compound of formula (I)] + [compound of formula (II) Compound] + [if present, a unit derived from the compound of formula (I) in the hydrolysis condensate] + [if present, a unit derived from the compound of formula (II) in the hydrolysis condensate]} × The composition for forming a fine unevenness pattern by the imprint method according to the above (5), characterized in that 100 = 5 to 70 mol%,
(7) The composition for forming a fine unevenness pattern according to (5) or (6) above, wherein the electromagnetic radiation curable compound is 80% by mass or less based on the total mass of the solid content of the composition. ,as well as,
(8) The fine concavo-convex pattern-forming composition as described in any one of (5) to (7) above, wherein the metal compound is a photosensitive compound.

Furthermore, the present invention includes (9) (A) a step of applying a composition for forming a fine uneven pattern on a substrate,
(B) a step of semi-curing the coated surface by heat and / or electromagnetic radiation to form a fine uneven pattern forming sheet,
(C) a step of pressing the mold to the fine uneven pattern forming sheet by an imprint method to transfer the fine uneven pattern;
(D) a step of curing by irradiating electromagnetic rays in a state where the mold is removed from the transferred sheet for forming a fine uneven pattern,
A method for forming a fine uneven pattern, characterized by comprising:
(10) The fine unevenness according to (9) above, wherein the composition for forming a fine unevenness pattern is the composition for forming a fine unevenness pattern according to any of (5) to (8) above. The present invention relates to a pattern forming method.

When the composition for forming a fine concavo-convex pattern according to the present invention is used for creating a fine concavo-convex pattern by an imprint method, it forms a fine concavo-convex pattern that is excellent in storage stability and has a certain degree of flexibility before use. After curing, the surface is mineralized while maintaining a fine uneven pattern and has a very high hardness, and therefore has excellent scratch resistance.
In addition, by applying the composition for forming a fine concavo-convex pattern of the present invention on a substrate and semi-curing it, after pressing the mold, the mold can be removed and irradiated with electromagnetic radiation. It is not necessary to use a base material or mold that transmits the electromagnetic waves required when irradiating electromagnetic waves with the mold pressed, as is done with optical imprinting, and inexpensive mold materials can be used. The base material can be any material, and the manufacturing cost can be greatly reduced.

Microscope observation image of Si wafer mold (L / S = 5μm / 5μm) Microscopic observation image of fine pattern produced in Example 1 Scanning electron microscope image of the fine pattern produced in Example 4

In this specification, “electromagnetic radiation” means ultraviolet rays, X-rays, radiation, ionizing radiation, and ionizing radiation (α, β, γ rays, neutron rays, electron rays).
Further, “semi-cured” means a state in which there is no tackiness and is cured to the extent that no crack is generated following the mold during molding. Furthermore, the “cured” means a state where it is cured to such an extent that it is hardly scratched by rubbing with steel wool.

1. Composition for forming fine concavo-convex pattern The composition for forming fine concavo-convex pattern in the present invention is a composition for laminating on a base material to form a hard coat layer for creating a fine concavo-convex pattern. contains.

a) Organosilicon compound The organosilicon compound in the composition for forming a fine uneven pattern of the present invention contains the following components.
a-1) Formula (I)
R ¹ _n SiX _4-n (I)
(In the formula, n represents 1 or 2, and when n is 2, R ¹ may be the same or different, R ¹ is an organic group, and one or more of R ¹ contains a vinyl group) Represents a hydrocarbon group, X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other.) Compound a-2) represented by formula (II)
R ² _n SiX _4-n (II)
(In the formula, n represents 1 or 2, and when n is 2, R ² may be the same or different, and R ² is a vinyl group-containing hydrocarbon in which a carbon atom is directly bonded to Si in the formula. Represents an organic group other than a group, X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other.) Compound a-3) represented by Condensate

  The organosilicon compound in the composition for forming a fine concavo-convex pattern of the present invention is composed of the compound represented by the formula (I) and the compound represented by the formula (II), and, if present, their hydrolytic condensates. Although it is a mixture, the compound represented by (II) and the hydrolysis condensate containing it as a unit do not necessarily exist. The hydrolysis condensate is a dimer or the like in which compounds are hydrolyzed and condensed to form a siloxane bond, and only a compound of formula (I) or formula (II) is hydrolyzed and condensed. It may be a product obtained by hydrolytic condensation of the compound of formula (I) and the compound of formula (II), or two or more of these may be mixed.

{[Compound of formula (I)] + [if present, unit derived from compound of formula (I) in hydrolysis condensate]} / {[compound of formula (I)] + [compound of formula (II) Compound] + [if present, a unit derived from the compound of formula (I) in the hydrolysis condensate] + [if present, a unit derived from the compound of formula (II) in the hydrolysis condensate]} × 100 is preferably 30 to 100 mol%, more preferably 30 to 95 mol%,
{[Compound of formula (II)] + [unit from the compound of formula (II) in the hydrolysis condensate if present]} / {[compound of formula (I)] + [compound of formula (II) Compound] + [if present, a unit derived from the compound of formula (I) in the hydrolysis condensate] + [if present, a unit derived from the compound of formula (II) in the hydrolysis condensate]} × 100 is preferably 0 to 70 mol%, more preferably 5 to 70 mol%.
The average particle size of the hydrolysis-condensation product is preferably 2 nm to 100 nm, and more preferably 5 nm to 30 nm. If the average particle size is larger than 100 nm, the film becomes cloudy, the solution becomes unstable, and gelation tends to occur. If the average particle size is smaller than 2 nm, the coating properties may be adversely affected.

In the formula (I), n represents 1 or 2, and n is preferably 1. When n is 2, R ¹ may be the same or different, R ¹ is an organic group, and one or more of R ¹ represent a vinyl group-containing hydrocarbon group. That is, when n is 1, R ¹ is a vinyl group-containing hydrocarbon group, and when n is 2, 1 or 2 of R ¹ is the vinyl group-containing hydrocarbon group, and groups other than the above Is an organic group.
Examples of the vinyl group-containing hydrocarbon group include alkenyl groups (preferably C2-8 alkenyl groups) such as vinyl group, allyl group, 3-butenyl group, and 4-hexenyl group, 2-cyclopropenyl group, and 2-cyclo And cycloalkenyl groups (preferably, C3-8 cycloalkenyl groups) such as a pentenyl group, 3-cyclohexenyl group, and 4-cyclooctenyl group.

Examples of the organic group include a hydrocarbon group that may have a substituent other than the above-mentioned vinyl group-containing hydrocarbon group, a group made of a polymer of a vinyl compound that may have a substituent, and the like. .
Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkynyl group, and an aryl group. Of these, an optionally substituted hydrocarbon group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms and an epoxyalkyl group having 1 to 10 carbon atoms are more preferable.
The organic group may contain a silicon atom or a group containing a polymer such as polysiloxane, polyvinylsilane, or polyacrylsilane.

Here, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, isoheptyl, tert-heptyl, n-octyl, Isooctyl, tert-octyl, 2-ethylhexyl and the like can be mentioned, and among them, an alkyl group having 1 to 10 carbon atoms is preferable.
Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like. Among these, a cycloalkyl group having 3 to 8 carbon atoms is preferable.
The alkynyl group includes ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2-methyl-3-butynyl group 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group and the like, among which alkynyl group having 2 to 6 carbon atoms is preferable.
The aryl group means a monocyclic or polycyclic aryl group. In the case of a polycyclic aryl group, a partially saturated group is also included in addition to a fully unsaturated group. Examples of the aryl group include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group. Of these, a C6-10 aryl group is preferable.

  Examples of the “substituent” in the above “optionally substituted” include a halogen atom, an alkoxy group, an alkenyloxy group, an alkenylcarbonyloxy group, and an epoxy group.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Alkoxy groups include methoxy, ethoxyl, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, neopentoxy, 1-methylbutoxy, n-hexyloxy, isohexyl Examples thereof include oxy and 4-methylpentoxy, and an alkoxy group having 1 to 10 carbon atoms is preferable.
An alkenyloxy group is a group in which an oxygen atom is bonded to an alkenyl group having a carbon-carbon double bond at any one or more positions, such as vinyloxy, 2-propenyloxy, 3-butenyloxy, 4-pentenyloxy and the like. An alkenyloxy group having 2 to 10 carbon atoms is preferable.
The alkenylcarbonyloxy group is a group in which the alkenyl group is bonded to the carbonyloxy group, and examples thereof include acryloxy, methacryloxy, allylcarbonyloxy, 3-butenylcarbonyloxy and the like, and an alkenylcarbonyloxy group having 2 to 10 carbon atoms is preferable.

As a polymer of a vinyl compound which may have a substituent, for example,
(Meth) acrylate esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate;
Carboxylic acids such as (meth) acrylic acid, itaconic acid, fumaric acid and acid anhydrides such as maleic anhydride;
Epoxy compounds such as glycidyl (meth) acrylate;
Amino compounds such as diethylaminoethyl (meth) acrylate and aminoethyl vinyl ether;
Amide compounds such as (meth) acrylamide, itaconic acid diamide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl (meth) acrylamide;
Examples thereof include vinyl polymers obtained by singly or copolymerizing vinyl compounds selected from acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, and the like.

In formula (II), n represents 1 or 2, and n is more preferably 1. When n is 2, R ² may be the same or different, and R ² represents an organic group other than a vinyl group-containing hydrocarbon group in which a carbon atom is directly bonded to Si in the formula. As the organic group for R ^2, the same organic groups as those for R ¹ can be exemplified.

  In formula (I) and formula (II), X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other. A hydrolyzable group is, for example, a group that can be hydrolyzed to form a silanol group or a siloxane condensate by heating at 25 ° C. to 100 ° C. in the presence of no catalyst and excess water. Specifically, an alkoxy group, an acyloxy group, a halogen atom, an isocyanate group and the like can be mentioned, and an alkoxy group having 1 to 4 carbon atoms or an acyloxy group having 1 to 4 carbon atoms can be used. preferable.

  Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, and a t-butoxy group. Examples of the acyloxy group include acyloxy groups such as formyloxy, acetyloxy and propanoyloxy.

Specifically, examples of the compound represented by the formula (I) include vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, and 3-butenyl. Trimethoxysilane, 2-cyclopropenyltrimethoxysilane, 2-cyclopentenyltrimethoxysilane, 2-cyclohexenyltrimethoxysilane, divinyldiaminosilane, divinyldichlorosilane, divinyldiacetoxysilane, divinyldimethoxysilane, diallyldimethoxysilane, Examples include di-3-butenyldimethoxysilane, vinylmethyldimethoxysilane, vinylethyldiethoxysilane, allylmethyltrimethoxysilane, and allylethyltriethoxysilane.
Examples of the compound represented by the formula (II) include methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxy Silane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, nonafluorobutylethyltrimethoxysilane, trifluoromethyltrimethoxysilane, dimethyldiaminosilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, Dibutyldimethoxysilane, trimethylchlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Silane, 3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane, oxacyclohexyltrimethoxysilane, methyltri (meth) acryloxysilane, methyl [2- (meth) acryloxyethoxy] silane, methyl-triglycidyl Examples include loxysilane and methyltris (3-methyl-3-oxetanemethoxy) silane.

These can be used alone or in combination of two or more.
When organic silicon compounds are used in combination, for example, a combination of vinyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane and a combination of vinyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane can be preferably exemplified.

  These organosilicon compounds may be condensates. Specific examples of the condensate include a dimer obtained by hydrolytic condensation of the organosilicon compound to form a siloxane bond.

Further, among the organosilicon compounds represented by the formula (I), those in which R ¹ has 3 or less carbon atoms are 30 mol% or more, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. It is. Further, among the organosilicon compounds represented by the formula (I), those in which R ¹ has 4 or more carbon atoms are 70 mol% or less, preferably 0 to 70 mol%, more preferably 0 to 50 mol%. It is.

b) Electromagnetic curable compound The electromagnetic curable compound of the present invention is a compound that is polymerized by irradiation with active energy rays. In particular, it is a compound or resin having a functional group that causes a polymerization reaction upon irradiation with ultraviolet light in the presence of a photopolymerization initiator, and includes (meth) acrylate compounds, epoxy resins, vinyl compounds other than acrylate compounds, and the like. . The number of functional groups is not particularly limited as long as it is 1 or more.
Examples of acrylate compounds include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyryl (meth) acrylate, polycarbonate diacrylate, and tripropylene glycol diacrylate. (Meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, siloxane polymer having (meth) acryloyloxy group, and the like, preferably polyester ( (Meth) acrylate, polyurethane (meth) acrylate, and epoxy poly (meth) acrylate, and more preferably polyurethane (meth) acrylate. ) Acrylate.
The molecular weight is not limited as long as it has compatibility with other hard coat layer compositions, but is usually 500 to 50,000, preferably 1,000 to 10,000 as a weight average molecular weight.

The epoxy (meth) acrylate can be obtained, for example, by an esterification reaction between an oxirane ring of a low molecular weight bisphenol type epoxy resin or a novolak epoxy resin and acrylic acid.
The polyester (meth) acrylate is obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends with acrylic acid, obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol. Alternatively, it can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with acrylic acid.
Urethane (meth) acrylate is a reaction product of an isocyanate compound obtained by reacting a polyol with diisocyanate and an acrylate monomer having a hydroxyl group, and examples of the polyol include polyester polyol, polyether polyol, and polycarbonate diol. .

As a commercial item of urethane (meth) acrylate used in the present invention, for example,
Product name: Beam set 102, 502H, 505A-6, 510, 550B, 551B, 575, 575CB, EM-90, EM92;
Product name: Photomer 6008, 6210, manufactured by San Nopco
Product name: NK Oligo U-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA, U-324A, U-4H, U-6H;
Product name: Aronix M-1100, M-1200, M-1210, M-1310, M-1600, M-1960;
Kyoeisha Chemical Co., Ltd. product name: AH-600, AT606, UA-306H;
Nippon Kayaku Co., Ltd. product name: Kayrad UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101;
Nippon Synthetic Chemical Industry Co., Ltd. Product name: Purple light UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV-7000, UV-7600B, UV-2010B, UV-7610B, UV-7630B, UV- 7550B;
Product name: Art Resin UN-1255, UN-5200, HDP-4T, HMP-2, UN-901T, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, H-61 HDP-M20;
Product name: Ebecryl 6700, 204, 205, manufactured by Daicel UCB Co., Ltd.
220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129, 6602, 8301;
Product name: ACA200M, ACAZ230AA, ACAZ250, ACAZ300, ACAZ320;
Etc.

  Examples of vinyl compounds other than acrylate compounds include N-vinyl pyrrolidone, N-vinyl caprolactam, vinyl acetate, styrene, and unsaturated polyester. Epoxy resins include hydrogenated bisphenol A diglycidyl ether, 3, 4 -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexyl) And methyl) adipate.

Examples of the photopolymerization initiator include (i) a compound that generates a cationic species by light irradiation, and (ii) a compound that generates an active radical species by light irradiation.
As a compound that generates a cationic species by light irradiation, for example, an onium salt having a structure represented by the following formula (III) can be given as a preferred example.
This onium salt is a compound that releases a Lewis acid by receiving light.
[R1aR2bR3cR4dW] + e [MLe + f] −e (III)
(In the formula (III), the cation is an onium ion, W is S, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, or N≡N—, and R1, R2 , R3 and R4 are the same or different organic groups, a, b, c and d are each an integer of 0 to 3, and (a + b + c + d) is equal to the valence of W. M is a halide complex. [MLe + f] is a metal or metalloid constituting the central atom, for example, B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co L is, for example, a halogen atom such as F, Cl, Br, etc. e is the net charge of the halide complex ion, and f is the valence of M.)

Specific examples of the anion (MLe + f) in the above formula (III) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoroarsenate. (AsF ₆ ⁻ ), hexachloroantimonate (SbCl ₆ ⁻ ) and the like.
An onium salt having an anion represented by the formula [MLf (OH) ⁻ ] can also be used. Furthermore, perchlorate ion (ClO ₄ ⁻ ), trifluoromethane sulfonate ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluene sulfonate ion, trinitrobenzene sulfonate anion, trinitrotoluene sulfonate The onium salt which has other anions, such as an acid anion, may be sufficient. These can be used alone or in combination of two or more.

  Examples of compounds that generate active radical species by light irradiation include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, and benzaldehyde. Fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoinpropyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1 -(4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxa , Diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2 , 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. .

  The blending amount of the photopolymerization initiator used in the present invention is preferably 0.01 to 20% by mass, preferably 0.1 to 10% by mass, based on the solid content of the (meth) acrylate-based ultraviolet curable compound. Is more preferable.

  In the present invention, a sensitizer can be added as necessary. For example, trimethylamine, methyldimethanolamine, triethanolamine, p-dimethylaminoacetophenone, p-dimethylaminoethyl benzoate, p- Isoamyl dimethylaminobenzoate, N, N-dimethylbenzylamine, 4,4′-bis (diethylamino) benzophenone and the like can be used.

  It is preferable that an ultraviolet curable compound is 80 mass% or less with respect to the total mass of solid content of the composition for fine uneven | corrugated pattern formation.

c) One or more metal compounds selected from Ti, Sn, Al and Zr (silanol condensation catalyst)
One or more kinds of metal compounds selected from Ti, Sn, Al and Zr used as silanol condensation catalysts are those which hydrolyze hydrolyzable groups in organosilicon compounds and condense silanols to form siloxane bonds. However, organic metal compounds, organic acid metal salts, metal chelate compounds and the like can be mentioned.
Examples of the organic metal include alkyl metal compounds such as tetramethyl titanium and tetrapropyl zirconium, and metal alcoholates such as tetraisopropoxy titanium and tetrabutoxy zirconium.
Examples of the organic acid metal salt include a carboxylic acid metal salt, a sulfonic acid metal salt, and a phenol metal salt.
Examples of the metal chelate compound include metal chelate compounds with β-ketocarbonyl compounds, β-ketoester compounds, α-hydroxyester compounds, and the like.

Among these, a photosensitive compound capable of removing the carbon component on the surface side by the action of light having a wavelength of 350 nm or less is particularly preferable.
The photosensitive compound is a compound capable of removing the carbon component on the surface side by the action of light having a wavelength of 350 nm or less irradiated from the surface side, regardless of the mechanism, preferably the surface The carbon content of the surface part in the depth direction from 2 nm to 80% or less of the carbon content of the part where the carbon content does not decrease (in the case of a film, for example, the back surface part in the depth direction from the film back to 10 nm), Preferably, it is a compound that can be made 2 to 60%, more preferably 2 to 40%, and particularly preferably, the carbon component is removed to a predetermined depth so that its removal amount gradually decreases from the surface side. A possible compound, that is, a compound capable of forming a layer in which the carbon content gradually increases from the surface to a predetermined depth. Specific examples include compounds that absorb and excite light having a wavelength of 350 nm or less.
Here, the light having a wavelength of 350 nm or less is light using a light source having light of any wavelength of 350 nm or less, preferably a light source having light of any wavelength of 350 nm or less as a main component. That is, light using a light source having a wavelength of 350 nm or less with the largest component amount.

  Examples of the photosensitive compound used in the present invention include metal chelate compounds selected from Ti, Sn, Al and Zr, organic acid salts, metal compounds having two or more hydroxyl groups or hydrolyzable groups, and their hydrolysis. And at least one compound selected from the group consisting of condensates thereof, preferably a hydrolyzate and / or a condensate, in particular, a hydrolyzate and / or condensate of a metal chelate compound. preferable. Examples of the compound derived therefrom include those obtained by further condensing a condensate of a metal chelate compound. As described above, the photosensitive compound and / or derivative thereof may be chemically bonded to the organosilicon compound, dispersed in a non-bonded state, or in a mixed state thereof. .

  The metal chelate compound is preferably a metal chelate compound having a hydroxyl group or a hydrolyzable group, and more preferably a metal chelate compound having two or more hydroxyl groups or hydrolyzable groups. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more. The metal chelate compound is preferably a β-ketocarbonyl compound, a β-ketoester compound, or an α-hydroxyester compound. Specifically, methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, acetoacetate β-ketoesters such as n-butyl, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane Β-diketones such as -2,4-dione, nonane-2,4-dione and 5-methyl-hexane-2,4-dione; compounds coordinated with hydroxycarboxylic acids such as glycolic acid and lactic acid Can be mentioned.

  The metal organic acid salt compound is a compound composed of a salt obtained from a metal ion and an organic acid. Examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid, benzoic acid; sulfonic acid, sulfinic acid, thiophenol. Organic compounds exhibiting acidity such as sulfur-containing organic acids such as phenol compounds, enol compounds, oxime compounds, imide compounds, aromatic sulfonamides, and the like.

  In addition, the metal compound having two or more hydroxyl groups or hydrolyzable groups excludes the metal chelate compound and the metal organic acid salt compound, and examples thereof include hydroxides, propoxides, isopropoxides, butoxides and the like. Examples thereof include metal alcoholates.

  Examples of the hydrolyzable group in the metal compound, metal chelate compound or metal organic acid salt compound include an alkoxy group, an acyloxy group, a halogen group, and an isocyanate group, and an alkoxy group having 1 to 4 carbon atoms and 1 to 1 carbon atoms. An acyloxy group of 4 is preferred. In addition, having two or more hydroxyl groups or hydrolyzable groups means that the sum of hydrolyzable groups and hydroxyl groups is 2 or more.

  Such a hydrolyzate and / or condensate of a metal compound is obtained by hydrolyzing 0.5 mol or more of water with respect to 1 mol of a metal compound having two or more hydroxyl groups or hydrolyzable groups. It is preferable that it is a thing hydrolyzed using 0.5-2 mol water.

  Further, the hydrolyzate and / or condensate of the metal chelate compound is preferably hydrolyzed using 5 to 100 mol of water with respect to 1 mol of the metal chelate compound, More preferably, it is hydrolyzed with water.

  The hydrolyzate and / or condensate of the metal organic acid salt compound is preferably one hydrolyzed using 5 to 100 mol of water with respect to 1 mol of the metal organic acid salt compound. More preferably, it is hydrolyzed with ˜20 mol of water.

  In the present invention, when two or more kinds of silanol condensation catalysts are used, the compound having the photosensitivity described above may be included, or the compound having the photosensitivity may not be included. Further, a compound having photosensitivity and a compound not having photosensitivity can be used in combination.

2. Preparation of the composition for forming a fine uneven pattern As a method for preparing the composition for forming a fine uneven pattern of the present invention, water and a solvent are added as necessary, and an organosilicon compound, an electromagnetic radiation curable compound, and Ti, Sn, One or more metal compounds selected from Al and Zr are mixed.
Specifically, it can be according to known conditions and methods, for example, it can be prepared by the method described in WO2008 / 69217.

The solvent to be used is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane and octane; alicyclic hydrocarbons such as cyclohexane and cyclopentane. Ketones such as acetone, methyl ethyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; esters such as ethyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; dimethyl sulfoxide And the like; alcohols such as methanol, ethanol, propanol and butanol; polyhydric alcohol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate; and the like. These solvents can be used alone or in combination of two or more.
When two or more types are combined, for example, a combination of butanol / ethyl acetate / ethanol is preferable.

The solid content of the composition for forming a fine concavo-convex pattern of the present invention (one or more metal compounds selected from an organic silicon component, an ultraviolet curable compound, Ti, Sn, Al and Zr, a photopolymerization initiator, etc.) is 1 It is preferable that it is -75 mass%, and it is more preferable that it is 10-60 mass%. For the total mass of solids such as one or more metal compounds selected from organosilicon compounds and / or their hydrolysis condensates, Ti, Sn, Al and Zr, ultraviolet curable compounds and photopolymerization initiators, ultraviolet rays The curable compound is not particularly limited, but is preferably 80% or less, more preferably 10 to 70%.
In addition, when a photosensitive compound is included as one or more kinds of metal compounds selected from Ti, Sn, Al, and Zr, the content of the photosensitive compound is generally organic silicon, although it depends on the type. It is preferable that the metal atom in a photosensitive compound is 0.01-0.5 molar equivalent with respect to Si in a compound, Preferably it is 0.05-0.2 molar equivalent.

  In addition, tetrafunctional silane or colloidal silica can be added to the composition for the purpose of improving the hardness of the obtained hard coat layer. Examples of the tetrafunctional silane include tetraaminosilane, tetrachlorosilane, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetrabenzyloxysilane, tetraphenoxysilane, tetra (meth) acryloxysilane, tetrakis [2 -(Meth) acryloxyethoxy] silane, tetrakis (2-vinyloxyethoxy) silane, tetraglycidyloxysilane, tetrakis (2-vinyloxybutoxy) silane, tetrakis (3-methyl-3-oxetanemethoxy) silane be able to. Examples of the colloidal silica include water-dispersed colloidal silica and organic solvent-dispersed colloidal silica such as methanol or isopropyl alcohol.

3. Fine uneven pattern forming sheet The fine uneven pattern forming sheet of the present invention is a sheet before forming a hard coat layer for creating a fine uneven pattern, and the fine uneven pattern formed on a substrate is formed. It is a hard-coat precursor layer containing the semi-hardened | cured material of the composition for an object.
The semi-cured product of the composition for forming a fine uneven pattern means that when it is heated, it contains a compound in which at least a part of the organosilicon compound in the composition is hydrolyzed and condensed. Moreover, when electromagnetic radiation is used, it means that at least a part of the organosilicon compound in the composition includes a compound obtained by hydrolysis and condensation and a compound in which the electromagnetic radiation curable compound is partially cured.

The semi-cured product of the composition for forming a fine uneven pattern of the present invention is
a) Formula (I)
R ¹ _n SiX _4-n (I)
(In the formula, n represents 1 or 2, and when n is 2, R ¹ may be the same or different, R ¹ is an organic group, and one or more of R ¹ contains a vinyl group) Represents a hydrocarbon group, X represents a hydroxyl group or a hydrolyzable group, and may be the same or different from each other.
R ² _n SiX _4-n (II)
(In the formula, n represents 1 or 2, and when n is 2, R ² may be the same or different, and R ² is a vinyl group-containing hydrocarbon in which a carbon atom is directly bonded to Si in the formula. And X represents a hydroxyl group or a hydrolyzable group, which may be the same or different from each other), and an organosilicon compound comprising a hydrolysis condensate thereof ,
b) An electromagnetic radiation curable compound or a partially cured electromagnetic radiation curable compound, and c) one or more metal compounds selected from Ti, Sn, Al, and Zr.
Here, the specific example of each substituent is the same as the specific example of the compound represented by Formula (I) and (II) in the said composition for fine uneven | corrugated pattern formation.

The organosilicon compound in the semi-cured product is a mixture of the compounds represented by the formulas (I) and (II) and their hydrolysis condensates, but most of them are usually hydrolysis condensates.
The composition of the organosilicon compound is as follows.
{[Compound of formula (I)] + [unit derived from compound of formula (I) in hydrolysis condensate]} / {[compound of formula (I)] + [compound of formula (II)] + [hydrolysis Unit derived from compound of formula (I) in decomposition condensate] + [unit derived from compound of formula (II) in hydrolysis condensate]} × 100 is preferably 30 to 100 mol%, more preferably 30 ~ 95 mol%,
{[Compound of formula (II)] + [unit derived from compound of formula (II) in hydrolysis condensate]} / {[compound of formula (I)] + [compound of formula (II)] + [hydrolysis Unit derived from compound of formula (I) in decomposition condensate] + [unit derived from compound of formula (II) in hydrolysis condensate]} × 100 is preferably 0 to 70 mol%, more preferably Is 5 to 70 mol%.

  Examples of the fine uneven pattern forming sheet include a press forming sheet, a vacuum forming sheet, a pressure forming sheet, a mat forming sheet, an emboss forming sheet, an in-mold lamination sheet, and the like. In these sheets, a hard coat precursor layer made of a semi-cured product of the hard coat layer forming composition is laminated on one surface of the substrate. Further, if necessary, a decorative layer such as a pattern layer or a metal vapor deposition layer may be laminated on the surface opposite to the hard coat layer, and a primer layer may be provided between the substrate and the hard coat layer. .

  As the base material, various materials can be applied depending on the application as long as they have heat resistance, mechanical strength, solvent resistance and the like. For example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as nylon 6, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, vinyl resins such as polyvinyl chloride, polymethacrylate and polymethyl Examples thereof include acrylic resins such as methacrylate, styrene resins such as polycarbonate and high impact polystyrene, cellulose films such as cellophane and cellulose acetate, and imide resins such as polyimide. Acrylic resins, polyester resins, and polycarbonates are preferable in terms of moldability, heat resistance, and mechanical strength. The thickness of the substrate is usually about 10 to 5000 μm, preferably 100 to 2000 μm.

  The substrate may be a copolymer resin containing these resins as a main component, a mixture (including an alloy), or a laminate composed of a plurality of layers. The substrate may be a stretched film or an unstretched film, but a film stretched in a uniaxial direction or a biaxial direction is preferable for the purpose of improving the strength. The substrate is used as a film, sheet or board formed of at least one layer of these resins. Prior to coating, the substrate is subjected to corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer (also called an anchor coat, adhesion promoter, or easy adhesive) coating treatment, pre-heat treatment, removal. Easy adhesion treatment such as dust treatment, vapor deposition treatment, and alkali treatment may be performed. Moreover, you may add additives, such as a filler, a plasticizer, a coloring agent, and an antistatic agent, as needed.

  The thickness of the hard coat precursor layer on the substrate is preferably 0.5 to 20 μm, particularly preferably about 1 to 10 μm, although it varies depending on the application.

  In addition, various additives such as antistatic agent, water repellent agent, oil repellent agent, stabilizer, conductive agent, antifogging agent, etc. are added to each layer as long as the physical properties and functions of each layer are not impaired. can do.

4). A method for forming a fine uneven pattern by an imprint method will be described in detail.
1st process: The process of apply | coating the composition for fine concavo-convex pattern formation on a base material 2nd process: The process of semi-hardening the coating surface with heat and / or electromagnetic radiation to make a sheet for forming a fine concavo-convex pattern Step: Step of transferring the fine concavo-convex pattern by pressing the mold onto the fine concavo-convex pattern forming sheet by the imprint method Fourth step: Irradiating electromagnetic waves with the mold removed from the transferred fine concavo-convex pattern forming sheet Curing process

(First step)
The composition for forming a fine concavo-convex pattern of the present invention can be performed by coating on a substrate, but various known laminating methods can be used. For example, each layer can be formed by methods such as microgravure coating, comma coating, bar coater coating, air knife coating, offset printing, flexographic printing, screen printing, spray coating, and the like.

(Second step)
Formation of the fine uneven pattern forming sheet on the substrate is semi-cured by applying a liquid containing the fine uneven pattern forming composition on the substrate and then irradiating with heat and / or electromagnetic radiation. Do it. By this step, the condensate of the organosilicon compound in the hard coat layer forming composition is cross-linked, and the hard coat layer is semi-cured. When an organic solvent is used as a diluting solvent or the like, the organic solvent is removed by heating. Heating is usually 40 to 200 ° C, preferably 50 to 150 ° C. The heating time is usually 10 seconds to 30 minutes, preferably 30 seconds to 5 minutes.

(Third step)
A sheet having a concavo-convex structure formed of a specific pattern is pressed against a sheet that is a semi-cured product of the composition for forming a fine concavo-convex pattern laminated on a substrate, thereby deforming the sheet for forming a fine concavo-convex pattern. For example, this is performed using a Si wafer mold in which a specific line is formed by a hydraulic press.
Although pressing of a mold can be performed by a well-known method, it is normally performed at a temperature of 20 to 200 ° C. for 30 seconds to 30 minutes.

(4th process)
Conventionally, electromagnetic radiation was applied while pressing the mold against the fine uneven pattern forming sheet. However, in the present invention, after removing the mold from the substrate on which the fine uneven pattern forming sheet was laminated, Irradiate the line.

As electromagnetic radiation, ultraviolet rays, X-rays, radiation, ionizing radiation, ionizing radiation (α, β, γ rays, neutron rays, electron beams) can be used, and light having a wavelength of 350 nm or less is preferable.
The irradiation of the active energy ray can be performed using a known apparatus such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer lamp, a carbon arc lamp, or a xenon arc lamp. The light source to be used is preferably a light source including light of any wavelength in the range of 150 to 350 nm, and more preferably a light source including light of any wavelength in the range of 250 to 310 nm.
Moreover, as light irradiation quantity of the light irradiated in order to fully harden the hard-coat layer of a semi-hardened state, about 0.1-100 J / cm < ² > is mentioned, for example, Film hardening efficiency (an irradiation energy and a film hardening grade considering the relationship), it is preferably about 1~10J / cm ^2, and more preferably about 1~5J / cm ^2.

  The hard coat layer formed from the composition for forming a fine unevenness pattern of the present invention preferably has a structure in which the carbon content of the front surface portion is less than the carbon content of the back surface portion, and the depth direction from the surface. The carbon content of the surface portion at 2 nm is more preferably 80% or less, and further preferably 2 to 60% of the carbon content of the back surface portion in the depth direction 10 nm from the back surface. Here, the fact that the carbon content of the front surface portion is smaller than the carbon content of the back surface portion means that the total carbon amount from the front surface to the central portion is less than the total carbon content from the back surface to the central portion. To do.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the technical scope of the present invention is not limited to these examples.

[Example 1] Synthesis of composition for forming fine irregular patterns Diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda Co., Ltd., T-50, solid content in terms of titanium oxide: 16.5% by weight) 303.0 g was ethanol. / Ethyl acetate (= 50/50:% by weight) was dissolved in 584.2 g of mixed solvent, and then 112.8 g of ion-exchanged water (10-fold mol / mol of titanium oxide) was slowly dropped and hydrolyzed while stirring. . One day later, the solution was filtered to obtain a yellow transparent titanium oxide nanodispersion [A-1] having a titanium oxide equivalent concentration of 5% by weight. The average particle size of titanium oxide was 4.1 nm and was monodispersed.
As organic silicon compounds, vinyltrimethoxysilane 264.8 g [B-1] (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003) and 3-methacryloxypropyltrimethoxysilane 190.2 g [B-2] (Shin-Etsu Chemical Co., Ltd.) Liquid [C-1] (vinyltrimethoxysilane / 3-methacryloxypropyltrimethoxysilane = 70/30: molar ratio) mixed with KBM-503, manufactured by Co., Ltd. was used.
[A-1] 453.1g and [C-1] 455.0g were mixed so that it might become an element ratio (Ti / Si = 1/9), and also ion-exchange water was 91.96g (2 times mole). / Mol of organosilicon compound) was slowly added dropwise, and a liquid [D-1] stirred for 12 hours was prepared.
As an electromagnetic radiation curable compound, urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., purple light UV7600B) is dissolved in a mixed solvent of ethanol / ethyl acetate (= 50/50: wt%) so as to be 40 wt%. It was. As a photopolymerization initiator in this solution, 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173, manufactured by Ciba Specialty Chemicals) was 4% by weight based on the solid content of the urethane acrylate oligomer. To obtain a solution [E-1].
The above-mentioned [D-1] liquid and [E-1] liquid are mixed so that the solid content is 70% by weight / 30% by weight = [D-1] / [E-1], thereby forming a fine uneven pattern. Solution [F-1] was prepared.

[Example 2] Production of sheet for forming fine uneven pattern Using [F-1] produced, produced on a polycarbonate sheet (Mitsubishi Engineering Plastics, Iupilon NF-2000) with a film thickness of 5 m by dip coating. Filmed. After forming the film, it was heated at 100 ° C. for 5 minutes to produce a fine uneven pattern forming sheet [G-1].

[Test Example 1] Evaluation of sheet roll-up property Tack in the coating film of the fine unevenness pattern forming sheet [G-1] was evaluated by finger touch and was satisfactory without any trace. Further, a polycarbonate sheet (Iupilon NF-2000) was overlaid on a 10 cm × 10 cm coating film, a 1 kg load was applied and the mixture was allowed to stand for 24 hours, and then the polycarbonate sheet was peeled off to evaluate the presence or absence of blocking. As a result, there was no trace after peeling and no blocking occurred.

[Test Example 2] Production of fine pattern Si wafer mold (manufactured by Kyodo International Co., Ltd.) on which a line having L / S = 5 μm / 5 μm and an aspect ratio of 1/1 was formed, and a fine uneven pattern forming sheet [G-1] Installed in a hydraulic press. The mold was pressed against this sheet for 2 minutes under the conditions of a press pressure of 7 MPa and 27 ° C. Thereafter, the mold was released, and the line shape was transferred to the coating film.
The transferred fine uneven pattern forming sheet was irradiated with an ultraviolet ray with an integrated irradiation amount of 2000 mJ / cm ² using a high-pressure mercury lamp (manufactured by Eye Graphics) and cured to prepare a fine uneven pattern.
Next, the shape of the transferred material was confirmed using a digital microscope (VHX-900 manufactured by Keyence). As a result, the produced transfer product had the same shape as the mold, and a fine pattern could be produced (see FIGS. 1 and 2).

[Comparative Example 1] Synthesis of composition for forming fine uneven pattern As an organosilicon compound, 102.9 g of vinyltrimethoxysilane [B-1] (KBM-1003, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-methacryloxypropyltri Liquid obtained by mixing 402.6 g of methoxysilane [B-2] (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) (vinyltrimethoxysilane / 3-methacryloxypropyltrimethoxysilane = 30/70: molar ratio) [ A coating film forming solution [F-2] was prepared in the same manner as in Example 1 except that C-2] was used.

[Comparative Example 2] Production of sheet for forming fine uneven pattern Using [F-2] produced, produced on polycarbonate sheet (Mitsubishi Engineering Plastics, Iupilon NF-2000) with a film thickness of 5 μm by dip coating. Filmed. After forming the film, it was heated at 100 ° C. for 5 minutes to produce a fine uneven pattern forming sheet [G-2].

[Comparative Test Example 1] Evaluation of sheet roll-up property Tackiness in the coating film of the fine unevenness pattern forming sheet [G-2] was evaluated by finger touch. Further, a polycarbonate sheet (Iupilon NF-2000) was overlaid on a 10 cm × 10 cm coating film, a 1 kg load was applied and the mixture was allowed to stand for 24 hours, and then the polycarbonate sheet was peeled off to evaluate the presence or absence of blocking. As a result, the sheets were separated, but a trace remained, and winding was impossible.

[Example 3] Synthesis of composition for forming fine uneven pattern 119.7 g of diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda Co., Ltd., T-50, solid content in terms of titanium oxide 16.5% by weight) was added to methyl isobutyl ketone 230. The solution [A-2] was prepared by dissolving in 7 g. 230.7 g of vinyltrimethoxysilane [B-1] (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1003) as an organosilicon compound and 3-methacryloxypropyltrimethoxysilane [B-2] (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) A liquid [C-1] (vinyltrimethoxysilane / 3-methacryloxypropyltrimethoxysilane = 70/30: molar ratio) mixed with 165.7 g was used. [A-2] 350.4 g and [C-1] 396.4 g were mixed so that the element ratio (Ti / Si = 1/9) was obtained, and ion-exchanged water was further added to 84.59 g (1 times mol / wt). [D-2] was prepared by adding 12 moles of organosilicon compound and stirring for 12 hours.
[D-2] To 831.4 g, urethane acrylate oligomer A 93.8 g (manufactured by Negami Kogyo, UN-952) and urethane acrylate oligomer B 70.34 g (manufactured by Negami Kogyo, UN-904M) are added as electromagnetic radiation curable compounds. Mixed. In this solution, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907, manufactured by Ciba Specialty Chemicals) was used as a photopolymerization initiator with respect to the solid content of the urethane acrylate oligomer. The solution was dissolved to 4 wt% to prepare a fine uneven pattern forming solution [F-2].

[Example 4] Production of sheet for forming fine uneven pattern Using [F-2] produced, PET film (Toyobo Co., Ltd., Cosmo Shine A4300) was dried with a microgravure coater at a drying temperature of 100 ° C and a drying time of 3 minutes. A film having a thickness of 3 μm was prepared under the above conditions, and a fine unevenness pattern forming sheet [G-2] was prepared.

[Test Example 3] Production of fine pattern Nanoimprint formation of a silicon wafer mold having an area of 8 mm ² on which a block having a side length of 1.5 μm and a height of 100 nm is formed, and a fine pattern forming sheet [G-2] It was set in an apparatus (manufactured by Myeongchang Kiko, NANOIMPRINTER NM-0402). The mold was pressed against this sheet for 180 seconds under conditions of a press pressure of 3 kN and 100 ° C. Thereafter, the mold was released to transfer the block pattern shape to the coating film.
Next, the shape of the transferred material was confirmed using a scanning electron microscope (manufactured by JEOL, JSM-7401F). As a result, it was confirmed that a fine pattern could be created (see FIG. 3).

[Test Example 4] Evaluation of surface hardness The fine unevenness pattern forming sheet [G-2] prepared in Example 4 was converted into a condensing high-pressure mercury lamp (light having a wavelength of 365 nm, 313 nm, or 254 nm as a main component. And made by Eye Graphics Co., Ltd., one lamp type, 120 W / cm, lamp height of 9.8 cm, conveyor speed of 5 m / min), and cured by irradiating with an ultraviolet ray with an integrated irradiation amount of 2000 mJ / cm ² . Then, the pencil hardness test of the coating film hardened | cured based on the pencil method of JISK5600-5-4 was done. As a result, the pencil hardness was 2H, and it was confirmed that the fine concavo-convex pattern-formed sheet after UV irradiation had a high hardness surface.

[Example 5] Production of sheet for forming fine uneven pattern Using [F-2] produced, a 2 µm coating film was formed on soda lime glass with a bar coater at a drying temperature of 100 ° C and a drying time of 3 minutes. It produced and the board | substrate for fine uneven | corrugated pattern formation [G-3] was produced.

[Test Example 4] Evaluation of indentation hardness of coating film Using a high-pressure mercury lamp (made by Eye Graphics, lamp output: 120 W / cm) as a substrate for forming a fine uneven pattern [G-3], an integrated irradiation amount of 2000 mJ / cm ² Were cured by irradiating UV rays. Next, this substrate was set in an ultra micro hardness test system (Fiscal Instruments, PICODENER HM500), and the hardness was measured when the indentation load was set to 0.5 mN. As a result, the Martens hardness was 324 N / mm ² , which proved to have sufficient hardness.

Claims (3)

(A) On a base material having a thickness of 10 to 5000 μm which is a polyester resin, polyamide resin, polyolefin resin, vinyl resin, acrylic resin, styrene resin, cellulose film or imide resin, a) formula (I )
R ¹ _n SiX _4-n (I)
(Wherein n represents 1 and R ¹ represents a C2-8 alkenyl group. X represents a hydroxyl group or a hydrolyzable group and may be the same or different from each other). ,
Formula (II)
R ² _n SiX _4-n (II)
(Wherein, n Represents a 1, R ² is .X representing the optionally may C1~10 alkyl group having a substituent represents a hydroxyl group or a hydrolyzable group, or mutually different and the same as each other And, if present, their hydrolytic condensates,
{[Compound of formula (I)] + [if present, unit derived from compound of formula (I) in hydrolysis condensate]} / {[compound of formula (I)] + [compound of formula (II) Compound] + [if present, a unit derived from the compound of formula (I) in the hydrolysis condensate] + [if present, a unit derived from the compound of formula (II) in the hydrolysis condensate]} × 100 = 70-95 mol%, and
{[Compound of formula (II)] + [unit from the compound of formula (II) in the hydrolysis condensate if present]} / {[compound of formula (I)] + [compound of formula (II) Compound] + [if present, a unit derived from the compound of formula (I) in the hydrolysis condensate] + [if present, a unit derived from the compound of formula (II) in the hydrolysis condensate]} × 100 = 5 to 30 mol%
Organic What silicon compound b) (meth) acrylate compound Monodea, electromagnetic radiation curing compound content is 80 wt% or less based on the total weight of the solid content of the composition, and c) a metal element is Is selected from Ti, Sn, Al and Zr, selected from the group consisting of chelate compounds, organic acid metal salts, metal compounds having two or more hydroxyl groups or hydrolyzable groups, hydrolysates thereof, and condensates thereof. A step of coating a composition for forming a fine concavo-convex pattern containing one or more kinds of metal compounds,
(B) a step of semi-curing the coated surface by heat and / or electromagnetic radiation to form a fine uneven pattern forming sheet,
(C) a step of pressing the mold to the fine uneven pattern forming sheet by an imprint method to transfer the fine uneven pattern;
(D) a step of curing by irradiating electromagnetic radiation in a state where the mold is removed from the transferred sheet for forming a fine concavo-convex pattern (however, heating is not performed after irradiation of electromagnetic radiation) ;
A method for forming a fine concavo-convex pattern, comprising: The method for forming a fine concavo-convex pattern according to claim 1 , wherein the metal compound is a photosensitive compound. The compound represented by formula (II) is
Methyltrichlorosilane,
Methyltrimethoxysilane,
Methyltriethoxysilane,
Methyltributoxysilane,
Ethyltrimethoxysilane,
Ethyltriisopropoxysilane,
Ethyl tributoxysilane,
Butyltrimethoxysilane,
Nonafluorobutylethyltrimethoxysilane,
Trifluoromethyltrimethoxysilane,
3- (meth) acryloxypropyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane,
3- (3-methyl-3-oxetanemethoxy) propyltrimethoxysilane,
Methyltri (meth) acryloxysilane,
Methyl-triglycidyloxysilane, or
Methyltris (3-methyl-3-oxetanemethoxy) silane
The method for forming a fine concavo-convex pattern according to claim 1 or 2, wherein: