JP2012000842A - Method of manufacturing molded body with fine pattern on surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a molded body with a fine pattern on its surface, while adequately preventing wrinkles and transfer failure.SOLUTION: The method of manufacturing a molded body includes: (a) supplying a photopolymerizable composition 20 to a surface of a mold 10; (b) curing the photopolymerizable composition 20 with an ultraviolet ray of relatively high luminance for achieving a cure degree X of 30-90%, in contact with air, to form a semi-cured product 22; (c) supplying the photopolymerizable composition 20 to a surface of the semi-cured product 22; (d) curing, in the same way as the process (b), the photopolymerizable composition 20 and the semi-cured product 22 to form a semi-cured laminated product 24; (e) supplying the photopolymerizable composition 20 to a surface of the semi-cured laminated product 24; (f) placing a transparent substrate 30 on the photopolymerizable composition 20; and (g) curing the photopolymerizable composition 20 and the semi-cured laminated product 24 with the ultraviolet ray at light intensity for achieving a cure degree X of 95% or higher not in contact with air, to form a cured laminated product 26.

Description

  The present invention relates to a method for producing a molded body having a fine pattern on its surface.

  In the production of optical elements (microlenses, etc.), recording media, semiconductor devices, etc., as a method of forming micropatterns from micrometer order to nanometer order in a short time, the surface of a mold having a reverse pattern of micropatterns on the surface A method is well known in which a photopolymerizable composition is supplied, and the photopolymerizable composition is irradiated with ultraviolet rays to cure the photopolymerizable composition to obtain a molded body having a fine pattern on the surface.

However, this method has the following problems.
(I) Bubbles entrained when supplying the photopolymerizable composition to the surface of the mold tend to remain in the molded body.
(Ii) Since the photopolymerizable composition is cured and shrunk, a fine pattern transfer failure tends to occur.

As a manufacturing method for solving this problem, the following method has been proposed (Patent Document 1).
A photopolymerizable composition is supplied to the surface of a mold having a reverse pattern of a fine pattern on the surface, and the photopolymerizable composition is irradiated with ultraviolet rays while the photopolymerizable composition is in contact with air. The product is semi-cured, a photopolymerizable composition is further supplied thereon, a transparent substrate is placed on the photopolymerizable composition, and then the photopolymerizable composition is irradiated with ultraviolet rays from the transparent substrate side. A method of completely curing and obtaining a molded body having a fine pattern on the surface.

JP-A-5-293835

  However, in the method of Patent Document 1, when the photopolymerizable composition is semi-cured, the photopolymerizable composition in a portion in contact with the surface of the mold is not hardened. Curing and shrinkage of the photopolymerizable composition is likely to occur at the portion in contact with the surface of the film, and a large number of wrinkles may occur on the surface of the molded product on the fine pattern side, or transfer failure of the fine pattern may occur. In particular, when a mold having a structure that cannot be pressurized from the transparent substrate side (for example, a mold having a weir portion on the periphery of the surface having a reversal pattern) is used, the photopolymerizable composition from the transparent substrate side due to restrictions of the apparatus and process. When pressure cannot be applied to an object, the above problem appears remarkably when the aspect ratio of the reversal pattern (fine pattern) of the mold is relatively large.

  Even if the photopolymerizable composition cannot be pressurized when the photopolymerizable composition supplied to the surface of the mold is cured or the aspect ratio of the fine pattern of the mold is large, the Provided is a method for producing a molded body having a fine pattern on its surface, which can sufficiently suppress the occurrence of defects.

  The manufacturing method of the molding which has the fine pattern of the present invention on the surface is the following method (I) or the following method (II).

Method (I):
The method which has the following process (a)-(c), a process (g '), and a process (h).
(A) A step of supplying a photopolymerizable composition to the surface of a mold having a reverse pattern of the fine pattern on the surface.
(B) In a state where the photopolymerizable composition is in contact with an atmosphere containing oxygen, the photopolymerizable composition is irradiated with ultraviolet rays having an illuminance of light having a wavelength of 365 nm of 300 mW / cm ² or more. A step of irradiating with a light amount such that the degree of cure X calculated in (30) is 30 to 90% to cure the photopolymerizable composition to obtain a semi-cured product.
(C) A step of supplying a photopolymerizable composition to the surface of the semi-cured product.
(G ′) In a state where the photopolymerizable composition is not in contact with an atmosphere containing oxygen, ultraviolet rays are applied to the photopolymerizable composition and the semi-cured product, and the curing degree X calculated by the following formula (1) is A step of irradiating with a light amount of 95% or more to cure the photopolymerizable composition and semi-cured product to obtain a cured laminate.
(H) A step of separating the molded body made of the cured laminate and the mold to obtain a molded body having a fine pattern on the surface.

Method (II)
A method comprising the following steps (a) to (e), a step (g) and a step (h).
(A) A step of supplying a photopolymerizable composition to the surface of a mold having a reverse pattern of the fine pattern on the surface.
(B) In a state where the photopolymerizable composition is in contact with an atmosphere containing oxygen, the photopolymerizable composition is irradiated with ultraviolet rays having an illuminance of light having a wavelength of 365 nm of 300 mW / cm ² or more. A step of irradiating with a light amount such that the degree of cure X calculated in (30) is 30 to 90% to cure the photopolymerizable composition to obtain a semi-cured product.
(C) A step of supplying a photopolymerizable composition to the surface of the semi-cured product.
(D) In a state where the photopolymerizable composition is in contact with an atmosphere containing oxygen, the photopolymerizable composition and the semi-cured product are irradiated with ultraviolet light having a wavelength 365 nm of light having an illuminance of 300 mW / cm ² or more. The process of irradiating with the light quantity from which the hardening degree X calculated by Formula (1) will be 30 to 90%, hardening the said photopolymerizable composition and semi-hardened material, and setting it as a semi-hardened laminated body.
(E) A step of supplying a photopolymerizable composition to the surface of the semi-cured laminate.
(G) In a state where the photopolymerizable composition is not in contact with an oxygen-containing atmosphere, ultraviolet rays are applied to the photopolymerizable composition and the semi-cured laminate, and the curing degree X calculated by the following formula (1) is A step of irradiating with a light amount of 95% or more to cure the photopolymerizable composition and the semi-cured laminate to obtain a cured laminate.
(H) A step of separating the molded body made of the cured laminate and the mold to obtain a molded body having a fine pattern on the surface.

X = (S ₀ −S _X ) / (S ₀ −S ₁₀₀ ) × 100 (1).
However,
S ₀ is a peak area A ₀ of C═C stretching vibration of carbon-carbon unsaturated double bond in the infrared absorption spectrum of the uncured photopolymerizable composition, and a specific value not affected by radical polymerization reaction. It is a ratio (A ₀ / B ₀ ) with the peak area B ₀ of the stretching vibration of the functional group,
S ₁₀₀ is C = C stretching of a carbon-carbon unsaturated double bond in an infrared absorption spectrum of a cured product obtained by completely curing the photopolymerizable composition by irradiating the photopolymerizable composition with excess ultraviolet rays. and the peak area _{a 100} of the vibration, a ratio of the peak area _{B 100} of the stretching vibration of the particular functional group that is not affected by the radical polymerization reaction _{(a 100 / B} 100),
S _X represents carbon-carbon in the infrared absorption spectrum of a cured product obtained by curing the photopolymerizable composition by irradiating the photopolymerizable composition with a predetermined amount of ultraviolet light in the same atmosphere and illuminance as in this step. The ratio (A _X / B _X ) between the peak area A _X of the C = C stretching vibration of the carbon unsaturated double bond and the peak area B _X of the stretching vibration of a specific functional group not affected by the radical polymerization reaction is there.

In the method (I), the following step (f) may be provided between the step (c) and the step (g ′),
In the method (II), the following step (f) may be provided between the step (e) and the step (g).
(F) A step of placing a substrate on the photopolymerizable composition.

In the method (II), the step (c) and the step (d) may be repeated twice or more.
The photopolymerizable composition preferably contains a monomer (A) having one or more carbon-carbon unsaturated double bonds.
The monomer (A) preferably includes a monomer (A1) having a fluorine atom and having one or more carbon-carbon unsaturated double bonds.
The photopolymerizable composition preferably further contains a fluorine-containing surfactant (B).

The manufacturing method of the present invention is suitable when the aspect ratio of the reversal pattern is 0.1 or more, and when the mold has a dam on the periphery of the surface having the reversal pattern.
The microlens of the present invention is manufactured by the method for manufacturing a molded body having the fine pattern of the present invention on the surface.

According to the method for producing a molded body having the fine pattern on the surface of the present invention, when the photopolymerizable composition supplied to the surface of the mold is cured, the photopolymerizable composition cannot be pressurized or the mold fine pattern. Even when the aspect ratio is large, generation of wrinkles and transfer defects on the surface of the molded body can be sufficiently suppressed.
In addition, in the conventional imprinting technique, burrs are easily generated in the obtained molded body, and processing such as removal of burrs is necessary. However, in the production method of the present invention, the photopolymerizable composition is supplied from the mold and cured in several steps, and finally fills the volume of the reversal pattern portion of the mold. The possibility of overflowing can be reduced, and the occurrence of burrs in the molded body can be suppressed.

It is a figure for demonstrating the peak area A of C = C stretching vibration and the peak area B of C = O stretching vibration in an infrared absorption spectrum. It is a figure for demonstrating the peak area A of C = C stretching vibration and the peak area B of CH stretching vibration in an infrared absorption spectrum. It is a graph of the time-dependent change (A / B) of the peak area A of C = C stretching vibration and the peak area B of C = O stretching vibration. It is a graph of the time-dependent change of the ratio (A / B) of the peak area A of C = C stretching vibration and the peak area B of C—H stretching vibration. It is process drawing which shows an example of the manufacturing method of the molded object which has a fine pattern on the surface. It is process drawing which shows the other example of the manufacturing method of the molded object which has a fine pattern on the surface. It is process drawing which shows the other example of the manufacturing method of the molded object which has a fine pattern on the surface. It is a top view which shows the mold A used in the Example. It is the top view and sectional drawing which show the mold B used in the Example. It is the top view and sectional drawing which show the mold C used in the Example.

In this specification, the definition is as follows.
A fine pattern or a reverse pattern refers to a shape composed of one or more protrusions and / or recesses having a minimum dimension of 1 nm to 50 mm among width, length and height (depth).
The cured product refers to a product obtained by irradiating the photopolymerizable composition with ultraviolet rays to cure a part or all of the photopolymerizable composition.
The semi-cured product is an ultraviolet ray applied to the photopolymerizable composition in an atmosphere, an illuminance and a light amount such that the curing degree X calculated by the formula (1) is 30 to 90% among the cured products. The photopolymerizable composition is cured.
The cured laminate is a laminate in which a plurality of layers made of the cured product are laminated.
The semi-cured laminate refers to the cured laminate in which at least the outermost layer is a layer made of the semi-cured product.
The photopolymerizable composition refers to a composition containing a radical polymerizable compound that causes a radical polymerization reaction upon irradiation with ultraviolet rays.
The (meth) acryloyloxy group refers to an acryloyloxy group or a methacryloyloxy group.
(Meth) acrylate refers to acrylate or methacrylate.

<Method for producing molded body having fine pattern on surface>
The method for producing a molded body having the fine pattern on the surface of the present invention is the following method (I) or the following method (II).

Method (I):
A method comprising the following steps (a) to (c), step (f), step (g ′) and step (h).
(A) A step of supplying a photopolymerizable composition to the surface of a mold having a reverse pattern of the fine pattern on the surface.
(B) In the state where the photopolymerizable composition is in contact with an atmosphere containing oxygen, ultraviolet rays having an illuminance of light having a wavelength of 365 nm of 300 mW / cm ² or more are given to the formula (1). The process of irradiating with the light quantity from which the cure degree X computed by 30-90% is hardened, the said photopolymerizable composition is hardened, and it is set as a semi-hardened material.
(C) A step of supplying a photopolymerizable composition to the surface of the semi-cured product.
(F) The process of mounting a board | substrate on the said photopolymerizable composition as needed.
(G ′) In a state where the photopolymerizable composition is not in contact with an atmosphere containing oxygen, ultraviolet rays are applied to the photopolymerizable composition and the semi-cured product, and the curing degree X calculated by the formula (1) is 95. The process of irradiating with the light quantity used as% or more, hardening the said photopolymerizable composition and semi-hardened material, and setting it as a hardening laminated body.
(H) A step of separating the molded body made of the cured laminate and the mold to obtain a molded body having a fine pattern on the surface.

Method (II):
A method comprising the following steps (a) to (h).
(A) A step of supplying a photopolymerizable composition to the surface of a mold having a reverse pattern of the fine pattern on the surface.
(B) In the state where the photopolymerizable composition is in contact with an atmosphere containing oxygen, ultraviolet rays having an illuminance of light having a wavelength of 365 nm of 300 mW / cm ² or more are given to the formula (1). The process of irradiating with the light quantity from which the cure degree X computed by 30-90% is hardened, the said photopolymerizable composition is hardened, and it is set as a semi-hardened material.
(C) A step of supplying a photopolymerizable composition to the surface of the semi-cured product.
(D) In the state where the photopolymerizable composition is in contact with an atmosphere containing oxygen, ultraviolet rays having a wavelength of 365 nm of light having an illuminance of 300 mW / cm ² or more are applied to the photopolymerizable composition and the semi-cured product. The process of irradiating with the light quantity from which the hardening degree X calculated in (1) will be 30 to 90%, hardening the said photopolymerizable composition and semi-hardened material, and setting it as a semi-hardened laminated body.
(E) A step of supplying a photopolymerizable composition to the surface of the semi-cured laminate.
(F) The process of mounting a board | substrate on the said photopolymerizable composition as needed.
(G) In a state where the photopolymerizable composition is not in contact with an atmosphere containing oxygen, ultraviolet rays are applied to the photopolymerizable composition and the semi-cured laminate, and the curing degree X calculated by the formula (1) is 95. The process of irradiating with the light quantity used as% or more, hardening the said photopolymerizable composition and a semi-hardened laminated body, and setting it as a cured laminated body.
(H) A step of separating the molded body made of the cured laminate and the mold to obtain a molded body having a fine pattern on the surface.

(Curing degree)
The degree of cure X depends on how much the carbon-carbon unsaturated double bond related to the radical polymerization reaction existing in the photopolymerizable composition has been reduced by ultraviolet irradiation, and the curing of the photopolymerizable composition has progressed. It is an index for estimating the degree of the above, and is calculated by the following equation (1).
X = (S ₀ −S _X ) / (S ₀ −S ₁₀₀ ) × 100 (1).

However,
S ₀ is a peak area A ₀ of C═C stretching vibration of carbon-carbon unsaturated double bond in the infrared absorption spectrum of the uncured photopolymerizable composition, and a specific value not affected by radical polymerization reaction. It is a ratio (A ₀ / B ₀ ) with the peak area B ₀ of the stretching vibration of the functional group,
S ₁₀₀ is C = C stretching of a carbon-carbon unsaturated double bond in an infrared absorption spectrum of a cured product obtained by completely curing the photopolymerizable composition by irradiating the photopolymerizable composition with excess ultraviolet rays. and the peak area _{a 100} of the vibration, a ratio of the peak area _{B 100} of the stretching vibration of the particular functional group that is not affected by the radical polymerization reaction _{(a 100 / B} 100),
S _X represents carbon-carbon in the infrared absorption spectrum of a cured product obtained by curing the photopolymerizable composition by irradiating the photopolymerizable composition with a predetermined amount of ultraviolet light in the same atmosphere and illuminance as in this step. The ratio (A _X / B _X ) between the peak area A _X of the C = C stretching vibration of the carbon unsaturated double bond and the peak area B _X of the stretching vibration of a specific functional group not affected by the radical polymerization reaction is there.

Specific functional groups that are not affected by the radical polymerization reaction include, for example, the following functional groups.
(Α) When the carbon-carbon unsaturated double bond related to the radical polymerization reaction is a carbon-carbon unsaturated double bond of a (meth) acryloyloxy group, a carbonyl group (C═O) of the (meth) acryloyloxy group ).
(Β) A methylene group (—CH ₂ —) when the carbon-carbon unsaturated double bond involved in the radical polymerization reaction is a carbon-carbon unsaturated double bond of a vinyl group or an allyl group.

In the case of (α), the peak area A of the C═C stretching vibration of the (meth) acryloyloxy group is, as shown in FIG. 1, the absorption curve of the C═C stretching vibration having a peak in the vicinity of 1600 cm ⁻¹ , The area of the region surrounded by the line connecting the two points where the absorption curve rises, and the peak area B of the C═O stretching vibration of the (meth) acryloyloxy group is around 1750 cm ^{−1 as} shown in FIG. It is an area of a region surrounded by an absorption curve of C = O stretching vibration having a peak and a line connecting two points where the absorption curve rises.

In the case of (β), the peak area A of the C═C stretching vibration of the vinyl group or allyl group, as shown in FIG. 2, is the absorption curve of the C═C stretching vibration having a peak in the vicinity of 1600 cm ⁻¹ and the absorption. the area of a region surrounded by the line connecting the two points at which the curve rises, -CH ₂ - is the peak area B of C-H stretching vibration of, -CH ₂ appears near 3000~2650cm ^-1 - stretching vibration It is the area of a region surrounded by an absorption curve and a line connecting two points where the absorption curve rises.

Hereinafter, in the case of (α), the procedure for obtaining the degree of cure will be specifically described.
(I) A silicon substrate having about 6 mL of the photopolymerizable composition dropped on the surface is set in a real-time FT-IR system for UV curable resin (manufactured by Thermo Fisher Sciences).
(Ii) Start real-time measurement of the infrared absorption spectrum of the photopolymerizable composition on the silicon substrate in a nitrogen gas atmosphere. The infrared absorption spectrum is measured by a reflection absorption method using FT-IR.
(Iii) After 10 seconds from the start of measurement, irradiation of ultraviolet rays (illuminance of light having a wavelength of 365 nm: 65 mW / cm ² ) to the photopolymerizable composition is started.
(Iv) From the infrared absorption spectrum for each elapsed time obtained by real-time measurement, the ratio of the peak area A of C = C stretching vibration to the peak area B of C = O stretching vibration (A A graph of change with time of / B) is obtained.
(V) In the graph, A / B from the start of measurement to 10 seconds becomes A ₀ / B ₀ , and the time when A / B does not decrease, that is, A / B after about 53 seconds from the start of measurement. , A ₁₀₀ / B ₁₀₀ . In the case of the graph of FIG. 3, A ₀ / B ₀ is 0.375 and A ₁₀₀ / B ₁₀₀ is 0.05.

(Vi) About 6 mL of the same photopolymerizable composition used in the procedures (i) to (v) is dropped onto the surface of the silicon substrate.
(Vii) The photopolymerizable composition on the silicon substrate is irradiated with ultraviolet rays using the same apparatus, atmosphere, illuminance and light intensity as in this step.
(Viii) The infrared absorption spectrum of the semi-cured product or cured product on the silicon substrate is measured. The infrared absorption spectrum is measured by a reflection absorption method using FT-IR.
(Ix) The ratio (A _X / B _X ) between the peak area A of C = C stretching vibration and the peak area B of C = O stretching vibration is determined from the obtained infrared absorption spectrum.
(X) The degree of curing X is calculated from the equation (1). For example, when A _X / B _X is 0.25, X = (0.375−0.25) / (0.375−0.05) × 100 = 38%.

Hereinafter, in the case of (β), the procedure for obtaining the degree of cure will be specifically described.
(I) A silicon substrate having about 6 mL of the photopolymerizable composition dropped on the surface is set in a real-time FT-IR system for UV curable resin (manufactured by Thermo Fisher Sciences).
(Ii) Start real-time measurement of the infrared absorption spectrum of the photopolymerizable composition on the silicon substrate in a nitrogen gas atmosphere. The infrared absorption spectrum is measured by a reflection absorption method using FT-IR.
(Iii) After 10 seconds from the start of measurement, irradiation of ultraviolet rays (illuminance of light having a wavelength of 365 nm: 65 mW / cm ² ) to the photopolymerizable composition is started.
(Iv) From the infrared absorption spectrum for each elapsed time obtained by real-time measurement, the ratio of the peak area A of C = C stretching vibration to the peak area B of C—H stretching vibration (A A graph of change with time of / B) is obtained.
(V) In the graph, A / B from the start of measurement to 10 seconds becomes A ₀ / B ₀ , and the time when A / B does not decrease, that is, A / B after about 55 seconds from the start of measurement. , A ₁₀₀ / B ₁₀₀ . In the graph of FIG. 4, A ₀ / B ₀ is 0.168, and A ₁₀₀ / B ₁₀₀ is 0.08.

(Vi) About 6 mL of the same photopolymerizable composition used in the procedures (i) to (v) is dropped onto the surface of the silicon substrate.
(Vii) The photopolymerizable composition on the silicon substrate is irradiated with ultraviolet rays using the same apparatus, atmosphere, illuminance and light intensity as in this step.
(Viii) The infrared absorption spectrum of the semi-cured product or cured product on the silicon substrate is measured. The infrared absorption spectrum is measured by a reflection absorption method using FT-IR.
(Ix) The ratio (A _X / B _X ) between the peak area A of C = C stretching vibration and the peak area B of C—H stretching vibration is determined from the obtained infrared absorption spectrum.
(X) The degree of curing X is calculated from the equation (1). For example, when A _X / B _X is 0.132, X = (0.168−0.132) / (0.168−0.08) × 100 = 41%.

(Photopolymerizable composition)
The photopolymerizable composition preferably contains the monomer (A), and further contains a fluorine-containing surfactant (B), a photopolymerization initiator (C), and other additives (D) as necessary.

Monomer (A):
The monomer (A) is a radically polymerizable compound that undergoes a radical polymerization reaction upon irradiation with ultraviolet rays, and is a monomer having one or more carbon-carbon unsaturated double bonds.
From the viewpoint of releasability, the monomer (A) preferably contains a monomer (A1) having a fluorine atom and having at least one carbon-carbon unsaturated double bond.

Monomer (A1):
Examples of the monomer (A1) include fluoro (meth) acrylates, fluorodienes, fluorovinyl ethers, fluoro cyclic monomers, and the like. From the viewpoint of curability and compatibility, fluorodienes or fluoro (meth) acrylates. Are preferred, and fluoro (meth) acrylates are particularly preferred.

As the fluorodienes, a compound represented by the following formula (A1a) (hereinafter referred to as monomer (A1a)) is preferable.
^{_{CF 2 = CR 1 -Q-CR}} 2 = CH 2 ··· (A1a).
However, R < ¹ > and R < ² > is respectively independently a hydrogen atom, a fluorine atom, a C1-C3 alkyl group, or a C1-C3 fluoroalkyl group, Q is an oxygen atom, following formula ( 2) or a divalent organic group which may have a functional group.
-NR < ³ > -... (2).
However, R < ³ > is a hydrogen atom, a C1-C6 alkyl group, an alkylcarbonyl group, or a tosyl group.

When Q is a divalent organic group, the main chain of Q is selected from the group consisting of methylene, dimethylene, trimethylene, tetramethylene, oxymethylene, oxydimethylene, oxytrimethylene, and dioxymethylene. The hydrogen atom in the main chain is a fluorine atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or a carbon number in which an etheric oxygen atom is inserted between carbon atoms. A group substituted with a group selected from 1 to 6 alkyl groups and a hydroxyalkyl group having 1 to 6 carbon atoms in which an etheric oxygen atom is inserted between a carbon atom and a carbon atom, and carbon in the group atom - group is preferably substituted by one or more fluorine atoms of the hydrogen atoms forming a hydrogen atom _{bonds, -CF 2 C (CF 3)} (OH) CH 2 -, - CF 2 C _{CF 3) (OH) -,} - CF 2 C (CF 3) (OCH 2 OCH 3) CH 2 -, - CH 2 CH (CH 2 C (CF 3) 2 OH) CH 2 -, or _-CH 2 CH _{(CH 2 C (CF 3)} 2 OH) - is particularly preferred. However, the direction of the group means that the left side is bonded to CF ₂ ═CR ¹ —.

Specific examples of the monomer (A1a) include the following compounds.
_{CF 2 = CFCH 2 CH (C} (CF 3) 2 OH) CH 2 CH = CH 2,
_{CF 2 = CFCH 2 CH (C} (CF 3) 2 OH) CH = CH 2,
_{CF 2 = CFCH 2 CH (C} (CF 3) 2 OH) CH 2 CH 2 CH = CH 2,
_{CF 2 = CFCH 2 CH (CH} 2 C (CF 3) 2 OH) CH 2 CH 2 CH = CH 2,
_{CF 2 = CFCH 2 C (CH} 3) (CH 2 SO 2 F) CH 2 CH = CH 2,
_{CF 2 = CFCF 2 C (CF} 3) (OCH 2 OCH 3) CH 2 CH = CH 2,
_{CF 2 = CFCF 2 C (CF} 3) (OH) CH = CH 2,
_{CF 2 = CFCF 2 C (CF} 3) (OH) CH 2 CH = CH 2,
CF ₂ ═CFCF ₂ C (CF ₃ ) (OCH ₂ OCH ₂ CF ₃ ) CH ₂ CH═CH ₂ ,
_{CF 2 = CFCF 2 C (CF} 3) (OCH 2 OCH 3) CH 2 CH = CH 2,
_{CF 2 = CFOCF 2 CF (O} (CF 2) 3 OC 2 H 5) CH 2 CH = CH 2,
CF ₂ = CFOCF ₂ CF (OCF ₂ CF ₂ CH ₂ NH ₂ ) CH ₂ CH═CH ₂ ,
_{CF 2 = CFOCF 2 CF (O} (CF 2) 3 CN) CH = CH 2,
CF ₂ = CFOCF ₂ CF (OCF ₂ CF ₂ SO ₂ F) CH ₂ CH═CH ₂ ,
CF ₂ = CFOCF ₂ CF (O (CF ₂ ) ₃ PO (OC ₂ H ₅ ) ₂ ) CH ₂ CH═CH ₂ ,
_{CF 2 = CFOCF 2 CF (OCF} 2 CF 2 SO 2 F) CH 2 CH = CH 2.

As the fluoro (meth) acrylates, a compound represented by the following formula (A1b) (hereinafter referred to as monomer (A1b)) is preferable.
^{_{CH 2 = C (R 11)}} -C (O) O-W-R f ··· (A1b).
R ¹¹ is a hydrogen atom or a methyl group.

W is a divalent linking group containing no single bond or fluorine atom. Examples of the divalent linking group include a linear or branched alkylene group, a linear or branched alkenylene group, an oxyalkylene group, a divalent 6-membered aromatic group, and a divalent 4- to 6-membered ring. A saturated or unsaturated aliphatic group, a divalent 5- to 6-membered heterocyclic group, or a divalent linking group represented by the following formula (3). The divalent linking group may be a combination of two or more, may be a condensed ring, or may have a substituent.
-YZ- (3).
Y represents a linear or branched alkylene group, a divalent 6-membered aromatic group, a divalent 4- to 6-membered saturated or unsaturated aliphatic group, and a divalent 5- to 6-membered group. A heterocyclic group of a ring, or a condensed ring group of these, and Z is —O—, —S—, —CO—, —C (O) O—, —C (O) S—, —N ( _{R) -, - SO 2 -} , - PO (OR) -, - N (R) -C (O) O -, - N (R) -C (O) -, - N (R) -SO 2 - Or —N (R) —PO (OR) —, wherein R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

W is preferably a single bond, a linear or branched alkylene group, a group represented by the following formula (4), or a combination of these groups: — (CH ₂ ) _p — (where p is 0) It is an integer of ˜6, and when p is 0, it represents a single bond.
^{-Y 1 -Z 1 - ··· (4} ).
Y ¹ represents a linear or branched alkylene group or a divalent 6-membered aromatic group, and Z ¹ represents —N (R) —, —SO ₂ —, or —N (R ) —SO ₂ —, wherein R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

R ^f is a polyfluoroalkyl group having 1 to 6 carbon atoms in the main chain and optionally having an etheric oxygen atom between carbon atoms. The boundary between W and R ^f is determined so that the carbon number of R ^f is the smallest.
The polyfluoroalkyl group means a group in which two or more hydrogen atoms of an alkyl group having 1 to 6 carbon atoms in the main chain (carbon number not including a side chain) are substituted with fluorine atoms. The main chain means the straight chain in the case of a straight chain and the longest carbon chain in the case of a branch. The side chain means a carbon chain other than the main chain among the carbon chains constituting the branched polyfluoroalkyl group. The side chain consists of an alkyl group, a monofluoroalkyl group or a polyfluoroalkyl group.

As the polyfluoroalkyl group, a partially fluoro-substituted alkyl group or a perfluoro-substituted group corresponding to a linear or branched alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.) An alkyl group is mentioned.
As the polyfluoroalkyl group having an etheric oxygen atom between carbon atoms, a polyfluoro (alkoxyalkylalkyl) group or a polyfluoro (polyoxyalkylene alkyl ether) group is preferable, and a polyfluoro (2-ethoxyethyl) group, poly A fluoro (2-methoxypropyl) group, a polyfluoro (polyoxyethylene methyl ether) group, a polyfluoro (polyoxypropylene methyl ether) group, etc. are mentioned.

R ^f is preferably linear. When R ^f is branched, it is preferable that the branched portion is present as close to the end of R ^f as possible.
R ^f is preferably a polyfluoroalkyl group, more preferably a perfluoroalkyl group in which all hydrogen atoms are substantially substituted with fluorine atoms, more preferably a linear perfluoroalkyl group, A linear perfluoroalkyl group having 4 to 6 carbon atoms is particularly preferable, and a linear perfluoroalkyl group having 6 carbon atoms is most preferable from the viewpoint of low accumulation and high releasability.

As the monomer (A1b), a compound represented by the following formula (5) is preferable.
^{_{CH 2 = C (R 11)}} -C (O) O- (CH 2) p -R F ··· (5).
However, R < ¹¹ > is a hydrogen atom or a methyl group, p is an integer of 0-6, R < ^F > is a C1-C6 linear perfluoroalkyl group.

Specific examples of the monomer (A1b) include the following compounds.
_{CH 2 = CH-C (O} ) O- (CH 2) 2 - (CF 2) 6 F,
_{CH 2 = CH-C (O} ) O- (CH 2) 2 - (CF 2) 4 F,
_{CH 2 = CH-C (O} ) O- (CH 2) 2 - (CF 2) 2 F,
_{CH 2 = CH-C (O} ) O- (CH 2) 2 -CF 3,
_{CH 2 = C (CH 3)} -C (O) O- (CH 2) 2 - (CF 2) 6 F,
_{CH 2 = C (CH 3)} -C (O) O- (CH 2) 2 - (CF 2) 4 F,
_{CH 2 = C (CH 3)} -C (O) O- (CH 2) 2 - (CF 2) 2 F,
_{CH 2 = CH-C (O} ) O-CH 2 - (CF 2) 2 F,
_{CH 2 = CH-C (O} ) O-CH 2 -CF 3,
_{CH 2 = CH-C (O} ) O-CH 2 CH (OH) CH 2 -CF 2 CF 2 CF (CF 3) 2,
_{CH 2 = CH-C (O} ) O-CH (CF 3) 2,
_{CH 2 = CH-C (O} ) O-CH 2 - (CF 2) 6 F,
_{CH 2 = C (CH 3)} -C (O) O-CH 2 - (CF 2) 6 F,
_{CH 2 = CH-C (O} ) O-CH 2 -CF 2 CF 2 H,
_{CH 2 = CH-C (O} ) O-CH 2 - (CF 2 CF 2) 2 H,
_{CH 2 = C (CH 3)} -C (O) O-CH 2 -CF 2 CF 2 H,
_{CH 2 = C (CH 3)} -C (O) O-CH 2 - (CF 2 CF 2) 2 H,
_{CH 2 = CH-C (O} ) O-CH 2 -CF 2 OCF 2 CF 2 OCF 3,
_{CH 2 = CH-C (O} ) O-CH 2 -CF 2 O (CF 2 CF 2 O) 3 CF 3,
_{CH 2 = C (CH 3)} -C (O) O-CH 2 -CF 2 OCF 2 CF 2 OCF 3,
_{CH 2 = C (CH 3)} -C (O) O-CH 2 -CF 2 O (CF 2 CF 2 O) 3 CF 3,
_{CH 2 = CH-C (O} ) O-CH 2 -CF (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F,
_{CH 2 = CH-C (O} ) O-CH 2 -CF (CF 3) O (CF 2 CF (CF 3) O) 2 (CF 2) 3 F,
_{CH 2 = C (CH 3)} -C (O) O-CH 2 -CF (CF 3) OCF 2 CF (CF 3) O (CF 2) 3 F,
_{CH 2 = C (CH 3)} -C (O) O-CH 2 -CF (CF 3) O (CF 2 CF (CF 3) O) 2 (CF 2) 3 F.

A monomer (A1) may be used individually by 1 type, and may use 2 or more types together.
The monomer (A) is a monomer (A2) having one (meth) acryloyloxy group (excluding the monomer (A1)) and / or a monomer (A3) having two or more (meth) acryloyloxy groups May be included.
When these monomers are used in combination, there may be a plurality of specific functional groups that are not affected by the radical polymerization reaction, which is a standard in the evaluation of the degree of cure (X). In this case, any functional group may be selected and the degree of curing may be evaluated based on the functional group. For example, when the photopolymerizable composition includes a monomer (A1a), a monomer (A2), and a monomer (A3), a carbonyl group of a (meth) acryloyloxy group as a specific functional group that is not affected by the radical polymerization reaction (C═O) and a methylene group (—CH ₂ —) in the monomer (A1a) are present. In this case, the selection may be made based on either a carbonyl group (C═O) or a methylene group (—CH ₂ —).

Monomer (A2):
Examples of the monomer (A2) include (meth) acrylates of monohydroxy compounds, mono (meth) acrylates of polyhydroxy compounds, and the like, (meth) acrylates of monohydroxy compounds are preferred, and acrylates of monohydroxy compounds are particularly preferred. Examples of monohydroxy compounds include alkanols having 4 to 20 carbon atoms in the alkyl moiety, monocyclic, condensed polycyclic or alicyclic monools having a bridged ring, and poly (or mono) alkylene glycol monoalkyl (or aryl) ethers. Are preferred, and alicyclic monools having an alkanol having 6 to 20 carbon atoms and a bridging ring are particularly preferred.

As the monomer (A2), the following compounds may be mentioned.
Phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypyrrolyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate 2- (meth) acryloyloxyethyl hexahydrophthalic acid, behenyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, stearyl (meth) acrylate, isostearyl (meth) acrylate, lauryl (meth) Acrylate, 2-ethylhexyl (meth) acrylate, 3- (trimethoxysilyl) propyl (meth) acrylate, butyl (meth) acrylate, ethoxyethyl (meth) acrylate , Methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N, N-diethylaminoethyl (meth) Acrylate, N, N-dimethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy- 1-adamantyl (meth) acrylate, 1-adamantyl (meth) acrylate, isobornyl (meth) acrylate, 2-carboxyethyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate 2- (tert-butylamino) ethyl (meth) acrylate, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) Acrylate, 4-tert-butylcyclohexyl (meth) acrylate, and the like.
A monomer (A2) may be used individually by 1 type, and may use 2 or more types together.

Monomer (A3):
The monomer (A3) is a compound having two or more (meth) acryloyloxy groups. The monomer (A3) may be a compound having a fluorine atom, but is usually a compound having no fluorine atom. 2-10 are suitable for the number of (meth) acryloyloxy groups in a monomer (A3), and 2-6 are preferable.

  The monomer (A3) is a poly (meth) acrylate of a polyhydroxy compound, and may have a hydroxyl group as long as the number of (meth) acryloyloxy groups is 2 or more. Polyhydroxy compounds include alkylene oxide adducts of compounds having two or more functional groups to which alkylene oxide can be added (alkane polyols, alkylene oxide adducts of alkane polyols, polyalkylene glycols, polyhydric phenols, polyamines, etc.), polycarbonates Examples include polyols and polyester polyols.

  The monomer (A3) may be urethane (meth) acrylate, which is a compound having a poly (meth) acrylate structure of a polyhydroxy compound. Urethane (meth) acrylate is a compound obtained by reacting an isocyanate alkyl (meth) acrylate with a polyhydroxy compound, a compound obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate, etc. And a compound having a urethane bond. As a polyhydroxy compound which is a raw material of urethane (meth) acrylate, polyether polyol (alkylene oxide adduct of alkane polyol, polyalkylene glycol, alkylene oxide adduct of polyhydric phenol, etc.) is preferable, and no polyisocyanate compound is used. A yellowing type polyisocyanate compound is preferred.

  As the monomer (A3), poly (meth) acrylates of polyhydroxy compounds selected from the group consisting of alkane polyols, alkylene oxide adducts of alkane polyols, polyalkylene glycols and alkylene oxide adducts of polyhydric phenols, and polyethers Urethane (meth) acrylate obtained using a polyol is preferred.

As the monomer (A3), the following compounds may be mentioned.
Bisphenol A di (meth) acrylate, di (meth) acrylate of bisphenol A alkylene oxide adduct (ethoxylated bisphenol A di (meth) acrylate, propoxylated bisphenol A di (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) ) Acrylate, bisphenol A glycerolate di (meth) acrylate, bisphenol A propoxylate glycerolate di (meth) acrylate, etc.), ethoxylated bisphenol F di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, full orange (Meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, glycerol 1,3-diglycerolate di (meth) acrylate, 1,6-hexanediol ethoxylate di (Meth) acrylate, 1,6-hexanediol propoxylate di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 3-hydroxy-2,2-dimethylpropionate di (meth) acrylate, 1 , 9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol propoxylate di (meth) acrylate, Polyethylene grease Di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol di (meth) acrylate, propylene glycol glycerolate di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol glycerolate di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, 2-methyl-1,3-propanediol diacrylate, trimethylolpropane benzoate di (meth) acrylate, pentaerythritol di (meth) ) Acrylate monostearyl acid, trimethylolpropane ethoxylate methyl ether di (meth) acrylate, di (meth) acrylate having two or more urethane bonds (UA-4200 made by Shin-Nakamura Chemical Co., Ltd., diurethane di (meth) acrylate, etc.) ), Di (meth) acrylate having a fluorene skeleton, 1,3-bis (3-methacryloyloxypropyl) -1,1,3,3-tetramethyldisiloxane, trimethylolpropane tri (meth) acrylate, trimethylol Propane ethoxytri (meth) acrylate, polyether triol tri (meth) acrylate, glycerin propoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated isocyanuric acid triacrylate, ethoxylation Limethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol Hexa (meth) acrylate, urethane di (meth) acrylate obtained using polyether diol, urethane tri (meth) acrylate obtained using polyether triol, urethane tetra (meth) acrylate obtained using polyether tetraol Urethane hexa (meth) acrylate obtained using polyether hexaol.
A monomer (A3) may be used individually by 1 type, and may use 2 or more types together.

The total amount of monomers (A1) to (A3) contained in the photopolymerizable composition is preferably 70 to 99.89% by mass, and 80 to 99% by mass in the photopolymerizable composition (100% by mass). Is particularly preferred.
The ratio of the monomer (A1) to the total amount of the monomers (A1) to (A3) is preferably 5 to 100% by mass when the total amount of the monomers (A1) to (A3) is 100% by mass, and preferably 15 to 70%. Mass% is particularly preferred.
The ratio of the monomer (A2) to the total amount of the monomers (A1) to (A3) is preferably 0 to 95% by mass, when the total amount of the monomers (A1) to (A3) is 100% by mass, and 5 to 50%. Mass% is particularly preferred.
The ratio of the monomer (A3) to the total amount of the monomers (A1) to (A3) is preferably 0 to 95% by mass when the total amount of the monomers (A1) to (A3) is 100% by mass, and preferably 35 to 85%. Mass% is particularly preferred.

  In addition, it is preferable that the photopolymerizable composition in this invention does not contain a solvent substantially. If the photopolymerizable composition does not substantially contain a solvent, without performing a special operation (for example, an operation of removing the solvent by heating the photopolymerizable composition to a high temperature, etc.) excluding ultraviolet irradiation, The photopolymerizable composition can be easily cured.

The solvent is a compound having the ability to dissolve at least one of the monomer (A), the fluorine-containing surfactant (B), the photopolymerization initiator (C), and other additives (D), and has a boiling point at normal pressure. Is a compound of 160 ° C. or lower.
“Substantially free of solvent” means that it contains no solvent at all, or preferably contains 1% by mass or less, particularly preferably 0.7% by mass or less of the solvent in the photopolymerizable composition (100% by mass). It means no case. In the present invention, the solvent used in preparing the photopolymerizable composition may be included as a residual solvent, but in this case as well, the residual solvent is preferably removed as much as possible, and the photopolymerizable composition 1 mass% or less is preferable in a thing (100 mass%).

Fluorine-containing surfactant (B):
The photopolymerizable composition preferably further contains a fluorine-containing surfactant (B) from the viewpoint of releasability.
The fluorine-containing surfactant (B) is preferably a fluorine-containing surfactant having a fluorine content of 10 to 70% by mass, and more preferably a fluorine-containing surfactant having a fluorine content of 10 to 40% by mass. The fluorine-containing surfactant may be water-soluble or fat-soluble.

  The fluorine-containing surfactant (B) is preferably an anionic fluorine-containing surfactant, a cationic fluorine-containing surfactant, an amphoteric fluorine-containing surfactant, or a nonionic fluorine-containing surfactant, and a photopolymerizable composition. Nonionic fluorine-containing surfactants are more preferable from the viewpoints of the compatibility in and the dispersibility in the cured resin.

As the anionic fluorine-containing surfactant, a polyfluoroalkyl carboxylate, a polyfluoroalkyl phosphate, or a polyfluoroalkyl sulfonate is preferable.
Specific examples of the anionic fluorine-containing surfactant include Surflon S-111 (trade name, manufactured by AGC Seimi Chemical Co., Ltd.), Florard FC-143 (trade name, manufactured by 3M), Megafark F-120 (trade name, DIC). Etc.).

As the cationic fluorine-containing surfactant, a trimethylammonium salt of polyfluoroalkylcarboxylic acid or a trimethylammonium salt of polyfluoroalkylsulfonic acid amide is preferable.
Specific examples of the cationic fluorine-containing surfactant include Surflon S-121 (trade name, manufactured by AGC Seimi Chemical Co., Ltd.), Florard FC-134 (trade name, manufactured by 3M), Megafark F-150 (trade name, DIC). Etc.).

As the amphoteric fluorine-containing surfactant, polyfluoroalkyl betaine is preferable.
Specific examples of amphoteric fluorine-containing surfactants include Surflon S-132 (trade name, manufactured by AGC Seimi Chemical Co., Ltd.), Florard FX-172 (trade name, manufactured by 3M), Megafark F-120 (trade name, DIC Corporation). Manufactured) and the like.

As the nonionic fluorine-containing surfactant, polyfluoroalkylamine oxide or polyfluoroalkyl / alkylene oxide adduct is preferable.
Specific examples of the nonionic fluorine-containing surfactant include Surflon S-145 (trade name, manufactured by AGC Seimi Chemical Co., Ltd.), Surflon S-393 (trade name, manufactured by AGC Seimi Chemical Co., Ltd.), Surflon KH-20 (trade name). , AGC Seimi Chemical Co., Ltd.), Surflon KH-40 (trade name, manufactured by AGC Seimi Chemical Co., Ltd.), Florard FC-170 (trade name, manufactured by 3M), Florad FC-430 (trade name, manufactured by 3M), Megafark F-141 (trade name, manufactured by DIC) and the like.

A fluorine-containing surfactant (B) may be used individually by 1 type, and may use 2 or more types together.
0.01-5 mass% is preferable among photopolymerizable compositions (100 mass%), and, as for content of a fluorine-containing surfactant (B), 0.1-1 mass% is more preferable.

Photopolymerization initiator (C):
It is preferable that a photopolymerizable composition contains a photoinitiator (C) further from a photocurable point.
As the photopolymerization initiator (C), acetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator, α-aminoketone photopolymerization initiator, α-hydroxy Ketone-based photopolymerization initiator, α-acyl oxime ester, benzyl- (o-ethoxycarbonyl) -α-monooxime, acylphosphine oxide, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram Sulfide, azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate, etc., and acetophenone photopolymerization initiator, benzoin photopolymerization initiator from the viewpoint of sensitivity and compatibility , Α-aminoketone photopolymerization An initiator or a benzophenone photopolymerization initiator is preferred.

A photoinitiator (C) may be used individually by 1 type, and may use 2 or more types together.
As for the ratio of a photoinitiator (C), 0.1-12 mass% is preferable among a photopolymerizable composition (100 mass%), and 0.5-6 mass% is more preferable.

Other additives (D):
The photopolymerizable composition is a photosensitizer, a polymerization inhibitor, a resin, metal oxide fine particles, a carbon compound, excluding the monomer (A), the fluorine-containing surfactant (B) and the photopolymerization initiator (C). Other additives (D) such as metal fine particles and other organic compounds may be included.

As photosensitizers, n-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzisoisouronium-p-toluenesulfinate, triethylamine, diethylaminoethyl methacrylate, triethylene Examples include tetramine and 4,4′-bis (dialkylamino) benzophenone.
Examples of the polymerization inhibitor include naphthalene derivatives (such as 4-methoxy-1-naphthol), hydroquinone derivatives (such as hydroquinone and hydroquinone monomethyl ether), and nitrosamine derivatives.

Examples of the resin include fluororesin, polyester, polyester oligomer, polycarbonate, poly (meth) acrylate, and the like.
Examples of the metal oxide fine particles include titania, silica, zirconia and the like.
Examples of the carbon compound include carbon nanotubes and fullerenes.
Examples of the metal fine particles include copper and platinum.
Examples of other organic compounds include porphyrin, metal-encapsulated porphyrin, ionic liquid (such as 1-hexyl-3-methylimidazolium chloride), and a dye.

  The proportion of the other additive (D) is preferably 20% by mass or less in the photopolymerizable composition (100% by mass). If other additive (D) is 20 mass% or less, a photopolymerizable composition can be mixed uniformly and a homogeneous photopolymerizable composition will be obtained.

(mold)
Examples of the mold include a non-translucent material mold or a translucent material mold.
Examples of the non-translucent material include silicon, nickel, copper, stainless steel, titanium, SiC, and mica.
Examples of the light transmitting material include quartz, glass, polydimethylsiloxane, cyclic polyolefin, polycarbonate, polyethylene terephthalate, and transparent fluororesin.
At least one of the mold and the substrate described later is made of a material that transmits 40% or more of light having a wavelength on which the photopolymerization initiator (C) acts.

The mold has a reverse pattern on the surface. The reverse pattern is a reverse pattern corresponding to the fine pattern on the surface of the molded body.
The reverse pattern has fine convex portions and / or concave portions.
As a convex part, the elongate ridge extending on the surface of a mold, the processus | protrusion scattered on the surface, etc. are mentioned.
Examples of the recess include a long groove extending on the surface of the mold and holes scattered on the surface.

Examples of the shape of the ridge or groove include a straight line, a curved line, a bent shape, and the like. A plurality of ridges or grooves may exist in parallel and have a stripe shape.
Examples of the cross-sectional shape of the ridge or groove in the direction perpendicular to the longitudinal direction include a rectangle, a trapezoid, a triangle, and a semicircle.
Examples of the shape of the protrusion or hole include a triangular prism, a quadrangular prism, a hexagonal prism, a cylinder, a triangular pyramid, a quadrangular pyramid, a hexagonal pyramid, a cone, a hemisphere, and a polyhedron.

  The average width of the ridges or grooves is preferably 1 nm to 50 mm, more preferably 50 nm to 5 mm, and even more preferably 100 nm to 500 μm. The width of the ridge means the length of the base in the cross section in the direction orthogonal to the longitudinal direction. The width of the groove means the length of the upper side in the cross section in the direction orthogonal to the longitudinal direction.

  The average width of the protrusions or holes is preferably 1 nm to 50 mm, more preferably 50 nm to 5 mm, and still more preferably 100 nm to 500 μm. The width of the protrusion means the length of the bottom side in a cross section perpendicular to the longitudinal direction when the bottom surface is elongated, and otherwise means the maximum length of the bottom surface of the protrusion. The width of the hole means the length of the upper side in the cross section perpendicular to the longitudinal direction when the opening is elongated, and otherwise means the maximum length of the opening of the hole.

As for the height of a convex part, 1 nm-50 mm are preferable on average, 50 nm-5 mm are more preferable, and 100 nm-500 micrometers are still more preferable.
The depth of the recess is preferably 1 nm to 50 mm on average, more preferably 50 nm to 5 mm, and still more preferably 100 nm to 500 μm.

  In a region where the reverse pattern is dense, the interval between adjacent convex portions (or concave portions) is preferably 1 nm to 50 mm on average, and more preferably 50 nm to 5 mm. The interval between adjacent convex portions means the distance from the end of the base of the cross section of the convex portion to the start of the base of the cross section of the adjacent convex portion. The interval between adjacent recesses means the distance from the end of the upper side of the cross section of the recess to the start end of the upper side of the cross section of the adjacent recess.

The minimum dimension of the convex portion is preferably 1 nm to 50 mm, more preferably 40 nm to 5 mm, and particularly preferably 1 μm to 500 μm. The minimum dimension means the minimum dimension among the width, length, and height of the convex portion.
The minimum dimension of the recess is preferably 1 nm to 50 mm, more preferably 40 nm to 5 mm, and particularly preferably 1 μm to 500 μm. The minimum dimension means the minimum dimension among the width, length and depth of the recess.

According to the manufacturing method of the present invention, in the conventional manufacturing method, a large number of wrinkles were generated on the surface on the fine pattern side of the molded body, or transfer failure of the fine pattern was likely to occur. It is suitable when the number is 1 or more, or when the mold has a weir portion on the periphery of the surface having the reverse pattern.
The aspect ratio of the reversal pattern is a ratio (height or depth / width) between the height of the convex portion or the depth of the concave portion and the width of the convex portion or the concave portion.

(substrate)
Examples of the substrate include an inorganic material substrate and an organic material substrate.
Examples of the inorganic material include silicon, glass, quartz glass, metal (aluminum, nickel, copper, etc.), metal oxide (alumina, etc.), silicon nitride, aluminum nitride, lithium niobate, compound semiconductor, and the like.
Examples of the organic material include fluorine resin, silicone resin, acrylic resin, polycarbonate, polyester (polyethylene terephthalate, etc.), polyimide, polypropylene, polyethylene, nylon resin, polyphenylene sulfide, and cyclic polyolefin.

As the substrate, a surface-treated substrate may be used from the viewpoint of excellent adhesion with the photopolymerizable composition. Examples of the surface treatment include primer coating treatment, ozone treatment, plasma etching treatment, and the like. Examples of the primer include polymethyl methacrylate, silane coupling agent, silazane and the like.
At least one of the substrate and the mold is made of a material that transmits 40% or more of light having a wavelength on which the photopolymerization initiator (C) acts.

(Process (a))
Examples of the application method (supply method) of the photopolymerizable composition include an ink jet method, a potting method, a spin coat method, a roll coat method, a cast method, a dip coat method, a die coat method, and a bar coat method. The inkjet method and the potting method are preferable from the viewpoint that the coating amount of the composition can be controlled.

  The coating amount of the photopolymerizable composition is preferably 50 to 100% of the volume of the reverse pattern portion of the mold. If the application amount is 50% or more, it is not necessary to apply the photopolymerizable composition many times in the subsequent step, and the cost can be reduced. When the coating amount is 100% or less, the photopolymerizable composition does not overflow from the mold.

  The photopolymerizable composition may be disposed on the entire surface of the mold having the reverse pattern of the fine pattern of the molded body on the surface, or may be disposed on a part of the surface of the mold. By disposing the photopolymerizable composition on the surface of the mold, it is possible to suppress bubble defects even if the reverse pattern has a concave shape.

  The photopolymerizable composition may be supplied under normal pressure or under reduced pressure of 700 Pa or more. Moreover, it is desirable to carry out in an environment (such as a yellow room) where the photopolymerizable composition is not exposed to light. Moreover, although it is preferable to carry out in air, you may carry out in inert gas atmospheres, such as nitrogen atmosphere and oxygen dioxide atmosphere.

(Process (b))
This step is performed in a state where the photopolymerizable composition is in contact with an atmosphere containing oxygen. Air is preferable as the atmosphere containing oxygen.
By irradiating the photopolymerizable composition with ultraviolet light in a state where the photopolymerizable composition is in contact with the oxygen-containing atmosphere, the radical polymerization reaction in the surface layer portion in contact with the oxygen-containing atmosphere is inhibited. Curing of the photopolymerizable composition is suppressed and fluidity is maintained. Therefore, even if the photopolymerizable composition in the portion in contact with the mold surface cures and shrinks, the photopolymerizable composition in the surface layer portion flows downward, and there is a dent on the surface of the photopolymerizable composition (semi-cured product). Even if it occurs, it is difficult to generate wrinkles or voids that cause transfer failure at the interface between the mold and the photopolymerizable composition (semi-cured product). On the other hand, when the photopolymerizable composition is cured in an atmosphere without oxygen such as a nitrogen atmosphere in a vacuum, the surface layer portion of the photopolymerizable composition is preferentially cured, and the photopolymerizability of the portion in contact with the mold On the surface of the semi-cured product of the composition, wrinkles and transfer defects due to curing shrinkage occur.

  Examples of ultraviolet light sources include germicidal lamps, fluorescent lamps for ultraviolet rays, carbon arc, xenon lamps, high pressure mercury lamps for copying, medium or high pressure mercury lamps, ultrahigh pressure mercury lamps, electrodeless lamps, metal halide lamps, natural light, etc., semi-cured From the viewpoint of simplicity of control, a high pressure mercury lamp is preferable.

The illuminance of light having an ultraviolet wavelength of 365 nm is 300 mW / cm ² or more, and preferably 500 mW / cm ² or more. If the illuminance of light with a wavelength of 365 nm is 300 mW / cm ² or more, the energy reaches the surface of the mold in a short time, and the photopolymerizable composition cures preferentially and sufficiently at the part in contact with the mold. Therefore, in the second and subsequent ultraviolet irradiations, the photopolymerizable composition (semi-cured product) in the portion in contact with the mold hardly undergoes curing shrinkage, and a molded product in which wrinkles and transfer defects are suppressed is obtained.

  The light amount of the ultraviolet light having a wavelength of 365 nm is set to a light amount at which the curing degree X calculated by the equation (1) is 30 to 90%. If the curing degree X is 90% or less, the photopolymerizable composition in the surface layer portion tends to flow downward, and causes wrinkles and transfer defects at the interface between the mold and the photopolymerizable composition (semi-cured product). It is difficult to generate voids. When the degree of cure X is 30% or more, a molded product in which the photopolymerizable composition (semi-cured product) is hard to shrink in the portion contacting the mold in the second and subsequent ultraviolet irradiations, and wrinkles and transfer defects are suppressed. Is obtained.

The amount of light with a wavelength of 365 nm at which the degree of cure X is 30 to 90% is determined in advance according to the above-described procedure for determining the degree of cure before this step. Specifically, for the photopolymerizable composition used in this step, A ₀ / B ₀ and A ₁₀₀ / B ₁₀₀ are obtained by procedures (i) to (v), and then the amount of light having a wavelength of 365 nm is changed. Then, the steps (vi) to (x) are repeated, and a graph (calibration curve) of the degree of cure X with respect to the amount of light with a wavelength of 365 nm is created, and the wavelength of 365 nm with respect to the target degree of cure X is obtained using the calibration curve. Determine the amount of light.

(Process (c))
An uncured photopolymerizable composition is supplied to the surface of the semi-cured product so as to fill the dent on the surface of the semi-cured product generated in the previous step.
Examples of the coating method (supply method) of the photopolymerizable composition in this step include the same method as in step (a), and the preferred embodiments are also the same.
What is necessary is just to determine the application quantity of a photopolymerizable composition suitably according to the desired thickness of a molded object.

(Process (d))
This step can be carried out in the same manner as in step (b), and the preferred embodiment is also the same.
Step (c) and step (d) may be repeated twice or more depending on the thickness of the molded body.

(Process (e))
An uncured photopolymerizable composition is supplied to the surface of the semi-cured product so as to fill the dent on the surface of the semi-cured laminate generated in the previous step.
Examples of the coating method (supply method) of the photopolymerizable composition in this step include the same method as in step (a), and the preferred embodiments are also the same.
What is necessary is just to determine the application quantity of a photopolymerizable composition suitably according to the desired thickness of a molded object.

(Process (f))
After placing the substrate on the photopolymerizable composition, it is preferable to pressurize from the mold side, the substrate side, or both. Examples of the pressurizing method include a mechanical pressing method, a pressing method using gas or liquid as a medium, and the like. The press pressure (gauge pressure) is preferably more than 0 to 10 MPa, more preferably 0.1 to 5 MPa. 0-100 degreeC is preferable and the temperature at the time of pressurizing has more preferable 10-60 degreeC.

(Process (g '), (g))
Since this step is intended to completely cure the photopolymerizable composition, it is performed in a state where the photopolymerizable composition is not in contact with an atmosphere containing oxygen. The state not in contact with an atmosphere containing oxygen means a state in contact with an atmosphere not containing oxygen such as a nitrogen atmosphere in a vacuum, or a state in which a substrate is placed on a photopolymerizable composition.
Examples of the ultraviolet light source include the same light source as in step (b), and the preferred embodiment is also the same.

The illuminance of ultraviolet light having a wavelength of 365 nm is preferably 1 mW / cm ² or more, and more preferably 50 mW / cm ² or more. When the illuminance of light having a wavelength of 365 nm is 1 mW / cm ² or more, the time until the photopolymerizable composition is cured does not become long, and the productivity is good.

  The light amount of the ultraviolet light having a wavelength of 365 nm is set to a light amount at which the curing degree X calculated by the equation (1) is 95% or more. The amount of light with a wavelength of 365 nm at which the curing degree X is 95% is determined in advance according to the above-described procedure for determining the curing degree before this step. Specifically, the amount of light having a wavelength of 365 nm with respect to the target curing degree X is determined using a calibration curve as in the step (b).

(Process (h))
As a method for separating a molded body made of a cured laminate and a mold, a method of fixing both by vacuum suction and moving them in the direction of separating one side, a method of mechanically fixing both and moving in a direction of separating one side Etc.

(Use)
The molded body having a fine pattern on the surface produced by the production method of the present invention can be used as, for example, the following article.
Optical elements: aspherical microlens array, spherical microlens array, optical waveguide element, optical switching element (grid polarization element, wave plate, etc.), Fresnel zone plate element, binary element, blaze element, photonic crystal, etc.
Antireflective member: AR (Anti Reflection) coating member, etc.
Chips: Biochips, μ-TAS (Micro-Total Analysis Systems) chips, microreactor chips, and the like.
Others: recording media, display materials, catalyst supports, filters, sensor members, semiconductor devices (including MEMS), electrolysis replicas, replica molds for mass production of the above articles, and the like.

(Function and effect)
In the method for producing a molded article having the fine pattern of the present invention described above on the surface, in step (b) (and further in step (d) if necessary), the photopolymerizable composition is in an atmosphere containing oxygen. Since the photopolymerizable composition is cured by irradiating the photopolymerizable composition with ultraviolet rays having a sufficiently high illuminance of light having a wavelength of 365 nm in the contact state, the mold and the photopolymerizable composition (semi-cured) In the interface between the photopolymerizable composition (semi-cured product) and the voids that cause defects and poor transfer at the interface with the product, and the portion that is in contact with the mold in the second and subsequent ultraviolet irradiations. Hateful. As a result, a molded body in which wrinkles and transfer defects are suppressed can be obtained.

<First to third embodiments>
Hereinafter, specific examples of the production method of the present invention will be described with reference to the drawings.

[First Embodiment]
FIG. 5 is a process diagram showing a first embodiment of a method for producing a molded body having a fine pattern on its surface according to the present invention.

(Process (a))
An uncured photopolymerizable composition 20 is formed on the surface of the mold 10 having a hemispherical protrusion 14 (reversal pattern) at the center of the surface of the flat mold base 12 and having a weir 16 on the periphery of the surface. Is supplied so that the space between the protrusion 14 and the weir 16 is completely filled.

(Process (b))
In a state where the photopolymerizable composition 20 is in contact with an atmosphere containing oxygen, ultraviolet rays having an illuminance of light having a wavelength of 365 nm of 300 mW / cm ² or more are calculated by the formula (1). Irradiated from the surface side of the photopolymerizable composition 20 with a light amount such that the curing degree X is 30 to 90%, the photopolymerizable composition 20 is cured to obtain a semi-cured product 22.

(Process (c))
The uncured photopolymerizable composition 20 is supplied to the surface of the semi-cured product 22 so as to fill the dent on the surface of the semi-cured product 22 generated in the step (b).

(Process (d))
In a state where the photopolymerizable composition 20 is in contact with an atmosphere containing oxygen, ultraviolet rays having a wavelength 365 nm of light having an illuminance of 300 mW / cm ² or more are applied to the photopolymerizable composition 20 and the semi-cured product 22 according to the formula (1 ) Is irradiated from the surface side of the photopolymerizable composition 20 with an amount of light such that the degree of cure X calculated in 30) is 30 to 90%, the photopolymerizable composition 20 and the semi-cured product 22 are cured, and semi-cured lamination Let it be an object 24.

(Process (e))
The uncured photopolymerizable composition 20 is semi-cured laminate 24 so as to fill the dents on the surface of the semi-cured laminate 24 generated in the step (d) and to obtain a desired thickness of the molded product. Supply to the surface.

(Process (g))
In an inert gas atmosphere, the photopolymerizable composition 20 and the semi-cured laminate 24 are irradiated with ultraviolet rays, and the photopolymerizable composition is used with a light amount such that the curing degree X calculated by the formula (1) is 95% or more. 20 is irradiated from the surface side to cure the photopolymerizable composition 20 and the semi-cured laminate 24 to obtain a cured laminate 26.

(Process (h))
By separating the molded body made of the cured laminate 26 and the mold 10, the molded body 1 having a semispherical concave portion 28 (fine pattern) on the surface is obtained.

[Second Embodiment]
FIG. 6 is a process diagram showing a second embodiment of a method for producing a molded body having a fine pattern on the surface according to the present invention.

(Process (a))
An uncured photopolymerizable composition 20 is formed on the surface of the mold 10 having a hemispherical protrusion 14 (reversal pattern) at the center of the surface of the flat mold base 12 and having a weir 16 on the periphery of the surface. Is supplied so that the space between the protrusion 14 and the weir 16 is completely filled.

(Process (b))
In a state where the photopolymerizable composition 20 is in contact with an atmosphere containing oxygen, ultraviolet rays having an illuminance of light having a wavelength of 365 nm of 300 mW / cm ² or more are calculated by the formula (1). Irradiated from the surface side of the photopolymerizable composition 20 with a light amount such that the curing degree X is 30 to 90%, the photopolymerizable composition 20 is cured to obtain a semi-cured product 22.

(Process (c))
The uncured photopolymerizable composition 20 is supplied to the surface of the semi-cured product 22 so as to fill the dent on the surface of the semi-cured product 22 generated in the step (b).

(Process (d))
In a state where the photopolymerizable composition 20 is in contact with an atmosphere containing oxygen, ultraviolet rays having a wavelength 365 nm of light having an illuminance of 300 mW / cm ² or more are applied to the photopolymerizable composition 20 and the semi-cured product 22 according to the formula (1 ) Is irradiated from the surface side of the photopolymerizable composition 20 with an amount of light such that the degree of cure X calculated in 30) is 30 to 90%, the photopolymerizable composition 20 and the semi-cured product 22 are cured, and semi-cured lamination It is assumed to be an object 24.

(Process (e))
The uncured photopolymerizable composition 20 is semi-cured laminate 24 so as to fill the dents on the surface of the semi-cured laminate 24 generated in the step (d) and to obtain a desired thickness of the molded product. Supply to the surface.

(Process (f))
A transparent substrate 30 is placed on the photopolymerizable composition 20.

(Process (g))
The photopolymerizable composition 20 and the semi-cured laminate 24 are irradiated with ultraviolet rays from the transparent substrate 30 side with a light amount such that the curing degree X calculated by the formula (1) is 95% or more. 20 and the semi-cured laminate 24 are cured to form a cured laminate 26.

(Process (h))
By separating the molded body made of the cured laminate 26 with the transparent substrate 30 and the mold 10, the molded body 1 having a semispherical concave portion 28 (fine pattern) on the surface is obtained.

[Third Embodiment]
FIG. 7 is a process diagram showing a third embodiment of a method for producing a molded body having a fine pattern on its surface according to the present invention.

(Process (a))
An uncured photopolymerizable composition 20 is formed on the surface of the mold 10 having a hemispherical protrusion 14 (reversal pattern) at the center of the surface of the flat mold base 12 and having a weir 16 on the periphery of the surface. Is supplied so that the space between the protrusion 14 and the weir 16 is completely filled.

(Process (b))
In a state where the photopolymerizable composition 20 is in contact with an atmosphere containing oxygen, ultraviolet rays having an illuminance of light having a wavelength of 365 nm of 300 mW / cm ² or more are calculated by the formula (1). Irradiated from the surface side of the photopolymerizable composition 20 with a light amount such that the curing degree X is 30 to 90%, the photopolymerizable composition 20 is cured to obtain a semi-cured product 22.

(Process (c))
The uncured photopolymerizable composition 20 is removed from the surface of the semi-cured product 22 so as to fill in the dents on the surface of the semi-cured product 22 generated in the step (b) and to obtain a desired thickness. To supply.

(Process (f))
A transparent substrate 30 is placed on the photopolymerizable composition 20.

(Process (g ′))
The photopolymerizable composition 20 and the semi-cured product 22 are irradiated with ultraviolet rays from the transparent substrate 30 side with a light amount such that the curing degree X calculated by the formula (1) is 95% or more. The semi-cured product 22 is cured to obtain a cured laminate 26.

(Process (h))
(H) The molded body made of the cured laminate 26 with the transparent substrate 30 and the mold 10 are separated to obtain the molded body 1 having a semicircular spherical recess 28 (fine pattern) on the surface.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
Examples 1 to 8 are preparation examples, examples 9 to 15 and examples 21 to 33 are examples, and examples 16 to 20 and example 34 are comparative examples.

(Curing shrinkage)
About 1.5 μL of the photopolymerizable composition was injected into a glass tube having an inner diameter of 0.8 mm, and the width (A) between the bottoms of the meniscus surfaces at both ends of the photopolymerizable composition was measured.
Then, under a nitrogen atmosphere, the photopolymerizable composition in the glass tube is irradiated with ultraviolet rays adjusted so that the illuminance of light having a wavelength of 365 nm is 28 mW / cm ² and the light amount is 420 mJ / cm ^2, and photopolymerization is performed. The composition was cured. The width (B) between the bottoms of the meniscus surfaces at both ends of the photopolymerizable composition after curing was measured. The cure shrinkage rate (%) was calculated from the following formula (6).
Curing shrinkage = ((A) − (B)) / (A) × 100 (6).

(Illuminance and light intensity)
The illuminance of light having a wavelength of 365 nm and the light amount of light having a wavelength of 365 nm were measured using an ultraviolet integrated light meter (UIT-250, manufactured by USHIO INC.).

(Curing degree)
Using a real-time FT-IR system for UV curable resin (manufactured by Thermo Fisher Scientific), the degree of cure X was calculated according to the procedures (i) to (x) described above.

(Releasability)
The pattern part at the time of mold release is divided into 9 parts, and the ratio of adhesion without being transferred for each division is evaluated on a five-point scale (0 (not adhered) to 4 (completely adhered)). Judged whether or not. That is, when the evaluation of each division is 0, 0, 1, 0, 3, 0, 2, 0, 1, it is calculated as (0 + 0 + 1 + 0 + 3 + 0 + 2 + 0 + 1) / 36 × 100 = 19%. When the ratio was 10% or less, it was judged that the releasability was good.

(Shape and appearance)
The shape of the mold and the molded body is measured with a laser microscope (VK-9500, manufactured by Keyence Corporation). The difference in the depth of the shape is 3% or more, x is 3 to 1%, and less than 1% is ○ And less than 1% were judged as good transfer accuracy.
Further, the appearance of the molded body was observed with a research system microscope (manufactured by Olympus Corporation, BX51) to confirm the presence of wrinkles and transfer defects.

(Adhesion)
After immersing the molded body in acetone for 5 minutes, the appearance of the molded body was observed with a research system microscope (manufactured by Olympus Corporation, BX51), and it was confirmed that there were no acetone-derived oil droplets or traces of oil droplets between the layers. .

(Mold A)
As shown in FIG. 8, a Fresnel lens-shaped convex mold (made of stainless steel, 9 steps in a diameter of 9 mm, groove height: 20 μm, interval: 1400 to 240 μm, aspect ratio: 0.08 at the maximum) Prepared.

(Mold B)
As shown in FIG. 9, an aspherical lens-shaped convex mold (made of nickel, aspherical lens height: 10 μm, aspherical lens diameter: 80 μm, aspect ratio: 0.13 at maximum) was prepared.

(Mold C)
A two-stage pyramid-shaped convex mold (made of copper, pyramid height: 80 μm, bottom of pyramid: 240 μm square, aspect ratio: 0.44 at the maximum) as shown in FIG. 10 was prepared.

(Mold D)
Mold with line and space pattern mixed with pillar and hole pattern (Kyodo International, silicon, size: 20 mm square, pattern size: 0.5 μm, 1 μm and 2 μm mixed, high 1 μm, aspect ratio: 2.00 at the maximum).

(Monomer (A1))
Monomer _{(A1-1): C 2 H 2} = CH-C (O) O- (CH 2) 2 - (CF 2) 6 F
Monomer _{(A1-2): CH 2 = C} (CH 3) -C (O) O- (CH 2) 2 - (CF 2) 4 F

Monomer _{(A1-3): CF 2 = CFCF} 2 C (CF 3) (OH) Synthesis of CH ₂ CH = CH 2.
A 2 L glass reactor was charged with 108 g CF ₂ ClCFClCF ₂ C (O) CF ₃ and 500 mL dehydrated tetrahydrofuran and cooled to 0 ° C. Under a nitrogen atmosphere, 200 mL of a 2 mol / L CH ₂ ═CHCH ₂ MgCl tetrahydrofuran solution further diluted with 200 mL dehydrated tetrahydrofuran was added dropwise over about 5.5 hours. After completion of the dropwise addition, the mixture was stirred at 0 ° C. for 30 minutes and stirred at room temperature for 17 hours, and then 200 mL of 2 mol / L hydrochloric acid was added dropwise. Furthermore, 200 mL of water and 300 mL of diethyl ether were added and separated to obtain a diethyl ether layer as an organic layer. The organic layer was dried over magnesium sulfate and then filtered to obtain a crude liquid. The crude liquid was concentrated with an evaporator and then distilled under reduced pressure to obtain 85 g of CF ₂ ClCFClCF ₂ C (CF ₃ ) (OH) CH ₂ CH═CH ₂ (60 to 66 ° C./0.7 kPa).

Subsequently, 81 g of zinc and 170 mL of dioxane were placed in a 500 mL glass reactor, and zinc was activated with iodine. Then heated to 100 ° C., was added dropwise over the _{CF 2 ClCFClCF 2 C (CF 3} ) (OH) CH 2 CH = CH 1.5 hours that was diluted ₂ of 84g in 50mL of dioxane. After completion of dropping, the mixture was stirred at 100 ° C for 40 hours. The reaction solution was filtered and washed with a small amount of dioxane. The filtrate was distilled under reduced pressure to obtain 30 g of monomer (A1-3) (36 to 37 ° C./1 kPa).

The ¹ H-NMR and ¹⁹ F-NMR data are shown below.
¹ H-NMR (399.8 MHz, solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 2.74 (d, J = 7.3, 2H), 3.54 (load s, 1H), 5.34 (m, 2H), 5.86 (m, 1H).
¹⁹ F-NMR (376.2 MHz, solvent: CDCl ₃ , reference: CFCl ₃ ) δ (ppm): −75.7 (m, 3F), −92.2 (m, 1F), −106.57 (m , 1F), -112.6 (m, 2F), -183.5 (m, 1F).

(Monomer (A2))
Monomer (A2-1): Compound represented by the following formula (A2-1) (manufactured by Idemitsu Kosan Co., Ltd.).

(Monomer (A3))
Monomer _{(A3-1): CH 2 = CHC} (O) O (CH 2 CH 2 O) 4 C (O) CH = CH 2
Monomer (A3-2): a compound represented by the following formula (A3-2) (where n is an integer of 1 to 2).

Monomer _{(A3-3): [CH 2 =} CHC (O) O (CH 2 CH 2 O) n CH 2] 3 CCH 2 CH 3 ( where, n is a number of 2-3).
Monomer _{(A3-4): [CH 2 =} C (CH 3) C (O) OCH 2] 2 C (CH 3) 2

(Fluorine-containing surfactant (B))
Fluorine-containing surfactant (B-1): Nonionic fluorine-containing surfactant, manufactured by Seimi Chemical Co., Surflon S-393.

(Photopolymerization initiator (C))
Photopolymerization initiator (C-1): Irgacure 651, manufactured by Ciba Geigy Specialty.

(Primer solution)
1 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) is put in a vial container (internal volume: 13 mL), and 9 g of xylene and 0.1 g of acetic acid may be added thereto. A primer solution was obtained by mixing and filtering with a filter made of polytetrafluoroethylene having a pore size of 0.2 μm.

(substrate)
Quartz wafer: 0.7 mm thick.
Polyethylene terephthalate (hereinafter referred to as PET) film: Lumirror U34 manufactured by Toray Industries, Inc.

(light source)
Light source 1: SP-9 manufactured by USHIO INC.
Light source 2: J-Cure 1500 manufactured by JATEC.

(Preparation of photopolymerizable composition)
[Example 1]
In a vial container (internal volume 13 mL), 0.88 g of monomer (A1-1), 0.02 g of fluorine-containing surfactant (B-1), 1.42 g of monomer (A2-1), monomer (A3- 0.76 g of 1) and 0.76 g of monomer (A3-3) were added, and then 0.16 g of photopolymerization initiator (C-1) was mixed, and a filter made of polytetrafluoroethylene having a pore diameter of 0.2 μm To obtain a photopolymerizable composition 1.

[Examples 2 to 8]
According to the ratio shown in Table 1, in the same manner as in Example 1, the monomer, the fluorine-containing surfactant, and the photopolymerization initiator were mixed, and then filtered through a polytetrafluoroethylene filter having a pore size of 0.2 μm. Thus, photopolymerizable compositions 2 to 8 were obtained.

(Manufacture of molded products with fine patterns on the surface)
[Example 9]
Step (a):
At 25 ° C., 50 μL of the photopolymerizable composition 1 was applied to the surface of the mold A.

Step (b):
25 ° C., under atmospheric, from the light source 1, the illuminance is 590mW / cm ² in the wavelength 365nm light, the wavelength of 365nm ultraviolet as the amount of light becomes 11800mJ / cm ^2, the photopolymerizable composition 1 of the surface Irradiated from the side, the photopolymerizable composition 1 was semi-cured. The degree of cure at this time was 83%.

Step (c):
At 25 ° C., 8 μL of the photopolymerizable composition 1 was applied on the semi-cured photopolymerizable composition 1.

Step (d):
25 ° C., under atmospheric, from the light source 1, the illuminance is 590mW / cm ² in the wavelength 365nm light, the wavelength of 365nm ultraviolet as the amount of light becomes 11800mJ / cm ^2, the photopolymerizable composition 1 of the surface Irradiated from the side, the photopolymerizable composition 1 was semi-cured. The degree of cure at this time was 84%.

Step (e):
At 25 ° C., 8 μL of the photopolymerizable composition 1 was applied on the semi-cured photopolymerizable composition 1.

Step (g):
25 ° C., under a nitrogen atmosphere, from the light source 1, illumination 70 mW / cm ² in the wavelength 365nm light, the amount of wavelength 365nm light the ultraviolet so as to 2100mJ / cm ^2, the photopolymerizable composition 1 Irradiated from the surface side, the photopolymerizable composition 1 was completely cured. The degree of curing at this time was 97%.

Step (h):
A cured product obtained by curing the photopolymerizable composition 1 from the mold A was separated to obtain a molded body. The adhesion ratio was 0%, and the releasability was good, and the shape, appearance and adhesion were also good. Table 2 shows the conditions in each step. The evaluation results are shown in Table 3.

[Example 10]
A molded body was obtained in the same manner as in Example 9 except that the conditions in each step were changed as described in Table 2. The evaluation results are shown in Table 3.

[Example 11]
Step (a):
At 25 ° C., 50 μL of the photopolymerizable composition 1 was applied to the surface of the mold A.

Step (b):
25 ° C., under atmospheric, from the light source 1, the illuminance is 590mW / cm ² in the wavelength 365nm light, the wavelength of 365nm ultraviolet as the amount of light becomes 11800mJ / cm ^2, the photopolymerizable composition 1 of the surface Irradiated from the side, the photopolymerizable composition 1 was semi-cured. The degree of cure at this time was 83%.

Step (c):
At 25 ° C., 8 μL of the photopolymerizable composition 1 was applied on the semi-cured photopolymerizable composition 1.

Step (d):
The surface of the photopolymerizable composition 1 is irradiated with ultraviolet rays from the light source 1 at 25 ° C. in the air so that the illuminance of light with a wavelength of 365 nm is 590 mW / cm ² and the light quantity of light with a wavelength of 365 nm is 11800 mJ / cm ^2. Irradiated from the side, the photopolymerizable composition 1 was semi-cured. The degree of cure at this time was 84%.

Step (e):
At 25 ° C., 0.6 μL of the photopolymerizable composition 1 was applied on the semi-cured photopolymerizable composition 1.

Step (f):
In advance, 1 mL of the primer solution was dropped on the surface of the quartz wafer, applied uniformly by a spin coat method, and then left to dry on a hot plate at 120 ° C. for 10 minutes to prepare a primer-treated quartz wafer. The primer-treated quartz wafer was placed on the photopolymerizable composition 1.

Step (g):
25 ° C., under a nitrogen atmosphere, from the light source 1, illumination 70 mW / cm ² in the wavelength 365nm light, the wavelength of 365nm ultraviolet as the amount of light is 2100mJ / cm ^2, was irradiated from the quartz wafer side, Photopolymerizable composition 1 was completely cured. The degree of curing at this time was 97%.

Step (h):
A cured product obtained by curing the photopolymerizable composition 1 from the mold A was separated to obtain a molded body. The adhesion ratio was 0%, and the releasability was good, and the shape, appearance and adhesion were also good. Table 4 shows the conditions in each step. The evaluation results are shown in Table 5.

[Examples 12 to 31]
Except for changing the conditions in each step as described in Table 4, moldings were obtained and evaluated in the same manner as in Example 11. However, in Example 29, a PET film was used as the substrate instead of the quartz wafer. The evaluation results are shown in Table 5.

[Example 32]
Step (a):
At 25 ° C., 0.4 μL of the photopolymerizable composition 1 was applied to the surface of the mold D.

Step (b):
The surface of the photopolymerizable composition 1 is irradiated with ultraviolet rays from the light source 2 at 25 ° C. in the atmosphere so that the illuminance of light with a wavelength of 365 nm is 734 mW / cm ² and the light quantity of light with a wavelength of 365 nm is 631 mJ / cm ^2. Irradiated from the side, the photopolymerizable composition 1 was semi-cured. The degree of cure at this time was 69%.

Step (c):
At 25 ° C., 0.2 μL of the photopolymerizable composition 1 was applied on the semi-cured photopolymerizable composition 1.

Step (f):
A quartz wafer primed in advance as in Example 11 was prepared and placed on the photopolymerizable composition 1.

Step (g ′):
Pressure is applied from the quartz wafer side at 25 ° C. under a nitrogen atmosphere at a press pressure of 0.4 MPa. In this state, the light source 1 emits light having a wavelength of 365 nm with an illuminance of 20 mW / cm ² and a light amount of 365 nm with a light amount of 600 mJ / The photopolymerizable composition 1 was completely cured by irradiating ultraviolet rays from the quartz wafer side so as to be cm ² . The degree of curing at this time was 96%.

Step (m):
A cured product obtained by curing the photopolymerizable composition 1 from the mold D was separated to obtain a molded body. The adhesion ratio was 0%, and the releasability was good, and the shape, appearance and adhesion were also good. Table 6 shows the conditions in each step. Table 7 shows the evaluation results.

[Example 33]
A molded body was obtained in the same manner as in Example 32 except that the conditions in each step were changed as described in Table 6. Table 7 shows the evaluation results.

[Example 34]
1 mL of the primer solution was dropped on the surface of the quartz wafer, applied uniformly by spin coating, and then allowed to stand on a 120 ° C. hot plate for 10 minutes to dry. After dropping 0.1 mL of the photopolymerizable composition 1 on the surface of the quartz wafer with the primer at 25 ° C., the mold B was pressed against the photopolymerizable composition 1 on the surface of the quartz wafer, and 0 Pressed at 5 MPa.

Next, while applying a pressure of 0.5 MPa at 25 ° C., the illuminance of light of wavelength 365 nm from the light source 1 is 28 mW / cm ² and the amount of light of wavelength 365 nm is 420 mJ / cm. ^The photopolymerizable composition 1 was cured by irradiating with ultraviolet rays from the quartz wafer side so as to obtain a cured resin.

  At 25 ° C., the mold B was separated from the cured resin on the surface of the quartz wafer to obtain a molded body in which a cured resin having a concave portion on the surface where the convex portion of the mold B was inverted was formed on the surface of the quartz wafer. . The adhesion rate was 0% and the releasability was good, but the difference in shape depth was 9%, and the appearance was also distorted at the bottom. Adhesion was good.

  The production method of the present invention is useful for the production of moldings having fine patterns on the surface, such as optical elements (microlenses, etc.), antireflection members, biochips, microreactor chips, recording media, catalyst carriers, semiconductor devices, etc. It is.

10 Mold 12 Mold substrate 14 Protrusion (reverse pattern)
16 Weir 20 Photopolymerizable composition 22 Semi-cured product 24 Semi-cured laminate 26 Cured laminate 28 Recessed portion (fine pattern)
30 Transparent substrate

Claims (10)

The manufacturing method of the molded object which has a fine pattern on the surface which has the following process (a)-(c), process (g '), and process (h).
(A) A step of supplying a photopolymerizable composition to the surface of a mold having a reverse pattern of the fine pattern on the surface.
(B) In a state where the photopolymerizable composition is in contact with an atmosphere containing oxygen, the photopolymerizable composition is irradiated with ultraviolet rays having an illuminance of light having a wavelength of 365 nm of 300 mW / cm ² or more. A step of irradiating with a light amount such that the degree of cure X calculated in (30) is 30 to 90% to cure the photopolymerizable composition to obtain a semi-cured product.
(C) A step of supplying a photopolymerizable composition to the surface of the semi-cured product.
(G ′) In a state where the photopolymerizable composition is not in contact with an atmosphere containing oxygen, ultraviolet rays are applied to the photopolymerizable composition and the semi-cured product, and the curing degree X calculated by the following formula (1) is A step of irradiating with a light amount of 95% or more to cure the photopolymerizable composition and semi-cured product to obtain a cured laminate.
(H) A step of separating the molded body made of the cured laminate and the mold to obtain a molded body having a fine pattern on the surface.
X = (S ₀ −S _X ) / (S ₀ −S ₁₀₀ ) × 100 (1).
However,
S ₀ is a peak area A ₀ of C═C stretching vibration of carbon-carbon unsaturated double bond in the infrared absorption spectrum of the uncured photopolymerizable composition, and a specific value not affected by radical polymerization reaction. It is a ratio (A ₀ / B ₀ ) with the peak area B ₀ of the stretching vibration of the functional group,
S ₁₀₀ is C = C stretching of a carbon-carbon unsaturated double bond in an infrared absorption spectrum of a cured product obtained by completely curing the photopolymerizable composition by irradiating the photopolymerizable composition with excess ultraviolet rays. and the peak area _{a 100} of the vibration, a ratio of the peak area _{B 100} of the stretching vibration of the particular functional group that is not affected by the radical polymerization reaction _{(a 100 / B} 100),
S _X represents carbon-carbon in the infrared absorption spectrum of a cured product obtained by curing the photopolymerizable composition by irradiating the photopolymerizable composition with a predetermined amount of ultraviolet light in the same atmosphere and illuminance as in this step. The ratio (A _X / B _X ) between the peak area A _X of the C = C stretching vibration of the carbon unsaturated double bond and the peak area B _X of the stretching vibration of a specific functional group not affected by the radical polymerization reaction is there. The manufacturing method of the molded object which has the fine pattern of Claim 1 on the surface which has the following process (f) between the said process (c) and the said process (g ').
(F) A step of placing a substrate on the photopolymerizable composition. The manufacturing method of the molding which has a fine pattern on the surface which has the following process (a)-(e), a process (g), and a process (h).
(A) A step of supplying a photopolymerizable composition to the surface of a mold having a reverse pattern of the fine pattern on the surface.
(B) In a state where the photopolymerizable composition is in contact with an atmosphere containing oxygen, the photopolymerizable composition is irradiated with ultraviolet rays having an illuminance of light having a wavelength of 365 nm of 300 mW / cm ² or more. A step of irradiating with a light amount such that the degree of cure X calculated in (30) is 30 to 90% to cure the photopolymerizable composition to obtain a semi-cured product.
(C) A step of supplying a photopolymerizable composition to the surface of the semi-cured product.
(D) In a state where the photopolymerizable composition is in contact with an atmosphere containing oxygen, the photopolymerizable composition and the semi-cured product are irradiated with ultraviolet light having a wavelength 365 nm of light having an illuminance of 300 mW / cm ² or more. The process of irradiating with the light quantity from which the hardening degree X calculated by Formula (1) will be 30 to 90%, hardening the said photopolymerizable composition and semi-hardened material, and setting it as a semi-hardened laminated body.
(E) A step of supplying a photopolymerizable composition to the surface of the semi-cured laminate.
(G) In a state where the photopolymerizable composition is not in contact with an oxygen-containing atmosphere, ultraviolet rays are applied to the photopolymerizable composition and the semi-cured laminate, and the curing degree X calculated by the following formula (1) is A step of irradiating with a light amount of 95% or more to cure the photopolymerizable composition and the semi-cured laminate to obtain a cured laminate.
(H) A step of separating the molded body made of the cured laminate and the mold to obtain a molded body having a fine pattern on the surface.
X = (S ₀ −S _X ) / (S ₀ −S ₁₀₀ ) × 100 (1).
However,
S ₀ is a peak area A ₀ of C═C stretching vibration of carbon-carbon unsaturated double bond in the infrared absorption spectrum of the uncured photopolymerizable composition, and a specific value not affected by radical polymerization reaction. It is a ratio (A ₀ / B ₀ ) with the peak area B ₀ of the functional group,
S ₁₀₀ is C = C stretching of a carbon-carbon unsaturated double bond in an infrared absorption spectrum of a cured product obtained by completely curing the photopolymerizable composition by irradiating the photopolymerizable composition with excess ultraviolet rays. and the peak area _{a 100} of the vibration, a ratio of the peak area _{B 100} of the particular functional group that is not affected by the radical polymerization reaction _{(a 100 / B} 100),
S _X represents carbon-carbon in the infrared absorption spectrum of a cured product obtained by curing the photopolymerizable composition by irradiating the photopolymerizable composition with a predetermined amount of ultraviolet light in the same atmosphere and illuminance as in this step. It is a ratio (A _X / B _X ) between the peak area A _X of C═C stretching vibration of a carbon unsaturated double bond and the peak area B _X of a specific functional group not affected by the radical polymerization reaction. The manufacturing method of the molded object which has the following fine process pattern of Claim 3 which has the following process (f) between the said process (e) and the said process (g).
(F) A step of placing a substrate on the photopolymerizable composition.   The manufacturing method of the molded object which has the fine pattern in any one of Claims 1-4 in which the said photopolymerizable composition contains the monomer (A) which has one or more carbon-carbon unsaturated double bonds. .   The said monomer (A) contains the monomer (A1) which has a fluorine atom and has one or more carbon-carbon unsaturated double bonds, The manufacture of the molded object which has the fine pattern on the surface of Claim 5 Method.   The manufacturing method of the molded object which has the fine pattern in any one of Claims 1-6 in which the said photopolymerizable composition contains a fluorine-containing surfactant (B) further.   The manufacturing method of the molding which has the fine pattern in any one of Claims 1-7 whose aspect ratio of the said inversion pattern is 0.1 or more.   The manufacturing method of the molded object which has the fine pattern in any one of Claims 1-8 whose said mold has a dam part in the periphery of the surface which has the said inversion pattern.   The microlens manufactured by the manufacturing method of the molded object which has the fine pattern in any one of Claims 1-9 on the surface.

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