JP2014051601A - Optical formed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical formed body excellent in scratch resistance and adhesiveness to a substrate which is expected to be used as optical materials used for applications including displays such as liquid crystal displays and organic electroluminescence (EL) displays, optical components such as lenses, lighting equipment and solar cells and the like.SOLUTION: In an optical formed body in which a resin layer is formed on a substrate and a fine uneven shape is structured on a surface of the resin layer, a polymer used for the resin layer is composed of a polymer having a cyclic structure containing a heteroatom in the backbone which is formed through cyclization polymerization of a monomer component comprising at least one diene structure-containing monomer selected from the group consisting of a 1, 5-diene structure-containing monomer containing a heteroatom and 1, 6-diene structure-containing monomer containing a heteroatom.

Description

  The present invention relates to an optical molded body. More specifically, the present invention relates to an optical molded article having excellent scratch resistance and adhesion to a substrate. The optical molded body of the present invention is used, for example, as an optical material used for a solar cell or the like including a display such as a liquid crystal display or an organic electroluminescence (EL) display, an optical member such as a lens, a lighting fixture, or the like. Is expected.

  In recent years, various molding materials have been developed for use in optical molded articles. Silicone-based thermosetting liquid resin compositions have been proposed as molding materials excellent in mold transferability and molding processability (see, for example, Examples 1 to 3 in Patent Document 1). However, an optical molded body produced using the molding material has a drawback of low scratch resistance due to the use of a silicone resin.

  In addition, in optical parts used in displays such as liquid crystal displays and organic electroluminescence (EL) displays, and optical members such as lenses, the reflection of light rays such as sunlight and illumination at the interface that comes into contact with air reduces visibility. There is. Therefore, in order to suppress the reflection of light rays on the surface of the optical member, it is considered that the optical member is subjected to an anti-glare [AG (Anti-Glare)] process, an anti-reflection [AR (Anti-Reflection)] process, or the like. It has been.

  Here, the anti-glare treatment refers to a treatment that imparts a concavo-convex structure to the surface by applying fine particles or the like to an optical member and scatters light rays to scatter the reflected image and blur the outline. The antireflection treatment is a treatment that causes interference of light rays and reduces the reflectance by forming a film having a refractive index different from that of the base material on the surface of the base material with a thickness of about the wavelength of light. Means.

  In order to prevent reflection of light rays, it has been proposed to impart a moth-eye structure to a substrate (for example, see Non-Patent Document 1). When the moth-eye structure is applied to the base material, a chevron-shaped projection smaller than the wavelength of visible light is formed on the surface of the base material. Therefore, the refractive index of the boundary region between the base material and air forms the projection. It is an intermediate value between the refractive index of the material and the refractive index of air. In the boundary region between the substrate and air, the occupancy ratio between the protrusions on the substrate and air changes in the height direction of the protrusions, so the refractive index of the boundary region between the substrate and air is the wavelength of visible light. Continuously changing at shorter distances. As a result, the interface between the base material and air does not function as an interface having a different refractive index, so that reflection of visible light at the interface can be suppressed.

An optical molded body having a moth-eye structure is produced, for example, by a method of transferring a nanometer-sized uneven structure carved into a mold onto a base material, a so-called nanoimprint method. As a nanoimprint method,
(1) A thermoplastic base material is softened by heating, and after forming by pressing a mold against the softened base material, cooling is performed, and then the mold is released from the base material to release the mold. A method for producing a molded article for use,
(2) An active energy ray-curable composition is filled between a stamper and a transparent optical molded article, and the active energy ray-curable composition is cured by irradiating the active energy ray to form an optical component. Method for manufacturing body (for example, see Patent Document 2)
Etc. are known.

  Among the methods, the method (2) has an advantage that the molding time can be shortened as compared with the method (1). However, the optical molded body obtained by the method (2) is inferior in adhesion to the substrate due to curing shrinkage and the like, and has a high degree of cross-linking so that it has high hardness and brittleness. When the concavo-convex shape is formed on the surface, the concavo-convex portion may be broken, and it cannot be said that the scratch resistance is sufficient.

JP 2011-093994 A JP 2008-209540 A

“OPTICA ACTA”, 1982, Vol. 29, No. 7, p. 993-1009

  This invention is made | formed in view of the said prior art, and makes it a subject to provide the molded object for optics excellent in abrasion resistance and the adhesiveness with respect to a base material.

The present invention
(1) An optical molded body in which a resin layer is formed on a substrate and a fine uneven shape is formed on the surface of the resin layer, and the polymer used for the resin layer is represented by the formula (I):

(Wherein R ¹ is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, R ² is a methylene group, R ³ is a direct bond or a methylene group, R ⁴ is a hydrogen atom, an alkyl having 1 to 4 carbon atoms) Group, phenyl group, carboxyl group, ester group or cyano group, R ⁵ is a direct bond or methylene group, X and Y are each independently a methylene group optionally having an alkyl group of 1 to 4 carbon atoms, imino A group, a carbonyl group, an oxygen atom or a sulfur atom, Z represents a direct bond, a methylene group which may have an alkyl group having 1 to 4 carbon atoms, an imino group, a carbonyl group, an oxygen atom or a sulfur atom; At least one group of Y and Z is an oxygen atom, a sulfur atom or an imino group which are not adjacent to each other)
An optical molded article characterized by being a polymer having a ring structure-containing unit represented by:
(2) A polymer having a ring structure-containing unit has the formula (Ia):

(Wherein R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms)
And (3) a resin layer is formed on the substrate, and a fine concavo-convex shape is formed on the surface of the resin layer. A molded article for optical use, wherein the polymer used for the resin layer is a 1,5-diene structure-containing monomer containing a heteroatom and a 1,6-diene structure-containing monomer containing a heteroatom It is formed of a polymer having a ring structure containing a heteroatom in the main chain formed by cyclopolymerizing a monomer component containing at least one diene structure-containing monomer selected from the group consisting of The present invention relates to an optical molded body characterized by

  In the present specification, “(meth) acrylate” means “acrylate” and / or “methacrylate”, and “(meth) acryl” means “acryl” and / or “methacryl”.

  ADVANTAGE OF THE INVENTION According to this invention, the molded object for optics excellent in abrasion resistance and the adhesiveness with respect to a base material is provided.

It is a schematic explanatory drawing which shows one embodiment of the manufacturing method of the optical molded object of this invention. It is a schematic sectional drawing which shows one embodiment of the optical molded object of this invention. It is a schematic sectional drawing which shows one embodiment of the polarizer protective film in which the molded object for optics of this invention was used. It is a schematic sectional drawing which shows one embodiment of the organic electroluminescent (organic EL) light-emitting device using the optical molded object of this invention.

  As described above, the optical molded body of the present invention is an optical molded body in which a resin layer is formed on a base material and a fine uneven shape is formed on the surface of the resin layer, and is used for the resin layer. The polymer is at least one diene structure-containing monomer selected from the group consisting of a 1,5-diene structure-containing monomer containing a heteroatom and a 1,6-diene structure-containing monomer containing a heteroatom. It is formed by the polymer which has the ring structure containing the hetero atom obtained by cyclopolymerizing the monomer component containing this in a principal chain.

  In the optical molded body of the present invention, since the resin layer formed on the base material in this way is formed of a polymer having a ring structure containing the heteroatom in the main chain, a conventional ultraviolet curable resin is used. Compared with the case of using, the adhesiveness of the resin layer to the substrate is excellent.

  Conventionally, in order to improve moldability when molding a resin layer, the polymer used in the resin layer preferably has a low glass transition temperature, but on the other hand, the glass transition temperature of the polymer is low. When it is low, it is considered that the scratch resistance of the resin layer is lowered. Further, when the glass transition temperature of the polymer is high, it is considered that not only the moldability is lowered, but the obtained molded body is brittle on the other hand, while its hardness is increased.

  On the other hand, according to the present invention, the polymer having a ring structure containing a heteroatom in the main chain used in the resin layer has a relatively low glass transition temperature, and thus has excellent moldability when molding the resin layer. In addition, the resin layer formed of a polymer having a ring structure containing a heteroatom in the main chain, although the glass transition temperature is relatively low, has excellent scratch resistance. Therefore, both an optical property and an abrasion resistance can be achieved at the same time, so that a molded article for optical use in which a fine concavo-convex shape is formed and a resin layer having a surface excellent in abrasion resistance is formed can be obtained.

  As described above, the optical molded body of the present invention is excellent in scratch resistance and adhesion to a substrate because the resin layer is formed of a polymer having a ring structure containing the hetero atom in the main chain. Therefore, for example, it is expected to be used as an optical material used for solar cells, etc., including displays such as liquid crystal displays and organic electroluminescence (EL) displays, optical members such as lenses, lighting fixtures, etc. is there.

  The polymer having a ring structure containing a heteroatom in the main chain has the formula (I): from the viewpoint of improving scratch resistance and adhesion to a substrate.

(Wherein R ¹ is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, R ² is a methylene group, R ³ is a direct bond or a methylene group, R ⁴ is a hydrogen atom, an alkyl having 1 to 4 carbon atoms) Group, phenyl group, carboxyl group, ester group or cyano group, R ⁵ is a direct bond or methylene group, X and Y are each independently a methylene group optionally having an alkyl group of 1 to 4 carbon atoms, imino Group, carbonyl group, oxygen atom or sulfur atom, Z is a direct bond, methylene group optionally having an alkyl group having 1 to 4 carbon atoms, imino group, carbonyl group, oxygen atom or sulfur atom, X, Y and At least one group of Z is an oxygen atom, sulfur atom or imino group which is not adjacent to each other)
A polymer having a ring structure-containing unit represented by formula (Ia):

(Wherein R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms)
The polymer which has a ring structure containing unit represented by these is more preferable.

In the formula (I) and the formula (Ia), R ¹ is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Suitable monovalent organic groups having 1 to 30 carbon atoms include, for example, a chain saturated hydrocarbon group having 1 to 30 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 30 carbon atoms, and 3 to 30 carbon atoms. Alicyclic hydrocarbon groups, aromatic hydrocarbon groups having 6 to 30 carbon atoms, cyclic ether groups having 2 to 30 carbon atoms, and the like. Some or all of the hydrogen atoms of these organic groups may be substituted with at least one substituent selected from the group consisting of an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group and a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Specific examples of R ¹ include, for example, hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-amyl group, sec-amyl. Group, tert-amyl group, n-hexyl group, sec-hexyl group, n-heptyl group, n-octyl group, sec-octyl group, tert-octyl group, 2-ethylhexyl group, capryl group, nonyl group, decyl group Chain saturated hydrocarbons having 1 to 30 carbon atoms such as a group, undecyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, cetyl group, heptadecyl group, stearyl group, nonadecyl group, eicosyl group, ceryl group, mesyl group Groups: methoxyethyl group, methoxyethoxyethyl group, methoxyethoxyethoxyethyl group, 3-methoxybutyl group, ethoxy group Alkoxy in which a part of hydrogen atoms of a chain saturated hydrocarbon group having 1 to 30 carbon atoms such as ethyl group, ethoxyethoxyethyl group, phenoxyethyl group, and phenoxyethoxyethyl group is substituted with an alkoxy group having 1 to 30 carbon atoms Group-containing chain saturated hydrocarbon group; a hydroxyl group-containing chain in which a part of hydrogen atoms of a chain saturated hydrocarbon group having 1 to 30 carbon atoms such as hydroxyethyl group, hydroxypropyl group, hydroxybutyl group and the like are substituted with a hydroxyl group A saturated hydrocarbon group; a part of hydrogen atoms of a chain saturated hydrocarbon group having 1 to 30 carbon atoms such as a fluoroethyl group, a difluoroethyl group, a chloroethyl group, a dichloroethyl group, a bromoethyl group and a dibromoethyl group are halogen atoms Substituted halogen-containing chain saturated hydrocarbon group; such as vinyl group, allyl group, methallyl group, crotyl group, propargyl group, etc. A chain unsaturated hydrocarbon group having 12 to 30 carbon atoms and a chain unsaturated hydrocarbon group in which part of the hydrogen atoms thereof is substituted with an alkoxy group, hydroxyl group or halogen atom having 1 to 30 carbon atoms; a cyclopropyl group; C3-C20 alicyclic carbonization such as cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-tert-butylcyclohexyl group, tricyclodecanyl group, isobornyl group, adamantyl group, dicyclopentadienyl group A hydrogen group and an alicyclic hydrocarbon group in which part of the hydrogen atom is substituted with an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group or a halogen atom; a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, 4 -Tert-butylphenyl group, benzyl group, diphenylmethyl group, diphenylethyl group, triphenyl An aromatic hydrocarbon group having 6 to 30 carbon atoms such as a til group, cinnamyl group, naphthyl group, and anthranyl group, and an aromatic group in which part of the hydrogen atoms is substituted with an alkoxy group, hydroxyl group, or halogen atom having 1 to 30 carbon atoms Group hydrocarbon group; carbon such as glycidyl group, β-methylglycidyl group, 3,4-epoxycyclohexylmethyl group, tetrahydrofurfuryl group, 3-methyl-3-oxetanylmethyl group, 3-ethyl-3-oxetanylmethyl group, etc. Examples of the cyclic ether group having 2 to 30 carbon atoms and a cyclic ether group in which a part of the hydrogen atom thereof is substituted with an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, or a halogen atom are included in the present invention. It is not limited. It is preferable that the said substituent is a C1-C30 alkoxy group, such as a methoxy group, an ethoxy group, a phenoxy group, for example.

Among R ¹ , a chain saturated hydrocarbon group having 1 to 20 carbon atoms and a chain saturated hydrocarbon group in which some of the hydrogen atoms are substituted with an alkoxy group having 1 to 30 carbon atoms; 4 to 20 carbon atoms Of the alicyclic hydrocarbon group and a part of the hydrogen atom thereof substituted with an alkoxy group having 1 to 30 carbon atoms; an aromatic hydrocarbon group having 6 to 20 carbon atoms and a hydrogen atom thereof An aromatic hydrocarbon group partially substituted with an alkoxy group having 1 to 30 carbon atoms; and a cyclic ether group having 4 to 20 carbon atoms and a part of the hydrogen atoms thereof being substituted with an alkoxy group having 1 to 30 carbon atoms. A cyclic ether group, a chain saturated hydrocarbon group having 1 to 20 carbon atoms and a chain saturated hydrocarbon group in which part of the hydrogen atoms are substituted with an alkoxy group having 1 to 30 carbon atoms; 20 alicyclic hydrocarbon groups; 6-20 carbon atoms An aromatic hydrocarbon group; and a cyclic ether group having 4 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a phenoxyethyl group, a cyclohexyl group, an isobornyl group, a benzyl group, and a tetrahydrofurfuryl group, A methyl group and a cyclohexyl group are even more preferred.

In the formula (I), R ² is a methylene group. R ³ is a direct bond or a methylene group. R ⁴ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group, an ester group or a cyano group. Of the alkyl groups having 1 to 4 carbon atoms, a methyl group is preferable. Examples of the ester group include a group represented by the formula: —COOR ⁶ (wherein R ⁶ represents a monovalent organic group having 1 to 30 carbon atoms). Examples of the monovalent organic group having 1 to 30 carbon atoms include the same monovalent organic groups having 1 to 30 carbon atoms as described above. Among monovalent organic groups having 1 to 30 carbon atoms, chain saturated hydrocarbon groups having 1 to 20 carbon atoms and a portion of the hydrogen atoms substituted with alkoxy groups having 1 to 30 carbon atoms. A hydrocarbon group; an alicyclic hydrocarbon group having 4 to 20 carbon atoms and an alicyclic hydrocarbon group in which some of the hydrogen atoms are substituted with an alkoxy group having 1 to 30 carbon atoms; an aromatic having 6 to 20 carbon atoms Aromatic hydrocarbon group and aromatic hydrocarbon group in which part of its hydrogen atoms are substituted with alkoxy group having 1 to 30 carbon atoms; and cyclic ether group of 4 to 20 carbon atoms and part of its hydrogen atoms having carbon number A cyclic ether group substituted with an alkoxy group having 1 to 30 carbon atoms is preferred, and a chain saturated hydrocarbon group having 1 to 20 carbon atoms and a chain in which some of the hydrogen atoms are substituted with alkoxy groups having 1 to 30 carbon atoms. Saturated hydrocarbon group; alicyclic carbon having 4 to 20 carbon atoms A hydrogen group; an aromatic hydrocarbon group having 6 to 20 carbon atoms; and a cyclic ether group having 4 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a phenoxyethyl group, a cyclohexyl group, an isobornyl group, and a phenyl group. Further, a benzyl group and a tetrahydrofurfuryl group are more preferable, and a methyl group and a cyclohexyl group are still more preferable. R ⁵ is a direct bond or a methylene group.

In the formula (I), X and Y are each independently a methylene group, an imino group, a carbonyl group, an oxygen atom or a sulfur atom which may have an alkyl group having 1 to 4 carbon atoms. Z is a direct bond, a methylene group optionally having an alkyl group having 1 to 4 carbon atoms, an imino group, a carbonyl group, an oxygen atom or a sulfur atom. At least one group of X, Y and Z is an oxygen atom, a sulfur atom or an imino group which are not adjacent to each other. Examples of the imino group include a —NR ⁷ — group (wherein R ⁷ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms). The above-mentioned “oxygen atom, sulfur atom or imino group not adjacent to each other” means that heteroatoms are not adjacent to each other, for example, —O—O—, —O—NR ⁷ — and the like. In the R ⁷ group, examples of the monovalent organic group having 1 to 30 carbon atoms include the same monovalent organic groups having 1 to 30 carbon atoms as described above. Among monovalent organic groups having 1 to 30 carbon atoms, chain saturated hydrocarbon groups having 1 to 20 carbon atoms and a portion of the hydrogen atoms substituted with alkoxy groups having 1 to 30 carbon atoms. A hydrocarbon group; an alicyclic hydrocarbon group having 4 to 20 carbon atoms and an alicyclic hydrocarbon group in which some of the hydrogen atoms are substituted with an alkoxy group having 1 to 30 carbon atoms; an aromatic having 6 to 20 carbon atoms Aromatic hydrocarbon group and aromatic hydrocarbon group in which part of its hydrogen atoms are substituted with alkoxy group having 1 to 30 carbon atoms; and cyclic ether group of 4 to 20 carbon atoms and part of its hydrogen atoms having carbon number A cyclic ether group substituted with an alkoxy group having 1 to 30 carbon atoms is preferred, and a chain saturated hydrocarbon group having 1 to 20 carbon atoms and a chain in which some of the hydrogen atoms are substituted with alkoxy groups having 1 to 30 carbon atoms. Saturated hydrocarbon group; alicyclic carbon having 4 to 20 carbon atoms A hydrogen group; an aromatic hydrocarbon group having 6 to 20 carbon atoms; and a cyclic ether group having 4 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an isopropyl group, a phenoxyethyl group, a cyclohexyl group, an isobornyl group, and a phenyl group. Further, a benzyl group and a tetrahydrofurfuryl group are more preferable, and a methyl group and a cyclohexyl group are still more preferable.

  1,5-diene structure-containing monomer containing a hetero atom and 1,6-diene structure-containing monomer containing a hetero atom as a diene structure-containing monomer giving a ring structure-containing unit represented by the formula (I) At least one diene structure-containing monomer selected from the group consisting of can be used. Among the diene structure-containing monomers that give the ring structure-containing unit represented by the formula (I), preferred monomers include the formula (II):

(Wherein R ¹ , X, Y and Z are the same as above, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, a carboxyl group, an ester group or a cyano group)
The diene structure containing monomer represented by these is mentioned. Of the alkyl groups having 1 to 4 carbon atoms, a methyl group is preferable. Examples of the ester group include a group represented by the formula: —COOR ⁶ (wherein R ⁶ is the same as described above).

  Specific examples of the diene structure-containing monomer represented by the formula (II) include the formula (IIa):

(Wherein R ¹ is the same as above)
1,6-diene structure-containing monomer represented by the formula (IIb):

(Wherein R ¹ is the same as above)
1,6-diene structure-containing monomer represented by the formula (IIc):

(Wherein, R ¹ is the same as above, and each R ¹ may be the same or different)
1,6-diene structure-containing monomer represented by the formula (IId):

(Wherein R ¹ and R ⁷ are the same as above)
1,6-diene structure-containing monomer represented by the formula (IIe):

(Wherein R ¹ is the same as above)
1,6-diene structure-containing monomer represented by the formula (IIf):

(Wherein R ¹ and R ⁷ are the same as above)
1,6-diene structure-containing monomer represented by the formula (IIg):

(Wherein R ¹ is the same as above)
1,6-diene structure-containing monomer represented by the formula (IIh):

(Wherein R ¹ is the same as above)
1,5-diene structure-containing monomer represented by the formula (IIi):

(Wherein R ¹ is the same as above)
1,5-diene structure containing monomers represented by these. Among these, from the viewpoint of improving scratch resistance and adhesion to a substrate, a 1,6-diene structure-containing monomer represented by the formula (IIa) and a 1,6-diene represented by the formula (IIb) A structure-containing monomer and a 1,6-diene structure-containing monomer represented by the formula (IIc) are preferred, and a 1,6-diene structure-containing monomer represented by the formula (IIa) is more preferred. These monomers can be prepared, for example, by the method described in JP-A-10-226669.

  Examples of the 1,6-diene structure-containing monomer represented by the formula (IIa) include α-allyloxymethyl acrylic acid, α-allyloxymethyl acrylate methyl, α-allyloxymethyl ethyl acrylate, α- Propyl allyloxymethyl acrylate, isopropyl α-allyloxymethyl acrylate, butyl α-allyloxymethyl acrylate, tert-butyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, α-allyloxy Cyclohexyl methyl acrylate, α-allyloxymethyl acrylate dicyclopentadienyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl acrylate adamantyl, α-allyloxymethyl acrylate benzyl, α-allyloxymethyl Acrylic acid Although such allyloxymethylacrylate esters such as tigers tetrahydrofurfuryl and the like, and the present invention is not limited only to those exemplified. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of improving scratch resistance and adhesion to the substrate, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, isopropyl α-allyloxymethyl acrylate, α-allyl Preferred are phenoxyethyl oxymethyl acrylate, cyclohexyl α-allyloxymethyl acrylate, isobornyl α-allyloxymethyl acrylate, benzyl α-allyloxymethyl acrylate and α-allyloxymethyl acrylate tetrahydrofurfuryl, α-allyl More preferred are methyl oxymethyl acrylate and cyclohexyl α-allyloxymethyl acrylate. In addition, methyl α-allyloxymethyl acrylate is particularly preferable from the viewpoint of improving scratch resistance and adhesion to the substrate.

  Examples of the 1,6-diene structure-containing monomer represented by the formula (IIb) include, for example, α-methallyloxymethyl acrylic acid, α-methallyloxymethyl acrylate methyl, α-methallyloxymethyl acrylate ethyl , Α-methallyloxymethyl propyl acrylate, α-methallyloxymethyl acrylate isopropyl, α-methallyloxymethyl acrylate butyl, α-methallyloxymethyl acrylate tert-butyl, α-methallyloxymethyl acrylate Phenoxyethyl acid, cyclohexyl α-methallyloxymethyl acrylate, dicyclopentadienyl α-methallyloxymethyl acrylate, isobornyl α-methallyloxymethyl acrylate, adamantyl α-methallyloxymethyl acrylate, α- Benzyl methallyloxymethyl acrylate, α-me Although such methallyl oxymethyl acrylate esters such as Lil oxymethyl tetrahydrofurfuryl acrylate and the like, and the present invention is not limited only to those exemplified. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of improving scratch resistance and adhesion to the substrate, methyl α-methallyloxymethyl acrylate, ethyl α-methallyloxymethyl acrylate, isopropyl α-methallyloxymethyl acrylate, Phenoxyethyl α-methallyloxymethyl acrylate, cyclohexyl α-methallyloxymethyl acrylate, isobornyl α-methallyloxymethyl acrylate, and benzyl α-methallyloxymethyl acrylate and α-methallyloxymethyl acrylic acid Tetrahydrofurfuryl is preferable, and methyl α-methallyloxymethyl acrylate and cyclohexyl α-methallyloxymethyl acrylate are more preferable.

  Examples of the 1,6-diene structure-containing monomer represented by the formula (IIc) include bis (α-hydroxymethylacrylic acid) ether, bis (α-hydroxymethylacrylic acid methyl) ether, and bis (α-hydroxy). Methyl acrylate) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl butyl) ether, bis (α-hydroxymethyl acryl) Acid tert-butyl) ether, bis (α-hydroxymethyl acrylate phenoxyethyl) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl acrylate dicyclopentadienyl) ether, bis ( α-Hydroxymethyl Α-hydroxymethyl acryl such as isobornyl acrylate) ether, bis (α-hydroxymethyl acrylate adamantyl) ether, bis (α-hydroxymethyl acrylate benzyl) ether, bis (α-hydroxymethyl acrylate tetrahydrofurfuryl) ether Examples include ethers of acid monomers, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of improving scratch resistance and adhesion to a substrate, bis (α-hydroxymethyl methyl acrylate) ether, bis (α-hydroxymethyl ethyl acrylate) ether, bis (α-hydroxymethyl) Isopropyl acrylate) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl acrylate) ether, bis (α-hydroxymethyl acrylate) Acid benzyl) ether and bis (α-hydroxymethyl acrylate tetrahydrofurfuryl) ether are preferred, bis (α-hydroxymethyl acrylate methyl) ether and bis (α-hydroxymethyl acrylate cyclohexyl) ) Ether is preferred.

  The content of the diene structure-containing monomer in the monomer component is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15 from the viewpoint of improving scratch resistance and adhesion to the substrate. From the viewpoint of improving adhesion and blocking resistance, it is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, and further preferably 90% by mass or less.

  The monomer component may contain a monomer other than the diene structure-containing monomer. Examples of the monomer other than the diene structure-containing monomer include, for example, a monomer having a carboxyl group, an acidic phosphate ester monomer, a monomer having a group having an active hydrogen, and a (meth) acrylic ester. A monomer having an epoxy group, a monomer having a nitrogen atom, a monomer having two or more polymerizable double bonds, an aromatic monomer, a monomer having a halogen atom, a vinyl ester Monomers, vinyl ether monomers, and the like that do not have a ring structure containing a hetero atom can be mentioned, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the monomer having a carboxyl group include aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride, but the present invention is not limited to such examples. Absent. These monomers having a carboxyl group may be used alone or in combination of two or more.

  Examples of acidic phosphate ester monomers include 2-acryloyloxyethyl acid phosphate and 2-methacryloyloxyethyl acid phosphate, but the present invention is not limited to such examples. These acidic phosphate ester monomers may be used alone or in combination of two or more.

  Examples of the monomer having a group having active hydrogen include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. Examples include hydroxyl group-containing (meth) acrylic acid esters; α-hydroxymethyl acrylate esters such as methyl α-hydroxymethyl acrylate and ethyl α-hydroxymethyl acrylate, but the present invention is limited to such examples. It is not a thing. These monomers having a group having active hydrogen may be used alone or in combination of two or more.

  Examples of (meth) acrylic acid esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and n-acrylate. (Meth) acrylic acid alkyl esters such as butyl, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate; isobornyl acrylate, isobornyl methacrylate, Cycloalkyl (meth) acrylates such as cyclohexyl acrylate and cyclohexyl methacrylate; cyclohexylmethyl acrylate, cyclohexylmethyl methacrylate, cyclohexylethyl acrylate, (Meth) acrylic acid cycloalkylalkyl such as cyclohexylethyl tacrylate, cyclohexylpropyl acrylate, cyclohexylpropyl methacrylate, 4-methylcyclohexylmethyl acrylate, 4-methylcyclohexylmethyl methacrylate, and the like, It is not limited only to such illustration. These (meth) acrylic acid esters may be used alone or in combination of two or more.

  Examples of the monomer having an epoxy group include epoxy group-containing (meth) acrylic acid esters such as glycidyl acrylate and glycidyl methacrylate, but the present invention is not limited to such examples. . These monomers having an epoxy group may be used alone or in combination of two or more.

  Examples of the monomer having a nitrogen atom include (meth) acrylamide such as acrylamide and methacrylamide, N, N′-dimethylaminoethyl acrylate, N, N′-dimethylaminoethyl methacrylate, and N, N acrylic acid. N-vinyl compounds such as nitrogen-containing (meth) acrylic acid such as' -diethylaminoethyl, N, N'-diethylaminoethyl methacrylate, acrylic imide and methacrylic imide, and N-vinyl pyrrolidone, etc. The invention is not limited to such examples. These monomers having a nitrogen atom may be used alone or in combination of two or more.

  Examples of the monomer having two or more polymerizable double bonds include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, and tripropylene glycol. Examples include dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and divinylbenzene. However, the present invention is not limited to such examples. These monomers having two or more polymerizable double bonds may be used alone or in combination of two or more.

  Examples of the aromatic monomer include styrene compounds such as styrene and α-methylstyrene, but the present invention is not limited to such examples. These aromatic monomers may be used alone or in combination of two or more.

  Examples of the monomer having a halogen atom include vinyl chloride, but the present invention is not limited to such examples. Only one type of monomer having a halogen atom may be used, or two or more types may be used in combination.

  Examples of the vinyl ester monomer include vinyl acetate, but the present invention is not limited to such examples. Only one type of vinyl ester monomer may be used, or two or more types may be used in combination.

  Examples of vinyl ether monomers include butyl vinyl ether and cyclohexyl vinyl ether, but the present invention is not limited to such examples. These vinyl ether monomers may be used alone or in combination of two or more.

  Among the monomers other than diene structure-containing monomers, benzotriazole monomers, benzophenone monomers, triazine monomers, etc. are used from the viewpoint of improving scratch resistance and adhesion to a substrate. Monomer having UV-absorbing group; monomer having UV-stable group; homopolymer such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tert-butyl (meth) acrylate A monomer having a property of imparting weather resistance such as a (meth) acrylic acid ester having a high glass transition temperature (hereinafter referred to as a weather resistant monomer) is preferred. A monomer having an ultraviolet absorbing group can be easily obtained commercially, for example, as Otsuka Chemical Co., Ltd., trade name: RUVA93, Osaka Organic Chemical Industry Co., Ltd., trade name: BP-1A. Can do. Monomers having a UV-stable group can be easily obtained commercially, for example, as ADK STAB series such as ADK STAB LA-82 and ADK STAB LA-87 manufactured by ADEKA Corporation.

  The content of the weatherable monomer in the monomer component is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, particularly preferably from the viewpoint of improving weatherability. Is 5% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and still more preferably from the viewpoint of improving scratch resistance and adhesion to a substrate. It is 50 mass% or less.

  From the viewpoint of improving the adhesion to the substrate, the monomer component contains a hydroxyl group (meth) such as 2-hydroxyethyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, and α-hydroxymethyl acrylate ester. Hydroxyl group-containing monomers typified by acrylic acid esters; nitrogen atom-containing monomers typified by nitrogen atom-containing (meth) acrylic acid esters such as (meth) acrylic imides and morpholino (meth) acrylates; It is preferable to contain a cyclic ether group-containing (meth) acrylic acid ester such as tetrahydrofurfuryl acrylate. As caprolactone-modified hydroxy (meth) acrylate, for example, commercially available as Daicel Chemical Industries, Ltd., trade name: Plaxel FM1, Plaxel FM1D, Plaxel FM2D, Plaxel FM3, Plaxel FA1DM, Plaxel FA2D, etc. Can do.

  The content of monomers that improve adhesion such as hydroxyl group-containing monomers, nitrogen atom-containing monomers, and cyclic ether group-containing (meth) acrylates in the monomer component improves adhesion to the substrate. From the viewpoint of making it preferable, it is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 1% by mass or more, and from the viewpoint of improving hydrolysis resistance and insulation resistance, preferably 40% by mass. % Or less, more preferably 35% by mass or less.

  The monomer component preferably contains acrylic acid having a basic structure of bisarylfluorene from the viewpoint of improving hydrolysis resistance and insulation resistance. Acrylic acid having bisarylfluorene as a basic structure is commercially easily available as, for example, Osaka Gas Chemical Co., Ltd., trade names: Ogsol EA-0200, Ogsol EA-0200, Ogsol EA-0500, Ogsol EA-1000, etc. Can be obtained.

Further, cyclohexyl alkyl esters of (meth) acrylic acid, dicyclopentenyl (meth) acrylic acid, dicyclopentenyloxyethyl (meth) acrylic acid, dicyclopentanyl as disclosed in JP-A-2002-69130. (Meth) acrylic acid, tricyclo [5.2.1.0 ^2.6 ] dec-8-yl (meth) acrylic acid, terpene (meth) acrylic acid, and the like can also be used.

  When polymerizing the monomer component, a chain transfer agent may be used as necessary from the viewpoint of suppressing an increase in molecular weight distribution and gelation. Examples of the chain transfer agent include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and n-octyl 3-mercaptopropionate. , Methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto Mercaptocarboxylic esters such as propionate); alkyl such as ethyl mercaptan, tert-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane Llucaptans; mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; tris [(3- Mercaptoisocyanurates such as mercaptopropionyloxy) -ethyl] isocyanurate; disulfides such as 2-hydroxyethyl disulfide and tetraethylthiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; dimers such as α-methylstyrene dimer Alkyl halides such as carbon tetrabromide, and the like, but the present invention is not limited to such examples. These chain transfer agents may be used alone or in combination of two or more. Among these chain transfer agents, mercaptocarboxylic acids, mercaptocarboxylic acid esters, alkyl mercaptans are obtained because they are easily available, have excellent anti-crosslinking properties, and have a low degree of decrease in polymerization rate. Compounds having a mercapto group such as mercaptoalcohols, aromatic mercaptans and mercaptoisocyanurates are preferred.

  The amount of the chain transfer agent may be appropriately set according to the composition of the monomer component, the polymerization conditions such as the polymerization temperature, the molecular weight of the target polymer, etc., and is not particularly limited, but the weight average molecular weight is several thousand to When obtaining tens of thousands of polymers, the amount is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass per 100 parts by mass of the monomer component.

  By polymerizing the monomer component, a polymer having a ring structure containing a hetero atom in the main chain is obtained. The content of the ring structure-containing unit represented by the formula (I) in the polymer having a ring structure containing a hetero atom in the main chain is preferably 5% by mass from the viewpoint of improving scratch resistance and adhesion to a substrate. Above, more preferably 10% by mass or more, and further preferably 15% by mass or more. From the viewpoint of improving the scratch resistance and adhesion to the substrate, 100% by mass or less, preferably 99% by mass or less, more preferably It is 95 mass% or less, More preferably, it is 90 mass% or less.

  The content of the ring structure-containing unit represented by the formula (I) in the polymer having a ring structure containing a hetero atom in the main chain is used as a raw material for the polymer having a ring structure containing a hetero atom in the main chain. It is calculated | required as a content rate of the diene structure containing monomer which gives the ring structure containing unit represented by Formula (I) in a monomer component.

A polymer having a ring structure containing a hetero atom in the main chain is, for example,
(1) Before applying the monomer component containing the diene structure-containing monomer to the substrate, the monomer component is previously obtained by a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or the like. A method of polymerizing
(2) A monomer component containing a diene structure-containing monomer can be prepared by, for example, a method in which the monomer component is polymerized by heating or irradiation with active energy rays after being applied to the substrate. The present invention is not limited to such examples.

  The weight average molecular weight of the polymer having a ring structure containing a heteroatom in the main chain obtained by polymerizing the monomer component as described above varies depending on the type of the molded product, and therefore can be generally determined. However, from the viewpoint of improving the weather resistance, it is preferably 10,000 or more, more preferably 50,000 or more, and still more preferably 100,000 or more. The upper limit of the weight average molecular weight of the polymer having a ring structure containing a hetero atom in the main chain is not particularly limited, but is preferably 1 million or less, more preferably 500,000 or less, from the viewpoint of improving moldability. More preferably, it is 300,000 or less.

  In addition, in this specification, a weight average molecular weight means the weight average molecular weight (polystyrene conversion) measured using the gel permeation chromatography.

  Before applying the monomer component containing the (1) diene structure-containing monomer to the substrate, the above-described method is performed in advance by a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or the like. As an example of a method for polymerizing a monomer component, a case where the monomer component is polymerized by an emulsion polymerization method will be described.

  When preparing a polymer by polymerizing the monomer component by an emulsion polymerization method, the monomer component containing the diene structure-containing monomer is subjected to emulsion polymerization. When the monomer component is polymerized by emulsion polymerization, the embodiment for carrying out the emulsion polymerization is not particularly limited. Emulsion polymerization of the monomer component can be performed, for example, by appropriately adding a monomer component, an emulsifier and, if necessary, a polymerization initiator in an aqueous medium and polymerizing the monomer component.

  In the present specification, the aqueous medium means water or a mixed solvent of water and a hydrophilic organic solvent having a water content of 50% by mass or more. Examples of the hydrophilic organic solvent include monohydric alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and allyl alcohol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, and dipropyleneglycol. Polyhydric alcohols such as acetone, methyl ethyl ketone, ketones such as methyl propyl ketone, aliphatic organic acid alkyl esters such as methyl formate, ethyl formate, methyl acetate, methyl acetoacetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, Diethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol mono Chirueteru, although such polyhydric alkyl ethers of alcohols, such as dipropylene glycol monomethyl ether, the present invention is not limited those exemplified only. These hydrophilic organic solvents may be used alone or in combination of two or more. Of the aqueous media, water is preferred.

  Moreover, in order to adjust the molecular weight of the obtained polymer, a polymerization chain transfer agent may be used as a monomer component, or the polymer may be cross-linked in the obtained emulsion particles.

  When the monomer component is polymerized by heating, electron beam irradiation or the like, a polymerization initiator is not particularly required, but a polymerization initiator is preferably used from the viewpoint of promoting the polymerization reaction.

  Examples of the polymerization initiator include water-soluble polymerization initiators and oil-soluble polymerization initiators such as ammonium persulfate, potassium persulfate, hydrogen peroxide, and butyl hydroperoxide. However, the present invention is limited to such examples. Is not to be done. In order to promote emulsion polymerization, for example, sodium bisulfite, L-ascorbic acid or the like may be used as a reducing agent. These reducing agents may be used alone or in combination of two or more.

  When a polymerization initiator is used, the amount of the polymerization initiator per 100 parts by mass of the monomer component may be appropriately set according to the type of the polymerization initiator, but preferably 0.01 to 2 parts by mass, More preferably, it is 0.03-1 mass part.

  Examples of the emulsifier include an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, and a polymer emulsifier. These emulsifiers may be used alone or in combination of two or more.

  Examples of the anionic emulsifier include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; Examples include polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formaldehyde condensates; fatty acid salts such as ammonium laurate and sodium stearate. It is not limited to illustration only.

  Nonionic emulsifiers include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Although the condensation product with an amine etc. are mentioned, this invention is not limited only to this illustration.

  Examples of the cationic emulsifier include alkylammonium salts such as dodecylammonium chloride, but the present invention is not limited to such examples.

  Examples of amphoteric emulsifiers include betaine ester type emulsifiers, but the present invention is not limited to such examples.

  Examples of the polymer emulsifier include poly (meth) acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinylpyrrolidone; polyhydroxyalkyl (meth) acrylates such as polyhydroxyethyl (meth) acrylate; and polymers thereof. Although the copolymer etc. which use 1 or more types of the monomer to comprise as a copolymerization component are mentioned, this invention is not limited only to this illustration.

  Moreover, as an emulsifier, the emulsifier which has a polymeric group, ie, what is called a reactive emulsifier, from a viewpoint of improving the water resistance of a molded object is preferable, and a non-nonylphenyl type emulsifier is preferable from a viewpoint of environmental protection.

  As the reactive emulsifier, for example, propenyl-alkylsulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt [for example, manufactured by Sanyo Chemical Industries, Ltd., Trade name: Eleminool RS-30, etc.], polyoxyethylene alkylpropenyl phenyl ether sulfonate salt [for example, product name: Aqualon HS-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], allyloxymethylalkyloxypolyoxy Sulfonate salt of ethylene, sulfonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene (for example, product name: Aqualon KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), allyloxymethylnonylphenoxyethylhydroxypolyoxye Sulfonate salt of Ren (for example, ADEKA Co., Ltd., trade name: ADEKA rear soap SE-10, etc.), allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfate salt [for example, ADEKA Corporation, trade name: ADEKA Rear soap SR-10, ADEKA rear soap SR-30, etc.], bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salts (for example, Nippon Emulsifier Co., Ltd., trade name: Antox MS-60, etc.), Allyloxymethylalkoxyethylhydroxypolyoxyethylene [for example, manufactured by ADEKA Corporation, trade name: Adekaria soap ER-20, etc.], polyoxyethylene alkylpropenyl phenyl ether [for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., product Name: Aqualon RN-20, etc.) Examples include allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, trade name: ADEKA rear soap NE-10 manufactured by ADEKA Corporation] and the like, but the present invention is not limited only to such illustration. .

  In the emulsion polymerization, if necessary, a chelating agent such as sodium ethylenediaminetetraacetate, a dispersing agent such as sodium polyacrylate, or an inorganic salt may be used. Examples of the method for adding a monomer component, a polymerization initiator, and the like include a batch addition method, a continuous addition method, a multi-stage addition method, and the like, but the present invention is not limited to such examples. . These addition methods may be used alone or in combination of two or more.

  What is necessary is just to set the reaction conditions in the case of emulsion polymerization suitably according to the composition of a monomer component, the kind of polymerization initiator, etc. The polymerization temperature is preferably 5 to 90 ° C, more preferably 20 to 85 ° C. The polymerization time is preferably about 3 to 8 hours, for example. Further, when the monomer component is polymerized, it is preferable to stir the reaction system.

  A resin emulsion is obtained by emulsion polymerization of the monomer component as described above. After preparing the resin emulsion, it is preferable to neutralize the obtained resin emulsion with a neutralizing agent from the viewpoint of stabilizing the resin emulsion. Examples of the neutralizing agent include tertiary amines such as triethanolamine, dimethylethanolamine, diethylethanolamine and morpholine; aqueous ammonia; sodium hydroxide and the like, but the present invention is limited only to such examples. It is not a thing. These neutralizing agents may be used alone or in combination of two or more.

  The amount of the neutralizing agent is preferably 0.3 to 1.4 equivalents, more preferably 0.5 to 1.2 equivalents per equivalent of the acid groups of the emulsion particles. It is preferable to use it.

  The nonvolatile content in the resin emulsion is preferably 10% by mass or more, more preferably 20% by mass or more from the viewpoint of improving productivity, and preferably 65% by mass or less, more preferably from the viewpoint of improving handleability. 60% by mass or less.

In the present specification, the nonvolatile content in the resin emulsion is determined by weighing 1 g of the resin emulsion and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour.
[Non-volatile content in resin emulsion (mass%)]
= [[Mass of residue] ÷ [Resin emulsion 1 g]] × 100
Means the value obtained based on

  The resin emulsion prepared as described above can be used as a molding material having thermoplasticity. In addition, the resin emulsion contains, as necessary, for example, a polymer having no ring structure containing a heteroatom in the main chain and a diene structure-containing monomer, as long as the object of the present invention is not impaired. Other types of resin emulsions such as resin emulsions containing emulsion particles consisting of polymers other than polymers having a ring structure containing a heteroatom in the main chain, such as polymers obtained by polymerizing body components, water-soluble A functional polymer or the like may be contained.

  In addition, the said molding material is the said resin emulsion, the monomer which has a 2 or more polymerizable double bond, and the polymerization start if needed from a viewpoint of improving the hardness of the resin layer formed and improving scratch resistance. It is preferable to prepare by mixing the agent. Thus, when the monomer which has a 2 or more polymerizable double bond is used, the minimum film forming temperature of a resin layer can be adjusted easily.

  Examples of the monomer having two or more polymerizable double bonds include ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate. , 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, etc., alkyl diol di (meth) acrylate having 2 to 10 carbon atoms, pentaerythritol monohydroxytri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol (monohydroxy) penta (meth) acrylate, ethylene oxide modified 1,6-hex Diol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane triethoxytri (meth) acrylate, bisphenol A di (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate, ethoxylated glycerin tri (meth) acrylate, triallyl isocyanurate, propylene oxide modified glycerol tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di Polyalkylene glycols such as (meth) acrylate and polypropylene glycol di (meth) acrylate Polyfunctional (meth) acrylic acid esters such as aldehyde di (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate; butadiene, isoprene, chloroprene, Although divinylbenzene, diallyl phthalate, etc. are mentioned, this invention is not limited only to this illustration. These monomers having two or more polymerizable double bonds may be used alone or in combination of two or more. As the monomer having two or more polymerizable double bonds, it is preferable to select and use a monomer suitable for improving desired properties such as hardness and moldability of an optical molded body. Among these monomers having two or more polymerizable double bonds, a polyfunctional (meth) acrylic acid ester is preferable from the viewpoint of improving the weather resistance.

  In the range where the object of the present invention is not inhibited, the monomer having two or more polymerizable double bonds is a monomer other than the monomer having two or more polymerizable double bonds. It may be used together.

  The amount of the monomer having two or more polymerizable double bonds per 100 parts by mass of the nonvolatile content of the resin emulsion is preferably 5 parts by mass or more, more preferably from the viewpoint of improving the hardness of the optical molded body. From the viewpoint of improving moldability, it is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 150 parts by mass or less.

  Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination. Some photopolymerization initiators act as thermal polymerization initiators, and some thermal polymerization initiators act as photopolymerization initiators, so those having both properties can be irradiated or heated. Thus, the optical molded body can be cured.

  Examples of the thermal polymerization initiator include 2,2′-azobis- (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4′- Oil-soluble initiators such as dimethylvaleronitrile), benzoyl peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, tert-butylperoxy-2-ethylhexanoate, Persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate; water-soluble peroxides such as hydrogen peroxide; water-soluble azo compounds such as 2,2′-azobis (2-amidinopropane) dihydrochloride; Although mentioned, this invention is not limited only to this illustration. These thermal polymerization initiators may be used alone or in combination of two or more.

  Examples of the photopolymerization initiator include benzophenone, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oxyphenyl-acetic acid 2- [ 2-oxo-2-phenylacetoxyethoxy] -ethyl ester, oxyphenylacetic acid 2- [2-hydroxyethoxy] -ethyl ester, 1-hydroxycyclohexyl phenyl ketone, bis (2,4,6-trimethylbenzoyl) phenyl Phosphine oxide, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [ 4- (Methylthio) phenyl] -2-morpholinopropan-1-one Examples include 2-morpholinopropan-1-one, (4-methylphenyl [4- (2-methylpropyl) phenyl])-hexafluorophosphate, diethylthioxanthone, isopropylthioxanthone, and the like. It is not limited to only. These photopolymerization initiators may be used alone or in combination of two or more.

  For example, the polymerization initiator may be added directly to the resin emulsion, or may be used by mixing with the monomer having two or more polymerizable double bonds.

  When a monomer having two or more polymerizable double bonds is used in the molding material, the minimum film-forming temperature of the molding material is a monomer having the two or more polymerizable double bonds. Can be made lower than the minimum film-forming temperature of a molding material in which no is used. Since the minimum film forming temperature of the molding material is usually 0 to 60 ° C., the molding material is excellent in moldability. The minimum film-forming temperature of the molding material can be easily adjusted by adjusting the type and amount of the monomer having two or more polymerizable double bonds.

  The minimum film-forming temperature of the molding material means the boundary temperature between the film-forming part and the non-film-forming part when the molding material is applied in a strip shape on a flat plate having an appropriate temperature gradient. Is defined as the "minimum temperature at which no uniform coating (resin layer) is formed". The minimum film-forming temperature of the molding material can be measured according to JIS K6828-2 (2003), for example. More specifically, using a MFT tester (manufactured by Tester Sangyo Co., Ltd., product number: TP-801 LT), a coating film (resin layer) made of a molding material having a thickness of 250 μm on a stainless steel grooveless flat plate. ) With an applicator, and the minimum temperature (° C.) when a uniform coating film (resin layer) without cracks is formed is measured. The presence or absence of cracks in the coating film (resin layer) can be determined visually according to JIS K6828-2. In addition, when the minimum film forming temperature of a molding material is 0 degreeC or less, the minimum film forming temperature of the said molding material is considered to be 0 degreeC.

  The minimum film-forming temperature of the molding material is preferably 15 ° C. or more lower than the molding temperature at the time of producing an optical molded body using the molding material, from the viewpoint of improving moldability. The molding temperature is, for example, when a pattern is formed by a nanoimprint method using a molding material, the molding material is applied to a base material, and the surface of the formed coating film (resin layer) has a predetermined uneven structure. This is the temperature at which the mold is pressed.

  The molding material obtained as described above may contain other components other than the polymer having a ring structure containing a hetero atom in the main chain within the range in which the object of the present invention is not inhibited. Examples of the other component include polymers such as a polymer not having a ring structure containing a hetero atom in the main chain, and a polymer obtained by polymerizing a monomer component not containing a diene structure-containing monomer. , Thickeners; antifoaming agents; leveling agents; surface conditioners; stabilizers such as light-resistant stabilizers, weather-resistant stabilizers and heat stabilizers; inorganics such as glass fibers, carbon fibers and silica Reinforcing materials such as fine particles; UV absorbers; Near infrared absorbers; Flame retardants; Antistatic agents; Colorants such as inorganic pigments, organic pigments and dyes; Fillers such as organic fillers and inorganic fillers; Pigment dispersions Although additives, such as an agent and an anti-settling agent, are mentioned, this invention is not limited only to this illustration. These additives may be used alone or in combination of two or more.

  The content of the volatile organic compound in the molding material is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of reducing the environmental load. The nonvolatile content in the molding material is preferably 10% by mass or more, more preferably 20% by mass or more from the viewpoint of improving productivity, and preferably 80% by mass or less from the viewpoint of improving moldability. Preferably it is 70 mass% or less. The non-volatile content in the molding material can be easily adjusted by adjusting the amount of solvent, the amount of additives, and the like.

The amount of non-volatile content in the molding material is obtained by weighing 1 g of the molding material and drying it with a hot air dryer at a temperature of 110 ° C. for 1 hour.
[Non-volatile content (% by mass) in molding materials]
= [[Residue mass] ÷ [molding material 1 g]] × 100
Means the value obtained based on

  Hereinafter, the embodiment of the method for producing an optical molded body of the present invention will be described in more detail with reference to FIG. 1, but the present invention is not limited to the embodiment shown in FIG. 1. .

  FIG. 1 is a schematic explanatory view showing one embodiment of a method for producing an optical molded body of the present invention. According to the embodiment shown in FIG. 1, the resin layer 1 made of the molding material is formed on the surface of the substrate 2 by applying the molding material to the substrate 2, and then the resin layer 1 is cured. Before, the mold 3 is pressed into the resin layer 1 to give the resin layer 1 a predetermined shape, and the resin layer 1 is cured in a state where the mold 3 is pressed or after the mold 3 is removed. Thus, an optical molded body in which the resin layer 1 having a predetermined shape is formed on the substrate 2 can be manufactured.

  In addition, as a material which comprises the base material 2, acrylic resin, such as a glass plate; polymethyl (meth) acrylate and the (meth) acrylic-type polymer which has a ring structure in a principal chain; Polyethylene terephthalate, polybutylene terephthalate, etc., for example Polyesters; Cyclic olefin polymers such as norbornene polymers; Cellulose polymers such as cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate; Polyolefin resins such as polyethylene and polypropylene; Polycarbonates; Polystyrene; Vinyl chloride resins ; ABS resin; AS resin; polyamide and the like are mentioned, but the present invention is not limited to such examples.

  Since the base material 2 is excellent in moldability, a film-like base material is preferably used. Examples of the film-like substrate include a transparent and heat-resistant film-like substrate (hereinafter referred to as a transparent heat-resistant film-like substrate). Examples of the transparent heat-resistant film-like substrate include a film-like substrate containing a polymer having a ring structure in the main chain, but the present invention is not limited to such illustration.

  Examples of the polymer having a ring structure in the main chain include, for example, a (meth) acrylic polymer having a ring structure in the main chain; a cyclic olefin polymer such as a norbornene polymer; cellulose triacetate, cellulose acetate propionate Cellulose polymers such as cellulose acetate butyrate may be mentioned, but the present invention is not limited to such examples. Among these polymers having a ring structure in the main chain, the light chain has a high light transmittance, a low refractive index, and is excellent in transparency, wavelength dependence, optical properties, and processability. (Meth) acrylic polymers having

  The (meth) acrylic polymer having a ring structure in the main chain has a structural unit derived from the ring structure and (meth) acrylic acid ester in the main chain. The ring structure of the (meth) acrylic polymer having a ring structure in the main chain has at least one selected from the group consisting of an ester group, an imide group and an acid anhydride from the viewpoint of improving its heat resistance. Is preferred. Suitable ring structures include, for example, lactone ring structures: ring structures derived from N-alkyl substituted maleimides, cyclic imide structures such as glutarimide rings; ring structures derived from maleic anhydride, rings derived from glutaric anhydride Examples of the structure include cyclic acid anhydride structures, but the present invention is not limited to such examples.

  Among (meth) acrylic polymers having a ring structure in the main chain, by giving positive intrinsic birefringence, the positive birefringence and the structure derived from the (meth) acrylate monomer By canceling out the negative birefringence, the (meth) acrylic polymer having a lactone ring structure in the main chain has a low birefringence even when the film-like substrate is stretched. At least one selected from the group consisting of a (meth) acrylic polymer having a glutarimide ring structure in the chain and a (meth) acrylic polymer having a glutaric anhydride structure in the main chain is preferred, and the wavelength dependency is small Therefore, a (meth) acrylic polymer having a lactone ring structure in the main chain is more preferable.

  The lactone ring structure may have a 4- to 8-membered ring. Since the lactone ring structure is excellent in the stability of the ring structure, it preferably has a 5- to 6-membered ring, more preferably a 6-membered ring. Among lactone ring structures, (meth) acrylic polymers with a high content of lactone ring structures can be easily prepared and have excellent copolymerizability with (meth) acrylic acid esters such as methyl methacrylate. From the formula (III):

(In the formula, R ⁹ , R ¹⁰ and R ¹¹ each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms which may have an oxygen atom)
The ring structure represented by is preferable. Examples of the organic group having 1 to 20 carbon atoms which may have an oxygen atom include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group; an ethenyl group and a propenyl group. An unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; the alkyl group, the unsaturated aliphatic hydrocarbon group, and the aromatic A group in which at least one hydrogen atom of the aromatic hydrocarbon group is substituted with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an ether group, and an ester group. It is not limited to illustration only.

  The (meth) acrylic polymer having a ring structure in the main chain can be obtained, for example, by polymerizing a monomer component having a ring structure and a (meth) acrylic acid ester.

  Examples of the monomer having a ring structure include N-substituted maleimides such as cyclohexylmaleimide, methylmaleimide, phenylmaleimide, and benzylmaleimide, and maleic anhydride, but the present invention is limited only to such examples. It is not a thing. These monomers having a ring structure may be used alone or in combination of two or more.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and tert- (meth) acrylic acid. (Meth) acrylic acid (cyclo) alkyl ester having 1 to 10 carbon atoms in the ester moiety such as butyl, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate; ester moiety such as benzyl (meth) acrylate Aralkyl (meth) acrylate having 7 to 20 carbon atoms; chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxy (meth) acrylate Propyl, (meth) acrylic acid 2,3,4,5,6-pentahydroxyhexyl, (meth) acrylic acid 2 (Meth) acrylic acid (cyclo) alkyl ester having a carbon atom number of 1 to 10 in the ester part such as 3,4,5-tetrahydroxypentyl and having a halogen atom or a hydroxyl group in the ester part may be mentioned. The invention is not limited to such examples. These (meth) acrylic acid esters may be used alone or in combination of two or more. Among these (meth) acrylic acid esters, methyl (meth) acrylate is preferable from the viewpoint of improving the optical properties and thermal stability of the film-like substrate.

  The monomer component may contain a monomer having a ring structure and another monomer other than the (meth) acrylic acid ester.

  Examples of the other monomers include styrene monomers such as styrene, vinyl toluene, α-methyl styrene, α-hydroxymethyl styrene, and α-hydroxyethyl styrene; nitrile monomers such as (meth) acrylonitrile; ethylene, Olefin-based monomers such as propylene and 4-methyl-1-pentene; oxygen atom-containing vinyl compounds such as vinyl acetate, 2-hydroxymethyl-1-butene and methyl vinyl ketone; nitrogen such as N-vinylpyrrolidone and N-vinylcarbazole Although an atom containing vinyl compound etc. are mentioned, this invention is not limited only to this illustration. These other monomers may be used alone or in combination of two or more.

  The (meth) acrylic polymer having a ring structure in the main chain is prepared by, for example, preparing a (meth) acrylic polymer and then subjecting the (meth) acrylic polymer to a cyclization reaction. It can also be prepared by introducing a ring structure derived from a lactone ring structure, glutaric anhydride structure, glutarimide structure, N-substituted maleimide and the like. In this case, the monomer component used as a raw material for the (meth) acrylic polymer having a ring structure in the main chain preferably contains a hydroxyl group-containing monomer or a carboxyl group-containing monomer. Both the hydroxyl group-containing monomer and the carboxyl group-containing monomer are changed to a ring structure by a cyclization reaction. The acrylic polymer having a ring structure in the main chain may contain a hydroxyl group derived from a hydroxyl group-containing monomer or a carboxyl group derived from a carboxyl group-containing monomer.

  Examples of the hydroxyl group-containing monomer include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, and butyl 2- (hydroxymethyl) acrylate. 2- (hydroxymethyl) acrylic acid (cyclo) alkyl ester having 1 to 10 carbon atoms in the ester portion; 2- (hydroxy) having 1 to 10 carbon atoms in the ester portion such as methyl 2- (hydroxyethyl) acrylate (Ethyl) acrylic acid (cyclo) alkyl ester; allyl alcohol, methallyl alcohol and the like can be mentioned, but the present invention is not limited to such examples. These hydroxyl group-containing monomers may be used alone or in combination of two or more.

  Examples of the carboxyl group-containing monomer include (meth) acrylic acid, crotonic acid, 2- (hydroxymethyl) acrylic acid, 2- (hydroxyethyl) acrylic acid, and the present invention is only such examples. It is not limited to. These carboxyl group-containing monomers may be used alone or in combination of two or more.

  The content of the ring structure in the (meth) acrylic polymer having a ring structure in the main chain is preferably 5% from the viewpoint of improving the heat resistance of the film-like substrate and improving the solvent resistance and surface hardness. % Or more, more preferably 10% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass from the viewpoint of improving the moldability and handleability of the film-like substrate. Hereinafter, it is still more preferably 50% by mass or less. The content of the structural unit derived from the (meth) acrylic acid ester in the (meth) acrylic polymer having a ring structure in the main chain is preferably 10 from the viewpoint of improving the moldability and handleability of the film-like substrate. % By mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, still more preferably 50% by mass or more, and still more preferably 70% by mass or more, improving the heat resistance of the film-like substrate. From the viewpoint of improving solvent resistance and surface hardness, it is preferably 95% by mass or less, more preferably 90% by mass or less.

  Moreover, the total content of the structural unit derived from the cyclic structure and the (meth) acrylic acid ester in the (meth) acrylic polymer having a cyclic structure in the main chain improves the optical properties and surface hardness of the film-like substrate. From the viewpoint, it is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and still more preferably 90% by mass or more.

  Examples of the (meth) acrylic polymer having a lactone ring structure in the main chain include, for example, JP 2000-230016, JP 2001-151814, JP 2002-120326, and JP 2002-254544. Examples include (meth) acrylic polymers having a lactone ring structure described in JP-A-2005-146084 and the like, but the present invention is not limited to such examples. These (meth) acrylic polymers having a lactone ring structure in the main chain may be used alone or in combination of two or more.

  Examples of the (meth) acrylic polymer having a glutarimide structure in the main chain include, for example, JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328329, and JP-A-2006-328334. JP, 2006-337491, JP 2006-337492, JP 2006-337493, JP 2006-337569, JP 2007-009182, etc. Although (meth) acrylic polymer etc. are mentioned, this invention is not limited only to this illustration. These (meth) acrylic polymers having a glutarimide structure in the main chain may be used alone or in combination of two or more.

  Examples of the (meth) acrylic polymer having a glutaric anhydride structure in the main chain include, for example, glutars described in JP-A-2006-283013, JP-A-2006-335902, JP-A-2006-274118, and the like. Examples include (meth) acrylic polymers having an acid anhydride structure, but the present invention is not limited to such examples. These (meth) acrylic polymers having a glutaric anhydride structure in the main chain may be used alone or in combination of two or more.

  The (meth) acrylic polymer having a ring structure in the main chain preferably has thermoplasticity. The glass transition temperature (Tg) of the (meth) acrylic polymer having a ring structure in the main chain is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, further preferably 115 ° C. or higher, and still more preferably 120 ° C. or higher. It is. The upper limit of the glass transition temperature (Tg) of the (meth) acrylic polymer having a ring structure in the main chain is not particularly limited, but is preferably 200 from the viewpoint of improving the moldability of the film-like substrate. C. or lower, more preferably 180.degree. C. or lower.

  The (meth) acrylic polymer having a ring structure in the main chain can be used in combination with other thermoplastic polymers. Examples of other thermoplastic polymers include olefin polymers such as polyethylene, polypropylene, ethylene-propylene copolymer, poly (4-methyl-1-pentene); vinyl chloride, vinylidene chloride, chlorinated vinyl resins, and the like. (Meth) acrylic polymer such as poly (meth) methyl acrylate; polystyrene, styrene-methyl (meth) acrylate copolymer, styrene-acrylonitrile copolymer, acrylonitrile-butadiene- Styrenic polymers such as styrene block copolymers; Polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyamides such as nylon 6, nylon 66, and nylon 610; Polyacetals; Polycarbonates; Polyphenyle Polyolefin sulfide; Polyetheretherketone; Polysulfone; Polyethersulfone; Polyoxybenzylene; Polyamideimide; Rubber materials such as ABS resin, MBS resin, ASA resin and the like containing rubber components such as polybutadiene rubber and acrylic rubber Although a polymer etc. are mentioned, this invention is not limited only to this illustration. These other thermoplastic polymers may be used alone or in combination of two or more.

  Among the other thermoplastic polymers, from the viewpoint of producing a film-like substrate having a low retardation by negating the positive retardation of the acrylic polymer having a ring structure in the main chain with a negative retardation. A styrene polymer is preferable, and a styrene-acrylonitrile copolymer is more preferable from the viewpoint of improving the compatibility with a (meth) acrylic polymer. Further, from the viewpoint of imparting both low retardation and flexibility to the film-like substrate, rubber polymers such as ABS resin, MBS resin, ASA resin and the like containing rubber components such as polybutadiene rubber and acrylic rubber are used. preferable.

  The amount of the other thermoplastic polymer per 100 parts by mass of the (meth) acrylic polymer having a ring structure in the main chain is not particularly limited, but is usually preferably 0 to 50 parts by mass, more preferably 0 to 0 parts by mass. 40 parts by mass, more preferably 0 to 30 parts by mass, still more preferably 0 to 20 parts by mass.

  The (meth) acrylic polymer having a ring structure in the main chain may contain an additive. Additives include, for example, antioxidants; stabilizers such as light resistance stabilizers, weather resistance stabilizers and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; ultraviolet absorbers; near infrared absorption Agents; Flame retardants; Antistatic agents such as anionic surfactants, cationic surfactants and nonionic surfactants; Colorants such as inorganic pigments, organic pigments and dyes; Fillers such as organic fillers and inorganic fillers An anti-blocking agent, a resin modifier, a plasticizer, a lubricant, a retardation reducing agent, and the like, but the present invention is not limited to such examples. These additives may be used alone or in combination of two or more. Among these additives, an ultraviolet absorber is preferable.

  Examples of the ultraviolet absorber include benzophenone-based compounds such as 2-hydroxybenzophenone; salicylate compounds such as phenyl silicate; benzoate compounds; triazole compounds such as (2,2′-hydroxy-5-methylphenyl) benzotriazole; 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-octyloxy-2-hydroxypropyloxy) -5-α-cumylphenyl] -s-triazine compound, 2, 4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-nonyloxy-2-hydroxypropyloxy) -5-α-cumylphenyl] -s-triazine compound, 2,4-bis (2,4-Dimethylphenyl) -6- [2-hydroxy-4- (3-decyloxy- 2-hydroxypropyloxy) -5-α-cumylphenyl] -s-triazine compounds, triazine compounds such as 2,4,6-tris (hydroxyphenyl) -1,3,5-triazine compounds, and the like. The invention is not limited to such examples. These ultraviolet absorbers may be used alone or in combination of two or more. Among these ultraviolet absorbers, triazine compounds and triazole compounds are preferable because they are excellent in compatibility with amorphous thermoplastic resins such as acrylic resins and have excellent ultraviolet absorption characteristics.

  Although the content rate of the ultraviolet absorber in a film-form base material is not specifically limited, From a viewpoint of improving the weather resistance of a film-form base material, Preferably it is 0.1 mass% or more, More preferably, it is 0.7 mass% or more, More preferably, it is 1% by mass or more, and from the viewpoint of improving the mechanical strength and yellowing resistance of the film-like substrate, it is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 2% by mass or less. It is.

  The amount of the additive per 100 parts by mass of the (meth) acrylic polymer having a ring structure in the main chain is not particularly limited, but is preferably 0 to 5 parts by mass, more preferably 0 to 2 parts by mass, and still more preferably. 0 to 0.5 parts by mass.

  Examples of (meth) acrylic polymers having a cyclic structure in the main chain, additives, etc. include mixers such as omni mixers, extruders such as single screw extruders and twin screw extruders, and mixers such as pressure kneaders. Can be mixed.

  Examples of methods for producing a film-like substrate include solution casting methods such as solution casting and solution casting; melt casting methods such as melt extrusion and extrusion; calendering; press molding and the like Although mentioned, this invention is not limited only to this illustration. Among these methods, the solution film forming method and the melt film forming method are preferable because of the excellent productivity of the film-like substrate.

  The film-like substrate may be stretched. The film-like substrate may be stretched by uniaxial stretching or biaxial stretching. Uniaxial stretching may be longitudinal stretching (stretching in the winding direction of the film-shaped substrate) or transverse stretching (stretching in the width direction of the film-shaped substrate). In the case of longitudinal stretching, it may be free end uniaxial stretching in which the change in the width direction of the film-like substrate is free, or may be fixed end uniaxial stretching in which the change in the width direction of the film-like substrate is fixed. . Biaxial stretching may be sequential biaxial stretching in which transverse stretching is performed after longitudinal stretching, or simultaneous biaxial stretching in which longitudinal and transverse stretching are simultaneously performed. Moreover, you may perform the extending | stretching of the diagonal direction with respect to the extending | stretching of the thickness direction of a film-form base material, or the roll of a film-form base material. The stretching method, stretching temperature, and stretching ratio can be appropriately selected according to the optical properties, mechanical strength, etc. of the target film-like substrate.

  A film-like base material is obtained as described above. From the viewpoint of increasing the film strength, the thickness of the film-like substrate is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 15 μm or more, and even more preferably 20 μm or more, from the viewpoint of thinning the resin layer. The thickness is preferably 350 μm or less, more preferably 250 μm or less, still more preferably 200 μm or less, still more preferably 150 μm or less, and particularly preferably 100 μm or less.

  The glass transition temperature of the resin used for the film-shaped substrate is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, more preferably 115 ° C. or higher, and still more from the viewpoint of improving the film-forming accuracy of the film-shaped substrate. Preferably it is 120 degreeC or more. The upper limit of the glass transition temperature of the resin is not particularly limited, but is preferably 200 ° C. or less, more preferably 180 ° C. or less, and still more preferably 170 ° C. from the viewpoint of improving the film-forming property of the film-like substrate. Hereinafter, it is 160 degrees C or less still more preferably.

  From the viewpoint of improving transparency, the total light transmittance of the film-like substrate measured in accordance with JIS K7361-1 (1997) is preferably 85% or more, more preferably 90% or more, and further preferably. Is 92% or more.

  It is preferable that the film-like substrate has ultraviolet absorptivity. The light transmittance of the film-like substrate at a wavelength of 380 nm is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less, from the viewpoint of preventing deterioration due to ultraviolet rays. In addition, the said light transmittance is a value when it measures according to prescription | regulation of JISK7361 (1997).

  The film-like substrate preferably has visible light permeability. From the viewpoint of improving optical properties, the light transmittance of the film-like substrate at a wavelength of 500 nm is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. In addition, the said light transmittance is a value when measured according to the prescription | regulation of JISK7361 (1997) similarly to the above.

  The haze value of the film-like substrate is preferably 3% or less, more preferably, when the film-like substrate is used for optical purposes, because the film-like substrate is desirably excellent in light transmittance. Is 1% or less, more preferably 0.5% or less. In addition, the haze value of a film-form base material is a value when it measures by the method as described in the Example mentioned later.

  Further, from the viewpoint of reducing the coloration of the film-like substrate, the b value at a thickness of 250 μm is preferably 0.5 or less, more preferably 0.3 or less. In addition, b value of a film-form base material is a value when it measures by the method as described in the Example mentioned later.

Film-like base materials include foreign substances contained in raw materials, foreign matters mixed in the production of film-like base materials, bubbles generated during molding, die lines and scratches by molding machines such as dies and rolls during molding, etc. Appearance defects may occur. It is preferable that there are few defects in appearance of such a film-like substrate. More specifically, the defect of the film-shaped substrate having a diameter of 20 μm or more is preferably 1000 pieces / m ² or less, more preferably 500 pieces / m ² or less, still more preferably 200 pieces / m ² or less, particularly preferably. Is 0 / m ² . Defects in appearance such as scratches in the film-like substrate can be reduced by filtering raw materials, cleaning at the manufacturing site, optimizing molding conditions, and the like.

  The film-like substrate is preferably excellent in heat resistance. In this specification, “heat resistance” means that the glass transition temperature (Tg) of the film-like substrate required in accordance with the provisions of JIS K7121 is 100 ° C. or higher. When the glass transition temperature of the film-like substrate is high, the temperature at the time of molding using a molding die can be increased, so the difference between the minimum film-forming temperature and the molding temperature of the optical molded body is increased. Therefore, the moldability of the optical molded body can be improved. Therefore, by increasing the glass transition temperature of the film-like substrate, it is possible to shorten the molding time when producing an optical molded body, and the pressure during molding can be reduced. Increases body productivity.

  The glass transition temperature of the film-like substrate is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 115 ° C. or higher, and still more preferably 120 ° C. or higher. Moreover, the upper limit of the glass transition temperature of a film-form base material is although it does not specifically limit, From a film forming viewpoint of a film-form base material, Preferably it is 200 degrees C or less, More preferably, it is 180 degrees C or less.

  A functional coating layer may be formed on the surface of the film-like substrate as necessary. Examples of the functional coating layer include an antistatic layer, an adhesive layer, an adhesive layer, an easy-adhesion layer, an easy-slip layer, a peelability-imparting layer, an antiglare layer (non-glare) layer, a photocatalyst layer and the like, Examples thereof include an antireflection layer, a hard coat layer, an ultraviolet ray shielding layer, a heat ray shielding layer, an electromagnetic wave shielding layer, and a gas barrier layer, but the present invention is not limited to such examples. The functional coating layer may be formed before the film-like substrate is stretched, or may be formed after the film-like substrate is stretched. Moreover, you may form a functional coating layer in any surface of the incident light surface and light-emitting surface of a film-form base material. Furthermore, the same type of functional coating layer may be formed on both surfaces of the film-like substrate, or different types of functional coating layers may be formed. The functional coating layer may have a single layer structure, or may have a multilayer structure in which functional coating layers of the same type or different types are laminated.

  The resin layer may be, for example, a spray, a roller, a brush, a trowel, or a roll coat, bar coat, die coat, comma coat, gravure coat, kiss coat, spin coat, dip coat, curtain coat, doctor blade coat, knife coat It can be easily formed by applying a molding material to a substrate by a method such as air knife coating, die coating, micro gravure coating, offset gravure coating, or lip coating. The formed resin layer may not be cured or may be cured as necessary.

  The optical molded body of the present invention can be produced by using the molding material, for example, by a stamping molding method, an in-mold molding method, a photolithographic method, a hot embossing method, a nanoimprint molding method, or a transfer method.

  For example, when the molding material is produced by a stamping molding method, the molding material is spray coat, roller coat, brush coat, iron coat, roll coat, bar coat, die coat, comma coat, gravure coat, kiss coat, spin coat, dip coat, curtain. A resin layer is formed by applying to a substrate by a method such as coating, doctor blade coating, knife coating, air knife coating, die coating, micro gravure coating, offset gravure coating, lip coating, etc., and a predetermined shape is formed on the formed resin layer After the resin layer is pressed with a mold so as to be imparted, an optical molded body having a predetermined shape can be produced by curing the resin layer.

  When producing a molded article for optics using the molding material by the nanoimprint method, for example, molding a resin layer made of the molding material on a film-like substrate, and forming the resin layer on the surface with a concavo-convex structure After pressing the mold, it can be produced by curing the resin layer in which the concavo-convex structure corresponding to the concavo-convex structure is formed. Examples of the nanoimprint method include the following methods, but the present invention is not limited to such examples.

(1) In the case of using a molding material that is cured by irradiation with active energy rays such as an electron beam and ultraviolet rays as the molding material of the present invention, for example, the molding material is applied to a base material and applied to the formed resin layer. A mold having a predetermined concavo-convex structure is pressed at room temperature or in a heated state, and in that state or after the mold is removed, the resin layer is irradiated with active energy rays to cure the resin layer, thereby forming a predetermined shape. Examples thereof include a method for producing an optical molded body having the same. In the method, at least one of the base material and the molding die is made of a material that transmits active energy rays, and the resin layer is irradiated with the active energy rays through the base material and / or the molding die. It can be cured.

(2) When a molding material that is cured by heating is used as the molding material, for example, the molding material is applied to a base material, and a molding die having a predetermined concavo-convex structure is formed at room temperature or heated. For example, a method for producing an optical molded body having a predetermined shape by heating the resin layer and curing the resin layer after pressing in the state, or after removing the mold.

(3) When a thermoplastic molding material is used as the molding material, for example, the molding material is applied to a base material, the formed resin layer is heated and softened, and a predetermined unevenness is formed on the softened resin layer. Examples include a method of manufacturing an optical molded body having a predetermined shape by pressing a mold having a structure and in that state or after removing the mold, cooling the resin layer and curing the resin layer.

(4) When a resin film made of a thermoplastic molding material is used as the molding material, for example, the resin film is placed on a base material as a resin layer, and the resin film is heated and softened to soften the resin. A method for producing an optical molded body having a predetermined shape by pressing a molding die having a predetermined concavo-convex structure on the film and in that state or after removing the molding die, cooling the resin film and curing the resin film Etc. Examples of the method for producing a resin film include solution casting methods such as a solution casting method and a solution casting method; melt film forming methods such as a melt extrusion method and an extrusion molding method; calendar methods; a press molding method and the like. However, the present invention is not limited to such examples. Among these methods, the solution film forming method and the melt film forming method are preferable because of the excellent productivity of the resin film. The resin film may be stretched. The stretching of the resin film may be uniaxial stretching or biaxial stretching. Uniaxial stretching may be longitudinal stretching (stretching in the winding direction of the resin film) or transverse stretching (stretching in the width direction of the resin film). In the case of longitudinal stretching, it may be free end uniaxial stretching in which the change in the width direction of the resin film is free, or may be fixed end uniaxial stretching in which the change in the width direction of the resin film is fixed. Biaxial stretching may be sequential biaxial stretching in which transverse stretching is performed after longitudinal stretching, or simultaneous biaxial stretching in which longitudinal and transverse stretching are simultaneously performed. Moreover, you may perform the extending | stretching of the diagonal direction with respect to the extending | stretching of the thickness direction of a resin film, or the roll of a resin film. The stretching method, stretching temperature, and stretching ratio are preferably selected as appropriate according to the optical properties, mechanical strength, and the like of the target resin film. The thickness of the resin film is preferably 1 μm or more, more preferably 2 μm or more, further preferably 5 μm or more, and even more preferably 10 μm or more from the viewpoint of increasing the film strength, and from the viewpoint of reducing the thickness of the resin film, Is not more than 350 μm, more preferably not more than 250 μm, still more preferably not more than 200 μm, still more preferably not more than 150 μm, particularly preferably not more than 100 μm.

  In addition, examples of the shape of the concavo-convex structure formed in the mold include a fine pattern having a pitch width of 10 μm or less, but the present invention is not limited only to such illustration.

  When the molding material is cured by irradiation with ultraviolet rays, a light source mainly having a wavelength region of 1900 to 3800 angstroms is used depending on the type of light source that generates ultraviolet rays and the distance between the light source and the molding material. The molding material can be cured by irradiating the molding material with ultraviolet rays for about 2 seconds to several minutes.

  When the molding material is cured by irradiation with an electron beam, the molding material can be cured by irradiating the molding material with an electron beam so that the absorption line is about 1 to 20 Mrad at an acceleration voltage suitable for the molding material. it can. The electron beam irradiation may be performed in the air, but is preferably performed in an inert gas such as nitrogen gas.

  When the molding material is cured by irradiating the molding material with ultraviolet rays or electron beams, the molding material has an advantage that it hardly receives a thermal history. In addition, after irradiating a molding material with an ultraviolet-ray or an electron beam, hardening may be accelerated | stimulated by heating within the range which does not inhibit the objective of this invention as needed.

  When the molding material is cured by heating, by heating the molding material for about 0.5 to 60 minutes, preferably about 5 to 20 minutes in a dryer having an in-machine temperature of 50 to 200 ° C, preferably 100 to 180 ° C, The molding material can be cured. Examples of the dryer include a jet oven and a hot air dryer, but the present invention is not limited to such examples. In addition, when heating a molding material, you may preheat as needed.

  Hereinafter, an embodiment of an optical molded body in which a resin layer is formed on a film-like substrate as a substrate will be described with reference to the drawings.

  FIG. 2 is a schematic sectional view showing an embodiment of the optical molded body of the present invention. In FIG. 2, the resin layer 1 having an uneven structure is formed on one surface of a base material 2. In the embodiment shown in FIG. 2, the resin layer 1 is formed only on one surface of the base material 2, but may be formed on both surfaces of the base material 2.

  In the concavo-convex structure provided on the surface of the resin layer, the average height of the convex portions and the average depth of the concave portions are each preferably 100 nm or more, more preferably 200 nm or more, and further preferably from the viewpoint of expressing desired optical characteristics. Is not less than 250 nm, more preferably not less than 280 nm, and from the viewpoint of easily forming a concavo-convex structure, it is preferably not more than 1000 nm, more preferably not more than 600 nm, still more preferably not more than 500 nm, still more Preferably it is 400 nm or less.

  In the present specification, the convex portion means a portion protruding from the reference surface, and the concave portion means a portion recessed from the reference surface. The reference surface means the surface of the resin layer.

  The average height of the convex part and the average depth of the concave part are obtained by scanning the surface of the concavo-convex structure using a scanning probe microscope such as an atomic force microscope and measuring the vertical displacement of the concavo-convex part. Can do.

  When the concavo-convex structure provided on the surface of the resin layer is wavy, the average length from the highest part (upper end of the convex part) to the deepest part (lower end of the concave part) of the wave, that is, the surface of the resin layer The average value of the length from the highest part to the deepest part of the wave in the vertical direction, in other words, the average height difference is preferably 100 nm or more, more preferably 200 nm or more, from the viewpoint of expressing desired optical characteristics. The thickness is preferably 250 nm or more, still more preferably 280 nm or more, and from the viewpoint of easily forming a concavo-convex structure, it is preferably 1000 nm or less, more preferably 600 nm or less, and even more preferably 500 nm or less.

  In this specification, the average value of the length from the highest part of the wave to the deepest part in the direction perpendicular to the surface of the resin layer is the same as the average height of the convex part or the average depth of the concave part. Can be sought.

  In the concavo-convex structure provided on the surface of the resin layer, the average interval between the convex portions and the convex portions, that is, the average value of the period of the convex portions (hereinafter referred to as the average cycle) and the average interval between the concave portions and the concave portions, The average period of the recesses is not more than the wavelength of visible light (wavelength: 400 to 830 nm), preferably not more than 400 nm, more preferably not more than 370 nm, from the viewpoint of improving the antireflection property of the resin layer and increasing the light extraction efficiency. More preferably, it is 350 nm or less, and in the same manner as described above, from the viewpoint of improving the antireflection property of the resin layer and increasing the light extraction efficiency, it is preferably 100 nm or more, more preferably 120 nm or more, and even more preferably 150 nm or more. Still more preferably, it is 200 nm or more.

  In the concavo-convex structure provided on the surface of the resin layer, it is preferable to appropriately select the shape of the convex portion and the shape of the concave portion according to the application of the optical molded body of the present invention. For example, when the optical molded body of the present invention is used for an antireflection film, examples of the shape of the convex portion and the shape of the concave portion include a conical shape, a triangular pyramid shape, a bell shape, and the like. It is not limited to only. The shape of the convex part and the concave part have a structure in which the refractive index continuously changes from the refractive index of air to the refractive index of the material forming the lower end of the concave part in the region from the upper end of the convex part to the lower end of the concave part. It is preferable that

  In the concavo-convex structure provided on the surface of the resin layer, the convex portions and the concave portions are regular, for example, a square arrangement, a three-way arrangement, etc. from the viewpoint of improving the antireflection property of the resin layer and increasing the light extraction efficiency. It is preferable that they are arranged.

  The occupied area ratio of the concavo-convex structure per unit area on the surface of the resin layer is preferably 40% or more, more preferably 60% or more, and further preferably 80% or more from the viewpoint of suppressing reflection on the surface of the resin layer. .

The total number of recesses and protrusions on the surface of the resin layer per unit area 1 μm ² of the surface of the resin layer is preferably 4 or more, more preferably 9 or more, from the viewpoint of suppressing reflection on the surface of the resin layer. More preferably, it is 16 or more, preferably 100 or less, more preferably 90 or less, and still more preferably 80 or less.

  In the concavo-convex structure provided on the surface of the resin layer, the average height of the protrusions or the average depth of the recesses is divided by the average value of the length from the highest part of the wave to the deepest part in the direction perpendicular to the surface of the resin layer. The value (hereinafter referred to as aspect ratio) is preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more from the viewpoint of improving the optical characteristics, and from the viewpoint of accurately forming the concavo-convex structure, Preferably it is 5 or less, More preferably, it is 3 or less.

  When forming the concavo-convex structure on the surface of the resin layer, a mold having a structure corresponding to the concavo-convex structure of the surface of the resin layer can be used. When using the said shaping | molding die, the uneven | corrugated shape currently formed in the surface of a shaping | molding die can be transcribe | transferred to the surface of a resin layer by pressing the said shaping | molding die on the surface of a resin layer. Therefore, when forming a convex part on the surface of a resin layer, the shaping | molding die which has the shape of the recessed part corresponding to the shape of the said convex part can be used. When forming the concave portion, a mold having a convex shape corresponding to the shape of the concave portion can be used. Moreover, when forming a convex part and a recessed part in the surface of a resin layer, the shaping | molding die which has the shape of the recessed part and convex part corresponding to the shape of the said convex part and a recessed part can be used.

  The mold having a structure corresponding to the concavo-convex structure of the surface of the resin layer is a base material made of silicon, quartz, etc., for example, through a resist pattern formed by photolithography, electron beam lithography or the like as a mask. And a method of producing a replica having a concavo-convex structure in which the concavo-convex structure is inverted by plating, using as a master a mold obtained by dry-etching the surface of a substrate made of silicon, quartz or the like. However, the present invention is not limited to such examples.

  Since the resin layer has low light reflectance and excellent light transmittance, the molded article of the present invention can be used as, for example, a polarizer protective film.

  FIG. 3 is a schematic cross-sectional view showing one embodiment of a polarizer protective film in which the optical molded body of the present invention is used. As shown in FIG. 3, the polarizer protective film has a film-like base in which the resin layer 1 having a concavo-convex structure on the surface is formed on one surface of the film-like substrate 2a and the resin layer 1 is not formed. A polarizer 4 is formed on the surface of the material 2a. A retardation film 5 is formed on the surface of the polarizer 4 on which the film-like substrate 2a is not formed.

  The polarizer protective film can be produced, for example, by integrating the film-like substrate 2a on which the resin layer 1 is formed and the polarizer 4 using an adhesive. As the polarizer 4, for example, a polyvinyl alcohol-based polarizer obtained by uniaxially stretching a polyvinyl alcohol-based resin film dyed with iodine, a dichroic dye, or the like; polyvinyl alcohol dehydrated material, polyvinyl chloride dehydrochlorinated material, or the like. A polyene polarizer, a reflective polarizer using a cholesteric liquid crystal, a thin film crystal film polarizer, and the like. However, the present invention is not limited to such examples. Among the polarizers 4, a uniaxially stretched polyvinyl alcohol polarizer is preferable. In general, the thickness of the polarizer 4 is preferably about 5 to 100 μm.

  Examples of the adhesive include an adhesive containing a polyvinyl alcohol resin, an acrylic resin, a polyurethane resin, and a polyester resin; an adhesive that cures with active energy rays such as ultraviolet rays and electron beams; an acrylic pressure-sensitive adhesive, and silicone Examples thereof include adhesives such as rubber-based adhesives and rubber-based adhesives, but the present invention is not limited to such examples. These adhesives may be used alone or in combination of two or more.

  An additive may be used for the adhesive. Additives include crosslinking agents, adhesion promoters, sensitizers, UV absorbers, anti-aging agents, dyes, pigments and other colorants, processing aids, ion scavengers, antioxidants, tackifiers, filling Although an agent, a plasticizer, a leveling agent, a foaming inhibitor, an antistatic agent, etc. are mentioned, this invention is not limited only to this illustration. These additives may be used alone or in combination of two or more.

  Examples of the method for bonding the film-like substrate 2a on which the resin layer 1 is formed using an adhesive and the polarizer 4 include kiss coat, spin coat, roll coat, dip coat, curtain coat, bar coat, and doctor blade. After applying an adhesive to the adhesive surface of the polarizer 4 by a method such as coating, knife coating, air knife coating, die coating, gravure coating, micro gravure coating, offset gravure coating, lip coating, spray coating, comma coating, the polarizer Although the method of superposing | stacking the adhesive surface of 4 and the film-form base material 2a in which the resin layer 1 was formed is mentioned, this invention is not limited only to this illustration. In addition, when bonding the film-like base material 2a on which the resin layer 1 is formed and the polarizer 4, the optical axis of the resin layer 1 and the absorption axis of the polarizer 4 are arranged so as to be orthogonal or parallel. Is preferred.

  In order to improve adhesiveness, the surface which contacts the polarizer 4 of the film-like base material 2a on which the resin layer 1 is formed may be subjected to an easy adhesion treatment. Examples of the easy adhesion treatment include plasma treatment, corona treatment, ultraviolet irradiation treatment, solvent treatment, flame (flame) treatment, saponification treatment, formation of an anchor layer, etc., but the present invention is limited to such examples only. Is not to be done. These methods may be used alone or in combination of two or more. Among these methods, corona treatment and formation of an anchor layer are preferable.

  When forming the anchor layer, for example, polymers such as acrylic polymer, cellulose polymer, urethane polymer, silicone polymer, polyester polymer, polyethyleneimine polymer, amino group-containing polymer are used as the anchor layer forming polymer. Can be used. These polymers may be used alone or in combination of two or more.

  Moreover, when forming an anchor layer, the coating composition containing the said polymer can be used. In addition to the polymer, the coating composition includes, for example, a crosslinking agent, an antiblocking agent, a dispersion stabilizer, a thixotropic agent, an antioxidant, an ultraviolet absorber, an antifoaming agent, a thickener, a dispersant, and a surfactant. In addition, additives such as a catalyst and an antistatic agent may be contained.

  Examples of the method of applying the coating composition to the contact surface of the film-like substrate 2a on which the resin layer 1 is formed with the polarizer 4 include a bar coater, a roll coater, and a gravure coater. Is not limited to such examples.

  Examples of the method for drying the applied coating composition include a method of drying at a temperature of preferably 50 to 130 ° C., more preferably 75 to 110 ° C. using a dryer such as a hot air dryer or an infrared dryer. However, the present invention is not limited to such examples. After the coating composition is dried, the formed film may be cured at a temperature of preferably 20 to 100 ° C., more preferably 20 to 50 ° C., if necessary.

  The thickness of the anchor layer after drying is preferably 0.01 μm or more, more preferably 0.05 μm or more, from the viewpoint of increasing the adhesive strength with the film-like substrate 2 a on which the polarizer 4 resin layer 1 is formed. The thickness is preferably 0.1 μm or more, and preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, and even more preferably 1 μm or less, from the viewpoint of preventing color loss and discoloration of the polarizer 4.

  The surface of the anchor layer may be subjected to surface treatment such as corona discharge treatment, plasma treatment, ozone spraying, solvent treatment, ultraviolet irradiation, flame treatment, chemical treatment, etc. from the viewpoint of improving wettability. .

  Since the polarizer protective film is excellent in optical characteristics and heat resistance, for example, VA type, IPS type liquid crystal display devices (LCD), organic electroluminescence light emitting devices (organic EL), plasma displays, electronic paper, and the like. It can be suitably used as an optical film for protecting a polarizer of an image display device such as a 3D display or a field emission display (FED).

  Since the optical molded body of the present invention has low light reflectance and high light extraction efficiency, it can be suitably used for an organic electroluminescence (organic EL) light emitting device.

  FIG. 4 is a schematic cross-sectional view showing an embodiment of an organic electroluminescence (organic EL) light-emitting device in which the optical molded body of the present invention is used. The organic electroluminescence (organic EL) light emitting device shown in FIG. 4 uses a laminate in which a resin layer 1 having a concavo-convex structure on the surface and a film-like substrate 2a are laminated. The laminate is disposed on the light extraction surface side of an organic electroluminescence (organic EL) light emitting device. An anode electrode 8 such as indium tin oxide (ITO) is connected to one surface of the light emitting layer 10 via a hole transport layer / hole injection layer 9. A cathode electrode 12 is connected to the other surface of the light emitting layer 10 via an electron transport layer / electron injection layer 11, and a transparent protective layer 13 is laminated on the cathode electrode 12. A glass substrate 7 is laminated on the anode electrode 8. The film-like substrate 2a of the laminate is disposed on the glass substrate 7 through the pressure-sensitive adhesive layer 6, and the resin layer 1 of the laminate is on the light extraction surface side of the organic electroluminescence (organic EL) light-emitting device. It is arranged like this. The light beam generated in the light emitting layer 10 passes through the pressure-sensitive adhesive layer 6 and the film-like base material 2a laminated on the glass base material 7, and is taken out from the surface of the resin layer 1.

  In the organic electroluminescence (organic EL) light emitting device shown in FIG. 4, the light extraction efficiency is enhanced because the surface on which the uneven structure of the resin layer is formed is on the light extraction surface side. Therefore, the film-like substrate 2a is laminated on the glass substrate 7 without performing complicated processing on the glass substrate 7 on the light extraction surface side of the light emitting layer 10 of the organic electroluminescence (organic EL) light emitting device. Thus, an excellent effect that the luminance can be increased is exhibited.

  In addition, as a method of bonding the film-like substrate 2a to the glass substrate 7, for example, a method of bonding the film-like substrate 2a of the laminate and the glass substrate 7 via the pressure-sensitive adhesive layer 6, Although the method etc. which heat-press the film-form base material 2a and the glass base material 7 are mentioned, this invention is not limited only to this method. Although the pressure-sensitive adhesive layer 6 is used in the embodiment shown in FIG. 7, an adhesive layer (not shown) may be used instead of the pressure-sensitive adhesive layer 6.

  Examples of the adhesive used for the adhesive layer 6 and the adhesive used for the adhesive layer (not shown) include an adhesive containing an acrylic resin, an adhesive containing a silicone resin, and an adhesive containing rubber. Adhesives including acrylic resins, adhesives including urethane resins, adhesives including polyester resins, and the like; adhesives that cure with active energy rays such as ultraviolet rays and electron beams However, the present invention is not limited to such a method. Among the pressure-sensitive adhesives and adhesives, the refractive index difference between the refractive index of the pressure-sensitive adhesive layer 6 or the adhesive layer (not shown) and the refractive index of the film-like substrate 2a, and the pressure-sensitive adhesive layer 6 or the adhesive layer. From the viewpoint of reducing both the refractive index difference between the refractive index of (not shown) and the refractive index of the glass substrate 7 and increasing the light extraction efficiency, an adhesive containing an acrylic resin and an adhesive containing a urethane resin An adhesive containing an agent, an acrylic resin, and an adhesive containing a urethane resin are preferred.

  In addition, the said adhesive and adhesive agent may contain the additive. Examples of the additive include a crosslinking agent, an adhesion promoter, a wettability improver, a sensitizer, an ultraviolet absorber, an anti-aging agent, a dye, a processing aid, an ion scavenger, an antioxidant, and a tackifier. Examples include fillers, plasticizers, leveling agents, foaming inhibitors, and antistatic agents, but the present invention is not limited to such examples.

  As described above, since the optical molded body of the present invention is excellent in scratch resistance and adhesion to a substrate, for example, displays such as liquid crystal displays and organic electroluminescence (EL) displays, and optics such as lenses. It is expected to be used as an optical material used for solar cells and the like as well as members and lighting fixtures.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example. In the following, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

Reference Example According to the description in JP-A-10-226669, 1,4-diazabicyclo [2.2.2] octane was used as a catalyst, and methyl α-hydroxymethyl acrylate was reacted with allyl alcohol. α-Allyloxymethyl methyl acrylate was prepared.

Preparation Example 1
63.0 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser.

  On the other hand, 25% aqueous solution of an anionic surfactant [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] as an emulsifier in the dropping funnel. 0 g, 42.8 g of deionized water and 100 g of methyl α-allyloxymethyl acrylate obtained in Reference Example were charged to prepare a pre-emulsion. Thereafter, the temperature was raised to 75 ° C. with stirring while gently blowing nitrogen gas into the dropping funnel, and 6.0 g of a 5% potassium persulfate aqueous solution was added to initiate the initial reaction.

  After completion of the initial reaction, the pre-emulsion obtained above was uniformly dropped into the flask over 5 hours while maintaining the inside of the flask at 80 ° C. After completion of dropping, the dropping funnel was washed with 5 g of deionized water, and the resulting cleaning solution was dropped into the flask. Thereafter, the contents in the flask were maintained at 80 ° C. for 1 hour to complete the polymerization. The obtained reaction liquid was cooled to room temperature to obtain a resin emulsion having a nonvolatile content of 44.8% by mass.

Preparation Example 2
63.0 g of deionized water was charged into a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser.

  On the other hand, 25% aqueous solution of an anionic surfactant [polyoxyethylene alkylphenyl ether sulfate ester, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon (registered trademark) HS-10] as an emulsifier in the dropping funnel. A pre-emulsion was prepared by charging 0 g, 42.8 g of deionized water, 68.0 g of methyl methacrylate, 20.0 g of cyclohexyl methacrylate, 10.0 g of styrene and 2.0 g of acrylic acid. Thereafter, while gradually blowing nitrogen gas into the flask, the temperature was raised to 75 ° C. with stirring, 6.0 g of 5% potassium persulfate aqueous solution was added, and an initial reaction was started.

  After completion of the initial reaction, the pre-emulsion obtained above was uniformly dropped into the flask over 5 hours while maintaining the inside of the flask at 80 ° C. After completion of dropping, the dropping funnel was washed with 5 g of deionized water, and the resulting cleaning solution was dropped into the flask. Thereafter, the contents in the flask were maintained at 80 ° C. for 1 hour to complete the polymerization. The obtained reaction liquid was cooled to room temperature to obtain a resin emulsion having a nonvolatile content of 44.7% by mass.

Production Example 1
In a reaction kettle equipped with a stirrer, a thermometer, a cooler and a nitrogen gas introduction tube, 40 parts of methyl methacrylate, 10 parts of methyl 2- (hydroxymethyl) acrylate, 50 parts of toluene and a phosphite antioxidant [( Made by ADEKA Co., Ltd., trade name: ADK STAB 2112], 0.025 part was charged, and the temperature of the contents of the reaction kettle was raised to 105 ° C. while passing nitrogen gas through the reaction kettle. When refluxing occurred, 0.05 part of tert-amyl peroxyisononanoate [manufactured by Atofina Yoshitomi Co., Ltd., trade name: Lupazole 570] was added as a polymerization initiator to the reaction kettle, and tert-amyl peroxy While 0.10 parts of isononanoate [manufactured by Atofina Yoshitomi Co., Ltd., trade name: Rupasol 570] was dropped into the reaction kettle over 2 hours, solution polymerization was performed under reflux (about 105 to 110 ° C.). A polymer solution was obtained by aging for 4 hours.

  0.05 parts of stearyl phosphate [manufactured by Sakai Chemical Industry Co., Ltd., trade name: Phoslex A-18] was added to the polymer solution obtained above, and the mixture was refluxed (about 90 to 110 ° C.) for 2 hours. The polycondensation reaction was performed.

  Next, after the cyclization condensation reaction was completed by passing the polymer solution subjected to the cyclization condensation reaction through a multi-tube heat exchanger heated to 240 ° C., the barrel temperature was 240 ° C. and the rotation speed was 120 rpm. , Decompression degree 13.3 to 400 hPa, rear vent number 1, fore vent number 4 (referred to as first, second, third, fourth vent from the upstream side) between the third vent and the fourth vent It was introduced into a vent type screw twin screw extruder (L / D = 52) having a side feeder at a processing rate of 20 parts / hour in terms of resin amount, and devolatilized. At that time, the antioxidant / deactivator mixed solution prepared in advance as described in “Preparation of Antioxidant / Deactivator Mixed Solution” below is fed into the high-pressure pump after the second vent. Injected at a dosing rate of 0.3 parts / hour. Further, after the first vent and after the side feeder, ion exchange water was injected at a charging rate of 0.33 part / hour by a high pressure pump.

  Further, an AS resin [manufactured by Asahi Kasei Chemicals Corporation, trade name: Stylac AS783L] was added from the side feeder at a supply rate of 2.12 parts / hour to obtain a melt-kneaded resin.

  Next, the melt-kneaded resin obtained above was filtered through a leaf disk type polymer filter (manufactured by Nagase Sangyo Co., Ltd., filtration accuracy: 5 μm) to obtain acrylic resin pellets.

[Preparation of mixed solution of antioxidant and quencher]
50 parts of a hindered phenolic antioxidant (manufactured by Nagase Sangyo Co., Ltd., trade name: Irganox 1010), 50 parts of a phenolic antioxidant [manufactured by ADEKA, trade name: ADK STAB AO-412S], and octylic acid A mixed solution of an antioxidant and a deactivator was prepared by dissolving 40 parts of zinc (manufactured by Nippon Chemical Industry Co., Ltd., trade name: 3.6% of Nikka octix zinc) in 160 parts of toluene.

  The weight average molecular weight and glass transition temperature of the acrylic resin used in the pellets obtained above were examined based on the following method. As a result, the acrylic resin had a weight average molecular weight of 132,000 and a glass transition temperature of 125 ° C.

[Method for measuring weight average molecular weight of acrylic resin]
The weight average molecular weight of the acrylic resin was determined by gel permeation chromatography (GPC) under the following conditions.
・ System: manufactured by Tosoh Corporation, product number: GPC system HLC-8220
・ Developing solvent: Chloroform (made by Wako Pure Chemical Industries, Ltd., special grade), flow rate: 0.6 mL / min ・ Standard sample: TSK standard polystyrene (made by Tosoh Corporation, trade name: PS-oligomer kit)
Measurement column configuration: guard column [manufactured by Tosoh Corporation, trade name: TSK guard column
SuperHZ-L], separation column [manufactured by Tosoh Corp., trade name: TSKgel SuperHZM-M] 2 series connection and reference side column configuration: reference column [manufactured by Tosoh Corp., trade name: TSKgel SuperH-RC]
-Column temperature: 40 ° C
・ Detector: Differential refractometer

〔Glass-transition temperature〕
The glass transition temperature (Tg) of the acrylic resin was determined in accordance with JIS K7121 regulations. More specifically, a differential scanning calorimeter [manufactured by Rigaku Corporation, product number: DSC-8230] was used, and about 10 mg of acrylic resin was increased from room temperature to 200 ° C. at a heating rate of 20 ° C./min in a nitrogen gas atmosphere. It calculated by the starting point method from the obtained DSC curve. Α-alumina was used as a reference.

  Next, the pellets obtained above were put into a single screw extruder equipped with a leaf disk type polymer filter (manufactured by Nagase Sangyo Co., Ltd., filtration accuracy: 5 μm) to prepare a melt kneaded product, and the obtained melt The kneaded product was extruded from a T die at a temperature of 280 ° C., and discharged onto a 110 ° C. cooling roll to prepare an unstretched film. The obtained unstretched film was successively biaxially stretched so that the stretch ratio was 2.0 times in both length and width, thereby obtaining a transparent film-like substrate having a thickness of 100 μm. The glass transition temperature of the obtained film-like substrate was measured in the same manner as described above, and was 125 ° C. Further, when the total light transmittance, haze value, b value, in-plane retardation Re and thickness direction retardation Rth of the film-like substrate were measured based on the following method, the total light transmittance was 92.3%. The haze value was 0.4%, the b value was 0.1, the in-plane retardation Re was 1 nm, and the thickness direction retardation Rth was 2 nm.

[Total light transmittance]
The total light transmittance of the film-like substrate was measured using a turbidimeter [manufactured by Nippon Denshoku Industries Co., Ltd., product number: NDH-5000] according to JIS K7361-1 (1997).

[Haze value]
The haze value of the film-like substrate was measured according to JIS K7136 (2000) using a turbidimeter [manufactured by Nippon Denshoku Industries Co., Ltd., product number: NDH-5000].

[B value (color difference)]
The b value (color difference) of the film-like substrate is based on the measured value of the film-like substrate measured using a colorimetric color difference meter [Nippon Denshoku Industries Co., Ltd., product number: ZE6000]. The film thickness was calculated as a value converted to 250 μm. In addition, b value is a value of b * in the hue display based on JISZ8729, and it calculated | required as an average value of ten places measured by putting a film-form base material on a standard white board.

[In-plane retardation Re]
The in-plane retardation Re of the film-like substrate was measured at a wavelength of 400 nm, 589 nm, or 750 nm using a retardation film / optical material inspection apparatus [manufactured by Otsuka Electronics Co., Ltd., product number: RETS-100].

[Thickness direction retardation Rth]
The retardation Rth in the thickness direction of the film-like substrate was measured at a wavelength of 400 nm, 589 nm or 750 nm using a retardation film / optical material inspection apparatus (manufactured by Otsuka Electronics Co., Ltd., product number: RETS-100). . Further, the retardation value Rth in the thickness direction of the film-like substrate is the average refractive index of the film-like substrate measured with an Abbe refractometer, the thickness d of the film-like substrate, and the position measured by tilting by 40 °. The phase difference value [Re (40 °)], the refractive index nx in the slow axis direction in the plane of the film substrate, the refractive index ny in the fast axis direction, and the refractive index nz in the thickness direction of the film substrate. After the formula:
[Thickness direction retardation Rth (nm)] = [(nx + ny) / 2−nz] × d
Based on.

  In addition, the thickness d of the film-like base material was measured using a Digimatic Micrometer [manufactured by Mitutoyo Corporation].

Production Example 2
Glutarimide resin [Evonik Degussa Japan Co., Ltd., trade name: Pleximimide 8813] 78 parts, AS resin [Asahi Kasei Chemicals Co., Ltd., trade name: Stylac AS783L], antioxidant [Adeka Co., Ltd.] Product, product name: ADK STAB AO-60] and 0.05 part of phenolic antioxidant [manufactured by ADEKA, product name: ADK STAB AO-412S] in the same manner as in Production Example 1, biaxial extrusion The mixture was kneaded with a machine to obtain acrylic resin pellets. When the weight average molecular weight and glass transition temperature of the acrylic resin contained in the obtained pellet were measured in the same manner as in Production Example 1, the weight average molecular weight of the acrylic resin was 128000, and the glass transition temperature was 129 ° C. It was.

  Next, the pellet obtained above was melt-extruded from a T-die at a temperature of 280 ° C. using a single-screw extruder equipped with a leaf disk type polymer filter (manufactured by Nagase Sangyo Co., Ltd., filtration accuracy: 5 μm), By discharging onto a 110 ° C. cooling roll, an unstretched film was obtained. The unstretched film obtained above was successively biaxially stretched so that the stretching ratio was 2.0 times in both length and width, thereby obtaining a transparent film-like substrate having a thickness of 100 μm. When the glass transition temperature, total light transmittance, haze value, b value, in-plane retardation Re and thickness direction retardation Rth of this film-like substrate were examined in the same manner as in Production Example 1, the glass transition temperature was 129. ° C, total light transmittance is 91.8%, haze value is 0.5%, b value is 0.3, in-plane retardation Re is 2 nm, thickness direction retardation Rth was 2 nm.

Example 1
224.2 g of the resin emulsion obtained in Preparation Example 1, and 2-methyl-1- [4- (methylthio) feyl] -2-morpholinopropan-1-one [manufactured by BASF Japan, as a photopolymerization initiator, Product name: IRGACURE 907] 3.8 g, 1,6-hexanediol dimethacrylate 50.0 g, dipentaerythritol hexaacrylate 25.0 g and deionized water 95 g were mixed with stirring to obtain a molding material. The minimum film forming temperature of the obtained molding material was 0 ° C.

  The thickness of the resin layer after drying with a bar coater on the surface of a polyethylene terephthalate film [Toyobo Co., Ltd., trade name: Cosmo Shine A4300, thickness: 188 μm] using the molding material obtained above as a base material is 5 μm. The laminated body in which the resin layer which consists of molding materials was formed in one side of the resin film was obtained by apply | coating like this and making it dry at 60 degreeC for 10 minutes.

  Next, using a quartz mold (vertical: 20 mm, horizontal: 20 mm) in which conical concave portions having a depth of 350 nm are arranged in three directions with an average period of 260 nm, the surface on which the concave and convex pattern of the mold is formed Was pressed against the surface on which the resin layer of the laminate obtained above was formed, and heated to 80 ° C. using an imprint apparatus (manufactured by Toshiba Machine Co., Ltd., product number: ST-02). After pressurizing for 10 minutes so that the pressure is uniformly applied to the surface of the resin layer, the laminate is cooled to 30 ° C., and the laminate is released from the molding die to obtain a laminate having fine irregularities formed on the surface. Obtained.

Next, an optical molded body was obtained by irradiating the surface on which the fine concavo-convex structure of the laminate was formed with ultraviolet light having an energy of 1 J / cm ² with a high-pressure mercury lamp (350 W, main wavelength 365 nm).

  When the surface having the fine concavo-convex structure of the optical molded body obtained above was observed with an atomic force microscope (AFM), a fine concavo-convex structure in which conical projections having a diameter of 270 nm and an average height of 350 nm were arranged in three directions was obtained. It was confirmed that there was no transfer defect.

  Next, as physical properties of the optical molded body obtained above, scratch resistance, adhesion, total light transmittance and luminous reflectance were examined based on the following methods. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “5”, the evaluation of adhesion was “5”, the total light transmittance was 89%, and the luminous reflectance was 0.12%. there were.

[Abrasion resistance]
A test piece was prepared by pasting on a glass plate so that the surface on which the fine concavo-convex structure of the optical molded body was formed became the test surface.

Next, # 0000 steel wool [manufactured by Nippon Steel Wool Co., Ltd., trade name: BON STAR] was attached so as to be uniform on a smooth vertical section of a cylinder having a diameter of 10 mm, a load of 200 g / cm ² , and a speed. The steel wool was reciprocated 10 times on the test surface under the condition of 30 mm / sec, and an abrasion resistance test was performed.

The haze value of the optical molded body before and after the scratch resistance test was measured using a turbidimeter [manufactured by Nippon Denshoku Industries Co., Ltd., product number: NDH-5000], and the formula:
[Absolute value of haze value difference (ΔHz)]
= | (Haze value after scratch resistance test) − (Haze value before scratch resistance test) |
Based on the above, the absolute value of the haze value difference (ΔHz) was obtained and evaluated based on the following evaluation criteria.

(Evaluation criteria)
5 points: ΔHz> 1
4 points: 1 <ΔHz <2
3 points: 2 <ΔHz <3
2 points: 3 <ΔHz <5
1 point: 5 <ΔHz

[Adhesion]
The adhesion between the resin layer of the optical molded body and the film-like base material was evaluated based on the following evaluation criteria, based on JIS K5600-5-6, tested by a grid pattern cut at 1 mm intervals. .

(Evaluation criteria)
5: The cut edge is smooth, and there is no peeling on any grid.
4: The peeled area is less than 5% of the cut grid area.
3: The peeled area is 5% or more and less than 15% of the cut grid area.
2: The peeled area is 15% or more and less than 35% of the area of the cut grid.
1: The peeled area is 35% or more and less than 65% of the cut grid area.
0: The peeled area is 65% or more of the cut grid area.

[Total light transmittance]
The total light transmittance of the surface on which the fine concavo-convex structure of the optical molded body was formed was measured according to JIS K7361-1 (1997) using a turbidimeter [manufactured by Nippon Denshoku Industries Co., Ltd., product number: NDH-5000]. Measured in conformity.

[Visual reflectance]
The luminous reflectance of the surface on which the fine concavo-convex structure of the optical molded body is formed is determined by applying a black tape on the surface opposite to the surface on which the fine concavo-convex structure of the optical molded body is formed, and then molding the optical Spectral reflectance was measured in the range of an incident angle of 5 ° and a wavelength of 380 to 780 nm using a spectrophotometer [manufactured by Shimadzu Corporation, product number: UV3700] on the surface on which the fine concavo-convex structure of the body was formed. The luminous reflectance was determined from the measurement result of the reflectance in accordance with JIS R 3106.

Example 2
224.2 g of the resin emulsion obtained in Preparation Example 1, 2-methyl-1- [4- (methylthio) feer] -2-morpholinopropan-1-one [manufactured by BASF Japan Ltd., trade name: IRGACURE 907 10 g, 200 g of pentaerythritol triacrylate and 255 g of deionized water were mixed with stirring to obtain a molding material. The minimum film forming temperature of the obtained molding material was 0 ° C.

  The thickness of the resin layer after drying with a bar coater on the surface of a polyethylene terephthalate film [Toyobo Co., Ltd., trade name: Cosmo Shine A4300, thickness: 188 μm] using the molding material obtained above as a base material is 5 μm. The laminated body in which the resin layer which consists of molding materials was formed in one side of the resin film was obtained by apply | coating like this and making it dry at 60 degreeC for 10 minutes.

  Next, using a quartz mold (vertical: 20 mm, horizontal: 20 mm) in which conical concave portions having a depth of 350 nm are arranged in three directions with an average period of 260 nm, the surface on which the concave and convex pattern of the mold is formed Was pressed against the surface on which the resin layer of the laminate obtained above was formed, and heated to 80 ° C. using an imprint apparatus (manufactured by Toshiba Machine Co., Ltd., product number: ST-02). After pressurizing for 10 minutes so that the pressure is uniformly applied to the surface of the resin layer, the laminate is cooled to 30 ° C., and the laminate is released from the molding die to obtain a laminate having fine irregularities formed on the surface. Obtained.

Next, an optical molded body was obtained by irradiating the surface on which the fine concavo-convex structure of the laminate was formed with ultraviolet light having an energy of 1 J / cm ² with a high-pressure mercury lamp (350 W, main wavelength 365 nm).

  When the surface having the fine concavo-convex structure of the optical molded body obtained above was observed with an atomic force microscope (AFM), a fine concavo-convex structure in which conical projections having a diameter of 270 nm and an average height of 350 nm were arranged in three directions was obtained. It was confirmed that there was no transfer defect.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “5”, the evaluation of adhesion was “5”, the total light transmittance was 88%, and the luminous reflectance was 0.11%. there were.

Example 3
In Example 1, the surface of the resin layer was the same as in Example 1 except that a cycloolefin polymer film [manufactured by Nippon Zeon Co., Ltd., trade name: ZEONOR] was used instead of the polyethylene terephthalate film as the substrate. An optical molded body having a fine concavo-convex structure was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “4”, the evaluation of adhesion was “4”, the total light transmittance was 90%, and the luminous reflectance was 0.12%. there were.

Example 4
In Example 2, instead of the polyethylene terephthalate film as the substrate, the surface of the resin layer was the same as in Example 2 except that a cycloolefin polymer film [manufactured by Nippon Zeon Co., Ltd., trade name: ZEONOR] was used. An optical molded body having a fine concavo-convex structure was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “4”, the evaluation of adhesion was “4”, the total light transmittance was 89%, and the luminous reflectance was 0.13%. there were.

Example 5
In Example 1, instead of the polyethylene terephthalate film as the substrate, a triacetyl cellulose film [manufactured by Fuji Film Co., Ltd., product number: TD-80U] was used in the same manner as in Example 1, except that the resin layer An optical molded body having a fine relief structure on the surface was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the scratch resistance evaluation of the optical molded body obtained above was “4”, the adhesion evaluation was “4”, the total light transmittance was 89%, and the luminous reflectance was 0.14%. there were.

Example 6
In Example 2, a resin layer was formed in the same manner as in Example 2 except that a triacetyl cellulose film [manufactured by Fuji Film Co., Ltd., product number: TD-80U] was used instead of the polyethylene terephthalate film. An optical molded body having a fine relief structure on the surface was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the scratch resistance evaluation of the optical molded body obtained above was “4”, the adhesion evaluation was “4”, the total light transmittance was 88%, and the luminous reflectance was 0.15%. there were.

Example 7
In Example 1, the surface of the resin layer has a fine concavo-convex structure in the same manner as in Example 1 except that the film-like substrate obtained in Production Example 1 was used instead of the polyethylene terephthalate film as the substrate. An optical molded body was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “5”, the evaluation of adhesion was “5”, the total light transmittance was 93%, and the luminous reflectance was 0.09%. there were.

Example 8
In Example 2, the surface of the resin layer has a fine concavo-convex structure in the same manner as in Example 2 except that the film-like substrate obtained in Production Example 1 was used instead of the polyethylene terephthalate film as the substrate. An optical molded body was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “5”, the evaluation of adhesion was “5”, the total light transmittance was 92%, and the luminous reflectance was 0.09%. there were.

Example 9
In Example 1, the surface of the resin layer has a fine concavo-convex structure in the same manner as in Example 1 except that the film-like substrate obtained in Production Example 2 was used instead of the polyethylene terephthalate film as the substrate. An optical molded body was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “5”, the evaluation of adhesion was “5”, the total light transmittance was 92%, and the luminous reflectance was 0.10%. there were.

Example 10
In Example 2, the surface of the resin layer has a fine concavo-convex structure in the same manner as in Example 2 except that the film-like substrate obtained in Production Example 2 was used instead of the polyethylene terephthalate film as the substrate. An optical molded body was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “5”, the evaluation of adhesion was “5”, the total light transmittance was 92%, and the luminous reflectance was 0.11%. there were.

Comparative Example 1
In Example 1, except that the resin emulsion was changed to the resin emulsion obtained in Production Example 2, an optical molded body having a fine concavo-convex structure on the surface of the resin layer was obtained in the same manner as in Example 1.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “3”, the evaluation of adhesion was “3”, the total light transmittance was 89%, and the luminous reflectance was 0.58%. there were.

Comparative Example 2
In Example 2, an optical molded body having a fine concavo-convex structure on the surface of the resin layer was obtained in the same manner as in Example 2 except that the resin emulsion was changed to the resin emulsion obtained in Production Example 2.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “3”, the evaluation of adhesion was “3”, the total light transmittance was 88%, and the luminous reflectance was 0.55%. there were.

Comparative Example 3
In Comparative Example 1, the surface of the resin layer was the same as Comparative Example 1 except that a cycloolefin polymer film [manufactured by Nippon Zeon Co., Ltd., trade name: ZEONOR] was used as the substrate instead of the polyethylene terephthalate film. An optical molded body having a fine concavo-convex structure was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “2”, the evaluation of adhesion was “2”, the total light transmittance was 90%, and the luminous reflectance was 0.71%. there were.

Comparative Example 4
In Comparative Example 2, the surface of the resin layer was the same as Comparative Example 2 except that a cycloolefin polymer film [manufactured by Nippon Zeon Co., Ltd., trade name: ZEONOR] was used as the substrate instead of the polyethylene terephthalate film. An optical molded body having a fine concavo-convex structure was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “2”, the evaluation of adhesion was “2”, the total light transmittance was 89%, and the luminous reflectance was 0.65%. there were.

Comparative Example 5
In Comparative Example 1, a resin layer was formed in the same manner as in Comparative Example 1 except that a triacetyl cellulose film [manufactured by Fuji Film Co., Ltd., product number: TD-80U] was used instead of the polyethylene terephthalate film. An optical molded body having a fine relief structure on the surface was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “2”, the evaluation of adhesion was “2”, the total light transmittance was 89%, and the luminous reflectance was 0.81%. there were.

Comparative Example 6
In Comparative Example 2, the resin layer was formed in the same manner as in Comparative Example 2 except that a triacetyl cellulose film [Fuji Film Co., Ltd., product number: TD-80U] was used instead of the polyethylene terephthalate film as the base material. An optical molded body having a fine relief structure on the surface was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “2”, the evaluation of adhesion was “2”, the total light transmittance was 88%, and the luminous reflectance was 0.92%. there were.

Comparative Example 7
In Comparative Example 1, the surface of the resin layer has a fine concavo-convex structure as in Comparative Example 1, except that the film-like substrate obtained in Production Example 1 was used instead of the polyethylene terephthalate film as the substrate. An optical molded body was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of scratch resistance of the optical molded body obtained above was “3”, the evaluation of adhesion was “3”, the total light transmittance was 93%, and the luminous reflectance was 0.43%. there were.

Comparative Example 8
In Comparative Example 2, the surface of the resin layer has a fine concavo-convex structure in the same manner as in Comparative Example 2 except that the film-like substrate obtained in Production Example 1 was used instead of the polyethylene terephthalate film as the substrate. An optical molded body was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of the scratch resistance of the optical molded body obtained above was “3”, the evaluation of adhesion was “3”, the total light transmittance was 92%, and the luminous reflectance was 0.45%. there were.

Comparative Example 9
In Comparative Example 1, the surface of the resin layer has a fine concavo-convex structure as in Comparative Example 1, except that the film-like substrate obtained in Production Example 2 was used instead of the polyethylene terephthalate film as the substrate. An optical molded body was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of the scratch resistance of the optical molded body obtained above was “3”, the evaluation of adhesion was “3”, the total light transmittance was 92%, and the luminous reflectance was 0.43%. there were.

Comparative Example 10
In Comparative Example 2, the surface of the resin layer has a fine concavo-convex structure in the same manner as in Comparative Example 2 except that the film-like substrate obtained in Production Example 2 was used instead of the polyethylene terephthalate film as the substrate. An optical molded body was obtained.

  Next, as the physical properties of the optical molded body obtained above, the scratch resistance, adhesion, total light transmittance and luminous reflectance were examined in the same manner as in Example 1. As a result, the evaluation of the scratch resistance of the optical molded body obtained above was “3”, the evaluation of adhesion was “3”, the total light transmittance was 92%, and the luminous reflectance was 0.41%. there were.

  In addition, Comparative Examples 1-10 respond | correspond to Examples 1-10 in order, respectively. Table 1 shows the measurement results of the physical properties of each example and each comparative example.

From the results shown in Table 1, the optical molded body obtained in each example has the same total light transmittance (%) as compared with the optical molded body obtained in each comparative example. It can be seen that the luminous reflectance is remarkably low, and the scratch resistance and adhesion are excellent.

DESCRIPTION OF SYMBOLS 1: Resin layer 2: Base material 2a: Film-like base material 3: Mold type 4: Polarizer 5: Retardation film 6: Adhesive layer 7: Glass base material 8: Anode electrode 9: Hole transport layer / hole Injection layer 10: Light emitting layer 11: Electron transport layer / electron injection layer 12: Cathode electrode 13: Transparent protective layer

Claims (3)

An optical molded body in which a resin layer is formed on a substrate and a fine uneven shape is formed on the surface of the resin layer, and the polymer used for the resin layer is represented by the formula (I):
(Wherein R ¹ is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, R ² is a methylene group, R ³ is a direct bond or a methylene group, R ⁴ is a hydrogen atom, an alkyl having 1 to 4 carbon atoms) Group, phenyl group, carboxyl group, ester group or cyano group, R ⁵ is a direct bond or methylene group, X and Y are each independently a methylene group optionally having an alkyl group of 1 to 4 carbon atoms, imino A group, a carbonyl group, an oxygen atom or a sulfur atom, Z represents a direct bond, a methylene group which may have an alkyl group having 1 to 4 carbon atoms, an imino group, a carbonyl group, an oxygen atom or a sulfur atom; At least one group of Y and Z is an oxygen atom, a sulfur atom or an imino group which are not adjacent to each other)
A molded article for optics, which is a polymer having a ring structure-containing unit represented by the formula: A polymer having a ring structure-containing unit is represented by the formula (Ia):
(Wherein R ¹ represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms)
The optical molded body according to claim 1, which is a polymer having a ring structure-containing unit represented by:   1. A molded article for optics in which a resin layer is formed on a substrate and a fine uneven shape is formed on the surface of the resin layer, wherein the polymer used for the resin layer contains 1,5-hetero atoms. Cyclopolymerization of a monomer component containing at least one diene structure-containing monomer selected from the group consisting of a diene structure-containing monomer and a 1,6-diene structure-containing monomer containing a hetero atom A molded article for optics, which is formed of a polymer having a ring structure containing a heteroatom in the main chain.