JP7210844B2 - Shaped film and photocurable composition - Google Patents

Description

The present invention relates to a shaped film and a photocurable composition.

With the rapid development of display technology such as liquid crystal display devices, there is an increasing demand for optical sheets (optical films) used therein that have new functions and are of higher quality. Such optical sheets include, for example, prism sheets used for backlights in liquid crystal display devices, etc., lenticular lens sheets used for stereoscopic photography, projection screens, etc., Fresnel lens sheets used for condenser lenses of overhead projectors, etc., color Diffraction gratings used in filters and the like, shaped films for lighting used in game machines, toys, home appliances and the like can be mentioned. Such an optical sheet is also called a shaping film, and usually comprises a substrate and a shaping layer laminated on the substrate. A fine shape is transferred to the shape-imparting layer by a mold or the like, and desired optical properties are imparted.

The optical sheet may be worn due to deformation or chipping of the surface and side surfaces of the shaping layer, such as the top of the fine structure, due to impact or vibration during manufacturing. Such abrasion of the optical sheet causes unevenness on the display surface of the display device, thereby degrading the display performance. In order to solve such problems, various proposals have been made regarding the material of the shaping layer (see, for example, Patent Document 1).

JP 2011-21114 A

In recent years, the use of optical sheets in in-vehicle liquid crystal display devices is increasing, and there is a demand for optical sheets that are not only resistant to abrasion but also excellent in durability under high-temperature and high-humidity environments. However, in the optical sheet disclosed in Patent Document 1, the adhesion of the imprinting layer to the substrate may deteriorate in a high-temperature and high-humidity environment. The present invention provides a shaped film having a shaped layer having high hardness and capable of maintaining the adhesion of the shaped layer to a substrate for a long time even under high temperature and high humidity conditions, and for producing the same. It is an object to provide a photocurable composition of.

A shaping film according to one aspect of the present disclosure includes a base material and a shaping layer laminated on the base material, wherein the shaping layer comprises (A) a photocurable composition containing a radically polymerizable component The (A) radically polymerizable component includes (A1) a urethane acrylate having two or more (meth)acryloyl groups, and (A2) a nitrogen-containing monofunctional (meth)acrylic monomer. include.

The shaping film contains (A) a urethane acrylate having two or more (meth)acryloyl groups (A1) as a radically polymerizable component, so that the cured product (i.e., the shaping layer) adheres to the substrate. becomes significantly stronger. By combining the (A1) component with the (A2) component, the shaping layer can maintain the adhesion to the substrate for a long period of time even under high-temperature and high-humidity conditions in which adhesion tends to decrease. . Moreover, the hardness of the cured product (that is, the shaping layer) is improved. By containing (A2) a nitrogen-containing monofunctional (meth)acrylic monomer as a radically polymerizable component, the adhesion of the cured product to the substrate can be improved from physical and mechanical aspects. Moreover, the hardness of the cured product is improved. A shaping film containing a cured product of a photocurable resin composition having a composition in which the above components (A1) and (A2) are combined in a shaping layer has a shaping layer having a high hardness, and Even under high humidity conditions, the adhesion of the imprinting layer to the substrate can be maintained for a long period of time.

［式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又はメチル基を示し、ｎ及びｍは、ｎ＋ｍ＝２０～４０となるように選ばれる正の整数を示す。］
このような成分を含むことで、光硬化型組成物が硬化する際の収縮が緩和されるため、光照射及び高温処理により光硬化型組成物の硬化反応が進行しても、基材に対する硬化物の密着性が長時間維持される。また、（Ａ３）エチレンオキサイド変性ビスフェノールＡジ（メタ）アクリレートは、硬化物の柔軟性を適度に向上させることができ、それによって硬化物の密着性を向上させることができる。The (A) radically polymerizable component may further contain (A3) an ethylene oxide-modified bisphenol A di(meth)acrylate represented by the following general formula (1).

[In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n and m represent positive integers selected so that n+m=20-40. ]
By containing such a component, shrinkage during curing of the photocurable composition is alleviated. The adhesion of objects is maintained for a long time. In addition, (A3) ethylene oxide-modified bisphenol A di(meth)acrylate can moderately improve the flexibility of the cured product, thereby improving the adhesiveness of the cured product.

The (A) radically polymerizable component may further contain (A4) an alicyclic monofunctional (meth)acrylic monomer. By containing such a component, shrinkage during curing of the photocurable composition is alleviated. The adhesion of objects is maintained for a long time.

The (A4) alicyclic monofunctional (meth)acrylic monomer may have a dicyclopentadiene skeleton. Since the alicyclic monofunctional (meth)acrylic monomer has a dicyclopentadiene skeleton, the adhesion of the imprinting layer to the substrate can be maintained for a longer time under high temperature conditions.

The (A) radically polymerizable component may further contain (A5) a polyfunctional (meth)acrylic monomer having two or more (meth)acryloyl groups. By containing such components, the hardness of the imprinting layer is increased, and the adhesion of the imprinting layer to the substrate can be maintained for a longer period of time under high temperature and high humidity conditions.

The (A1) urethane acrylate may have a polycarbonate structure. Since the urethane acrylate has a polycarbonate structure, the adhesion of the shaping layer to the substrate is further enhanced.

The photocurable composition may further contain (B) a photopolymerization initiator. (B) The photopolymerization initiator is useful for efficient curing of the photocurable composition by photoradical polymerization.

［式中、Ｒ^３は、ｔｅｒｔ－ブチル基又はメチル基を示す。］
（Ｃ）フェノール系酸化防止剤は硬化物の熱酸化劣化を抑制することで、硬化物の耐熱黄変性、基材に対する賦形層の密着性、及び高分子の寿命といった長期信頼性を高める効果がある。The photocurable composition may further contain (C) a phenolic antioxidant having a structure represented by the following general formula (2).

[In the formula, R ³ represents a tert-butyl group or a methyl group. ]
(C) Phenolic antioxidant suppresses thermal oxidation deterioration of the cured product, and has the effect of improving long-term reliability such as thermal yellowing of the cured product, adhesion of the imprinting layer to the base material, and life of the polymer. There is

The photocurable composition may further contain (D) a light stabilizer. (D) Light stabilizers are useful for obtaining better adhesion, hardness, and light stability of the shaping layer.

The content of the (A1) urethane acrylate in the photocurable composition may be 0.1 to 50% by mass based on the total amount of the (A) radically polymerizable component. When the content of the urethane acrylate is within this range, the adhesion of the imprinting layer to the substrate can be maintained for a longer period of time under high temperature and high humidity conditions.

The content of the ethylene oxide-modified bisphenol A di(meth)acrylate (A3) in the photocurable composition may be 0.1 to 20% by mass based on the total amount of the radically polymerizable component (A). . When the content of the ethylene oxide-modified bisphenol A di(meth)acrylate is at least the above lower limit value, it is possible to provide more suitable flexibility for obtaining excellent adhesion, and the photocurable composition is cured. The contraction at the time can be more relaxed. Moreover, when the content of the ethylene oxide-modified bisphenol A di(meth)acrylate is equal to or less than the above upper limit, the glass transition temperature of the cured product can be maintained at a certain level or higher. When the Tg of the cured product is at least a certain level, it is possible to suppress deterioration in adhesion due to movement of the molecules of the cured product under high temperature conditions.

The content of the alicyclic monofunctional (meth)acrylic monomer (A4) in the photocurable composition may be 30 to 75% by mass based on the total amount of the radically polymerizable component (A). When the content of the alicyclic monofunctional (meth)acrylic monomer is 30 to 75% by mass, the adhesion of the imprinting layer to the substrate can be maintained for a longer period of time under high temperature conditions.

The substrate may be a polycarbonate film. The shaping layer of the shaping film according to the aspect of the present disclosure exhibits excellent adhesion even when the substrate is a polycarbonate film.

A photocurable composition according to one aspect of the present disclosure includes (A) a radically polymerizable component, and the (A) radically polymerizable component is (A1) a urethane acrylate having two or more (meth)acryloyl groups and (A2) a nitrogen-containing monofunctional (meth)acrylic monomer.

［式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又はメチル基を示し、ｎ及びｍは、ｎ＋ｍ＝２０～４０となるように選ばれる正の整数を示す。］The (A) radically polymerizable component may further contain (A3) an ethylene oxide-modified bisphenol A di(meth)acrylate represented by the following general formula (1).

[In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n and m represent positive integers selected so that n+m=20-40. ]

The (A) radically polymerizable component may further contain (A4) an alicyclic monofunctional (meth)acrylic monomer.

The (A4) alicyclic monofunctional (meth)acrylic monomer may have a dicyclopentadiene skeleton.

The (A) radically polymerizable component may further contain (A5) a polyfunctional (meth)acrylic monomer having two or more (meth)acryloyl groups.

The (A1) urethane acrylate may have a polycarbonate structure.

The photocurable composition may further contain (B) a photopolymerization initiator.

［式中、Ｒ^３は、ｔｅｒｔ－ブチル基又はメチル基を示す。］The photocurable composition may further contain (C) a phenolic antioxidant having a structure represented by the following general formula (2).

[In the formula, R ³ represents a tert-butyl group or a methyl group. ]

The photocurable composition may further contain (D) a light stabilizer.

The photocurable composition may have a viscosity of 40 to 1000 mPa·s at 25°C. When the viscosity is within this range, it is advantageous from the viewpoint of the coatability of the photocurable composition and from the viewpoint of transferring the fine shape from the mold to the shaping layer.

According to the present invention, a shaping layer having a high hardness is provided, and the adhesion of the shaping layer to a substrate is maintained for a long time even under high temperature and high humidity conditions (for example, temperature of 85° C. or higher and humidity of 85% RH or higher). A shaped film that can be maintained for a long time (for example, 50 hours or more) and a photocurable composition for producing the same can be provided. In particular, the shaping film can maintain the adhesion of the shaping layer to the substrate for a long time under high-temperature and high-humidity conditions even if the substrate is a polycarbonate film.

1 is a schematic cross-sectional view showing one embodiment of a shaped film. FIG. 1 is a schematic cross-sectional view showing one embodiment of a shaped film. FIG.

Several embodiments of the invention are described in detail below. However, the present invention is not limited to the following embodiments. As used herein, the term "(meth)acryl" means methacryl or acryl. The same applies to terms such as "(meth)acryloyl" and "(meth)acrylate".

A shaping film according to one aspect of the present disclosure includes a base material and a shaping layer laminated on the base material, and the shaping layer is a cured product of a photocurable composition containing a radically polymerizable component. (hereinafter also simply referred to as "cured material"). FIG. 1 schematically shows one embodiment of the shaped film. The shaping film 10 shown in FIG. 1 includes a base material 5 and a shaping layer 1 laminated on the base material 5. The shaping layer 1 is a cured product of a photocurable composition containing a radically polymerizable component. including. The shaping layer 1 may consist of only a cured product of the photocurable composition. Since the shaping layer is laminated so that the cured product and the substrate are in contact with each other, in the present specification, high adhesion of the cured product to the substrate means that the adhesiveness of the shaping layer to the substrate is high. synonymous with high. In the present specification, "adhesion of the cured product to the substrate" may be expressed as "adhesion of the cured product", and "adhesion of the imprint layer to the substrate" may be expressed as "adhesion of the imprint layer". These are sometimes simply referred to as "adhesion".

FIG. 2 schematically shows another embodiment of the shaped film. The shaping film 20 shown in FIG. 2 includes a base material 5 and a shaping layer 4 laminated on the base material 5. The shaping layer 4 is a cured product of a photocurable composition containing a radically polymerizable component. including. More specifically, the shaping layer 4 includes a first shaping layer 2 (also referred to as a primer layer), which is a cured product of a photocurable composition, and a second shaping layer 2 laminated on the first shaping layer 2. and a shaping layer 3 of The material of the second shaping layer 3 is not particularly limited as long as it is a material capable of forming a fine structure in the second shaping layer 3, and may be a material conventionally used for shaping films. Alternatively, the second shaping layer 3 may be a cured product of the same photocurable composition as the first shaping layer 2 . In the latter case, it can be said that the shaping layer 4 consists only of a cured product of a photocurable composition.

The shaping layer of the present disclosure may have a fine structure on its surface. For example, the shaping layer 1 in FIG. 1 may have a microstructure (not shown) on its surface. Similarly, the shaping layer 4 in FIG. 2, more precisely the second shaping layer 3 in FIG. 2, may have a microstructure (not shown) on its surface. In the present disclosure, the shape-imparting layer contains a cured product of a photocurable composition, and thus has high hardness. A shape-imparting layer having high hardness has good shape retention. Here, good shape retention means that the surface and side surfaces of the shaping layer are resistant to deformation and chipping. For example, one example of good shape retention is that the top of the fine structure optionally formed on the surface of the shaping layer is resistant to deformation and chipping.

Each of the shaping layers 1 and 4 may have a thickness of 0.5 μm or more or 1 μm or more, and may be 200 μm or less or 100 μm or less. When the shaping layer is thick, shaping into the shaping layer tends to be easy (that is, formation of a fine structure is facilitated), and when the shaping layer is thin, the haze of the shaping layer becomes small, The optical properties of shaped films tend to be excellent. When the thickness of the shaping layer is within the above range, both ease of shaping into the shaping layer and optical properties can be achieved at a higher level. When the shaping layer consists of two layers as in the embodiment shown in FIG. Well, the thickness of the second shaping layer 3 can be appropriately designed according to the thickness of the first shaping layer 2 .

The substrate may be a film of polycarbonate (PC), polyethylene terephthalate (PET), polyester, cycloolefin polymer (COP), polyimide, etc. PC film is preferred. Conventionally, the adhesion of the shaping layer to the PC film tends to be lower than the adhesion of the shaping layer to the PET film. The shaping layer of the shaping film according to the above aspects of the present disclosure exhibits excellent adhesion even when the substrate is a PC film. Although the thickness of the base material is not particularly limited, it is, for example, 10 to 125 μm.

The photocurable composition will be described below. The photocurable composition contains (A1) urethane acrylate and (A2) a nitrogen-containing monofunctional (meth)acrylic monomer as (A) radically polymerizable components. (A) The radically polymerizable component is radically polymerized by light irradiation to form a crosslinked polymer. This cures the photocurable composition.

(A1) Urethane acrylate Urethane acrylate (also referred to as "component (A1)") has two or more (meth)acryloyl groups. By containing such a urethane acrylate, the adhesion of the cured product to the base material is significantly strengthened. By combining with the component (A2), which will be described later, the shaping layer can maintain the adhesion to the substrate for a long time even under high temperature and high humidity conditions where the adhesion tends to decrease. Moreover, the hardness of hardened|cured material improves because a photocurable composition contains a urethane acrylate. Urethane acrylate is obtained, for example, by reacting a polyurethane chain, which is a polycondensate of polyol and polyisocyanate, with a monofunctional (meth)acrylic monomer having a hydroxyl group.

Examples of polyols used as raw materials for urethane acrylate include diols such as polycarbonate diols, polyester diols, polyether diols, and polycaprolactone diols. These polyols may be used singly or in combination of two or more. Generally, urethane acrylates obtained using polycarbonate diols, polyester diols, polyether diols, or polycaprolactone diols are referred to as polycarbonate urethane acrylates, polyester urethane acrylates, polyether urethane acrylates, or caprolactone urethane acrylates, respectively.

Examples of polyisocyanates used as raw materials for urethane acrylate include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, and hydrogenated tolylene diisocyanate. , hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, m-phenylene diisocyanate, biphenylene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate. These polyisocyanates may be used singly or in combination of two or more.

Monofunctional (meth)acrylic monomers having a hydroxyl group, which are used as raw materials for urethane acrylates, include, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylate. These (meth)acrylic monomers may be used singly or in combination of two or more.

As the urethane acrylate, a urethane acrylate having a polycarbonate (PC) structure is preferable, and a urethane acrylate having a PC structure and not having an alicyclic structure is more preferable. By using urethane acrylate having a PC structure, the adhesion of the imprinting layer is further enhanced. Moreover, by using a urethane acrylate that does not have an alicyclic structure, it is possible to obtain a cured product with high transparency (that is, small haze).

Although the weight average molecular weight of the urethane acrylate is not particularly limited, it is preferably 1,000 or more and 30,000 or less, more preferably 2,000 or more and 20,000 or less, and even more preferably 3,000 or more and 10,000 or less. When the weight-average molecular weight of the urethane acrylate is 1000 or more, the viscosity of the photocurable composition is favorable for roll-to-roll coating, and the coatability of the photocurable composition tends to improve. . When the weight-average molecular weight is 30,000 or less, the amount of diluent monomer that can be used to maintain coatability can be reduced, so that the hardness and adhesion of the cured product tend to be improved. The weight average molecular weight of the urethane acrylate can be adjusted, for example, by the molar ratio of polyol and polyisocyanate or their molecular weights. As used herein, the weight average molecular weight (Mw) is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC).

The number of (meth)acryloyl groups in the urethane acrylate is not particularly limited as long as it is 2 or more, but it is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. When the number of (meth)acryloyl groups in the urethane acrylate is within the above range, the adhesion of the imprinting layer to the substrate can be maintained for a longer period of time under high temperature and high humidity conditions.

The content of urethane acrylate in the photocurable composition may be 0.1 to 90% by mass based on the total amount of the radically polymerizable component. From the viewpoint of maintaining the adhesiveness of the imprinting layer for a longer period of time under high temperature and high humidity conditions, the content of the urethane acrylate may be 5 to 90% by mass based on the total amount of the radically polymerizable component. From the viewpoint of making the viscosity of the photocurable composition a value suitable for forming the imprinting layer, the content of the urethane acrylate may be 10 to 70% by mass based on the total amount of the radically polymerizable component. It may be up to 50% by mass, or 15 to 35% by mass. Also, the content of the urethane acrylate may be 0.1 to 50% by mass based on the total amount of the radically polymerizable component.

(A2) Nitrogen-containing monofunctional (meth)acrylic monomer A nitrogen-containing monofunctional (meth)acrylic monomer (also referred to as “(A2) component”) has only one (meth)acryloyl group and has a nitrogen atom. It is a monofunctional (meth)acrylic monomer with a functional group it contains. By including such a monofunctional (meth)acrylic monomer, the adhesion of the imprinting layer to the substrate can be improved from the physical and mechanical aspects. More specifically, by including this component, a chemical interaction occurs between the cured product and the substrate (physical aspect), and the cured product exhibits an anchoring effect on the substrate. (mechanical aspect), the adhesion of the cured product to the substrate is improved. Moreover, the hardness of the cured product is also improved.

Nitrogen-containing monofunctional (meth)acryl monomers include, for example, (meth)acrylamide, acryloylmorpholine, dialkylaminoalkyl(meth)acrylate and derivatives thereof, and (meth)acrylamide and derivatives thereof are preferred. The nitrogen-containing monofunctional (meth)acryl monomer may be a (meth)acrylamide derivative (including (meth)acrylamide) represented by the following general formula (3a) or (3b). In general formulas (3a) and (3b), R is a hydrogen atom or a methyl group. In general formula (3a), R ¹ and R ² each independently represent a monovalent group consisting of at least one atom selected from carbon, hydrogen and oxygen atoms. R ¹ and R ² may each independently be an alkyl group having 1 to 3 carbon atoms with or without a substituent, or a hydrogen atom, particularly a methyl group, an ethyl group, an isopropyl group or a hydroxyethyl group. There may be. R ¹ and R ² may each independently be a hydrogen atom or a methyl group. In general formula (3b), R ³ and R ⁴ each independently represent a divalent group consisting of at least one atom selected from carbon, hydrogen and oxygen atoms. R ³ , R ⁴ and nitrogen atom (N) may form a tetrahydro-1,4-oxazine ring.

Specific examples of nitrogen-containing monofunctional (meth)acrylic monomers include acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropylacrylamide, N,N-dimethylacrylamide, (meth)acryloylmorph Phosphorus, N-isopropylacrylamide, N,N-diethylacrylamide, and N-hydroxyethylacrylamide. These nitrogen-containing monofunctional (meth)acrylic monomers may be used singly or in combination of two or more.

The content of the nitrogen-containing monofunctional (meth) acrylic monomer in the photocurable composition may be 5 to 70% by mass, based on the total amount of the radically polymerizable component, and may be 5 to 40% by mass. It may be 5.5 to 30% by mass, or 6 to 25% by mass. When the content of the nitrogen-containing monofunctional (meth)acrylic monomer is within the above range, the hardness of the shaping layer can be improved, and the adhesion of the shaping layer to the substrate under high temperature and high humidity conditions. can be maintained for a longer time. Moreover, when the content of the nitrogen-containing monofunctional (meth)acrylic monomer is 40% by mass or less, the haze of the cured product can be made smaller than when the content exceeds 40% by mass.

(A3) Ethylene oxide-modified bisphenol A di(meth)acrylate The photocurable composition contains (A) as a radically polymerizable component, an ethylene oxide-modified bisphenol A di(meth)acrylate represented by the following general formula (1): It may further contain "EO-modified bisphenol A di(meth)acrylate" or "(A3) component"). By including such EO-modified bisphenol A di(meth)acrylate, the glass transition temperature (Tg) of the cured product is moderately improved, and the flexibility is moderately improved, so the adhesion of the cured product is further improved. do. In addition, since shrinkage during curing of the photocurable composition is alleviated, the adhesiveness of the cured product is maintained even when the curing reaction of the photocurable composition proceeds due to light irradiation and high-temperature treatment.

［式中、Ｒ^１及びＲ^２は、それぞれ独立に水素原子又はメチル基を示し、ｎ及びｍは、ｎ＋ｍ＝２０～４０となるように選ばれる正の整数を示す。］

[In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n and m represent positive integers selected so that n+m=20-40. ]

In the general formula (1), from the viewpoint of increasing the flexibility of the cured product, n and m are preferably positive integers selected so that n + m = 22 to 37, and n + m = 25 to 35. is more preferably a positive integer selected for . From the viewpoint of the photocurability of the photocurable composition and the Tg of the cured product of the photocurable composition, R ¹ and R ² are preferably hydrogen atoms. In other words, the compound represented by formula (1) is preferably EO-modified bisphenol A diacrylate.

Specific examples of the (A3) component include FA-323A (manufactured by Hitachi Chemical Co., Ltd.) and A-BPE-30 (manufactured by Shin-Nakamura Chemical Co., Ltd.). All of these are diacrylates of bisphenol A modified with ethylene oxide (EO), where n+m=30.

The content of the EO-modified bisphenol A di(meth)acrylate in the photocurable composition may be 0.1 to 20% by mass, preferably 5 to 19% by mass, based on the total amount of the radically polymerizable component. may be 10 to 15% by mass. When the content of the EO-modified bisphenol A di(meth)acrylate is 0.1% by mass or more, the flexibility is more suitable for obtaining excellent adhesion, and the photocurable composition is cured during curing. Shrinkage can be more relaxed. When the content of EO-modified bisphenol A di(meth)acrylate is 20% by mass or less, the Tg of the cured product can be maintained at a certain level or higher. When the Tg of the cured product is at least a certain level, it is possible to suppress deterioration in adhesion due to movement of the molecules of the cured product under high temperature conditions.

(A4) Alicyclic monofunctional (meth)acrylic monomer The photocurable composition contains an alicyclic monofunctional (meth)acrylic monomer (also referred to as “(A4) component”) as (A) a radically polymerizable component. It may contain further. An alicyclic monofunctional (meth)acrylic monomer is a monofunctional (meth)acrylic monomer having only one (meth)acryloyl group and having an alicyclic structure. By containing such a monofunctional (meth)acrylic monomer, shrinkage during curing of the photocurable composition is reduced, so that the curing reaction of the photocurable composition proceeds by light irradiation and high temperature treatment. Also, the adhesiveness of the cured product is maintained.

Examples of alicyclic structures include cyclohexyl skeleton, dicyclopentadiene skeleton, adamantane skeleton, isobornyl skeleton, cycloalkane skeleton (cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton, cycloundecane skeleton, cyclododecane skeleton, etc.), Cycloalkene skeletons (cycloheptene skeleton, cyclooctene skeleton, etc.), norbornene skeletons, norbornadiene skeletons, polycyclic skeletons (cubane skeleton, basketane skeleton, Hausan skeleton, etc.), spiro skeletons and the like can be mentioned. Among these, a cyclohexyl skeleton, a dicyclopentadiene skeleton, an adamantane skeleton, or an isobornyl skeleton is preferable from the viewpoint of maintaining the adhesiveness of the imprinting layer for a longer period of time under high-temperature conditions.

As the alicyclic monofunctional (meth)acrylic monomer, (meth)acrylates are preferable, and specifically, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth) Acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate and the like. Among these, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, or dicyclopentenyloxyethyl (meth)acrylate is preferable from the viewpoint of maintaining the adhesion of the imprinting layer for a longer time under high temperature conditions. . These may be used individually by 1 type, and may use 2 or more types together.

The content of the alicyclic monofunctional (meth)acrylic monomer in the photocurable composition is 0 based on the total amount of the radically polymerizable component, from the viewpoint of maintaining the adhesion of the imprinting layer for a longer period of time under high temperature conditions. .1 to 75 mass %, 0.1 to 70 mass %, 40 to 65 mass %, or 45 to 60 mass %. Also, from the same point of view, the content of the alicyclic monofunctional (meth)acrylic monomer may be 30 to 75% by mass, preferably 30 to 70% by mass, based on the total amount of the photocurable composition. 35 to 65% by mass, 40 to 60% by mass, or 45 to 57% by mass.

(A5) Polyfunctional (meth) acrylic monomer The photocurable composition includes, as (A) a radically polymerizable component, a polyfunctional (meth) acrylic monomer having two or more (meth) acryloyl groups ("(A5) component ”) may further be included. By containing such a polyfunctional (meth)acrylic monomer, the adhesion of the imprinting layer to the substrate can be maintained for a longer period of time under high temperature and high humidity conditions. In addition, the hardness of the cured product becomes higher. The (A5) component is a component that does not correspond to either the (A1) component or the (A3) component.

Polyfunctional (meth)acrylic monomers include, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(meth)acrylate, (Meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxypivalate ester neopentyl glycol di(meth) Acrylate, trimethylolpropane di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, α,ω-di(meth)acrylbisdiethylene glycol phthalate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth) ) acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(acryloxyethyl)isocyanurate, tris(methacryloxyethyl) Isocyanurate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol monohydroxypenta(meth)acrylate, polyglycerin polyacrylate, and alkylene oxide-modified poly(ethylene oxide-modified or propylene oxide-modified) thereof. Functional (meth)acrylates, and caprolactone-modified polyfunctional (meth)acrylates obtained by modifying these with caprolactone. These polyfunctional (meth)acrylic monomers may be used singly or in combination of two or more. Among these, polyethylene glycol di(meth)acrylate is preferred.

The content of the polyfunctional (meth)acrylic monomer in the photocurable composition is preferably 0.1 to 90% by mass, preferably 0.5 to 50% by mass, based on the total amount of the radically polymerizable component. is more preferable, and 1 to 40% by mass is even more preferable.

The photocurable composition may further contain (A) a radically polymerizable component other than the above components (A1) to (A5). Examples of (A) radically polymerizable components other than components (A1) to (A5) include diluted monomers such as tetrahydrofurfuryl acrylate and orthophenylphenoxyethyl acrylate. The content of radically polymerizable components other than components (A1) to (A5) may be 90% by mass or less, or 0.1 to 90% by mass, based on the total amount of the radically polymerizable component (A). 0.5 to 80% by mass, 1 to 75% by mass, or 1 to 50% by mass.

(B) Photopolymerization Initiator The photocurable composition further contains a photopolymerization initiator (also referred to as "(B) component") for efficient curing of the photocurable composition by photoradical polymerization. may be The photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization when irradiated with active energy rays. Examples of active energy rays include, for example, ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. Examples of photopolymerization initiators include benzophenone-based photopolymerization initiators, anthraquinone-based photopolymerization initiators, benzoyl-based photopolymerization initiators, sulfonium salt-based photopolymerization initiators, diazonium salt-based photopolymerization initiators, and onium salt-based photopolymerization initiators. A photopolymerization initiator such as an acylphosphine oxide-based photopolymerization initiator can be used. The photopolymerization initiator may be a photopolymerization initiator that initiates polymerization by abstracting hydrogen from the molecule.

Specific examples of photopolymerization initiators include benzophenone, 4-methylbenzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N,N',N' -tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, α-hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 1,2-benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, Aromatic ketone compounds such as 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin, methyl benzoin compounds such as benzoin and ethylbenzoin; benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, and benzoin phenyl ether; benzyl compounds such as benzyl and benzyl dimethyl ketal; fragrances such as 2,2-diethoxyacetophenone group ketone compounds; β-(acridin-9-yl) (meth) ester compounds of acrylic acid, 9-phenylacridine, 9-pyridylacridine, 1,7-diacridinoheptane and other acridine compounds; 2-(o- chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5- Diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-di( p-Methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methylmercaptophenyl)-4,5-diphenyl 2,4,5-triarylimidazole dimers such as imidazole dimers; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, α-aminoalkylphenone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propane; bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2, 4,6-trimethylbenzoyldiphenylphosphine oxide; and oligo(2-hydroxy-2-methyl-1-(4-(1-methylvinyl)phenyl)propanone). These compounds may be used singly or in combination of two or more.

The content of the photopolymerization initiator in the photocurable composition is 0.01 parts by mass or more, 0.1 parts by mass or more, or 0.5 parts by mass or more with respect to 100 parts by mass of the radically polymerizable component. It may be 10 parts by mass or less, 6 parts by mass or less, or 5 parts by mass or less. When the content of the photopolymerization initiator is within this range, particularly good photopolymerizability can be obtained.

(C) Phenolic antioxidant The photocurable composition may further contain a phenolic antioxidant (also referred to as "(C) component") having a structure represented by the following general formula (2): good. The phenol-based antioxidant suppresses thermal oxidative deterioration of the cured product, and thus has the effect of improving long-term reliability such as thermal yellowing of the cured product, adhesion of the imprint layer to the base material, and life of the polymer.

［式中、Ｒ^３は、ｔｅｒｔ－ブチル基又はメチル基を示す。］

[In the formula, R ³ represents a tert-butyl group or a methyl group. ]

Phenolic antioxidants include, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate], n-octadecyl-3-(4′-hydroxy-3′,5′-di-tert-butyl-phenyl)propionate, N,N′-hexane-1,6-diylbis [3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9 -bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5. 5] undecane, diethyl {[3,5-bis(1,1-dimethylethyl)-4-hydroxylphenyl]methyl}phosphonate, etc. These antioxidants may be used alone. Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate], or 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4, 8,10-tetraoxaspiro[5.5]undecane is preferred.

The content of the phenolic antioxidant in the photocurable composition is preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass as the total amount of the radically polymerizable component and the photopolymerization initiator.

(D) Light Stabilizer The photocurable composition may further contain a light stabilizer (ultraviolet absorber) (also referred to as “component (D)”). Examples of light stabilizers include radical scavengers such as thiol compounds, thioether compounds, and hindered amine compounds, or UV absorbers such as benzotriazole UV absorbers and hydroxyphenyltriazine (HPT) UV absorbers. can do. These light stabilizers may be used singly or in combination of two or more. Among them, HPT-based ultraviolet absorbers are preferable from the viewpoint of obtaining excellent adhesion, hardness, and light stability, and from the viewpoint of compatibility with the (meth)acrylic monomer contained in the photocurable composition.

Examples of HPT UV absorbers include 85% 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl and oxirane ( In particular, a 15% 1-methoxy-2-propanol solution (trade name: TINUVIN ( 400), 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidate Reaction product (trade name: TINUVIN 405), 2,4-bis "2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine (trade name: TINUVIN 460), TINUVIN 477, and TINUVIN 479 (both of which are manufactured by BASF Japan Ltd.) Among them, the (meth) acrylic monomer contained in the viewpoint of obtaining excellent photostability and the photocurable composition from the viewpoint of compatibility with TINUVIN 479. TINUVIN 479 is 4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]benzene-1,3 - is the reaction product of a diol with an alkyl 2-bromopropanoate, where the alkyl 2-{4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazine-2 -yl]-3-hydroxyphenoxy}propanoate as the main component, and the above “alkyl” refers to branched alkyl having 8 carbon atoms.

The content of the light stabilizer in the photocurable composition is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the radically polymerizable component and the photopolymerization initiator, from the viewpoint of preventing yellowing of the cured product at high temperatures. parts, more preferably 0.1 to 5 parts by mass.

The photocurable composition may further contain a release agent. Adding a mold release agent to a photocurable composition is useful when a mold is used to form a microstructure in a mold layer. The fine structure optionally formed in the shape-imparting layer can be transferred from the mold having the fine shape to the shape-imparting layer before curing, for example, when the photocurable composition contains a release agent. is easy to release the shaping layer from the mold. Release agents include, for example, polyether-modified polydimethylsiloxanes containing or not containing (meth)acryloyl groups. Among these, polyether-modified polydimethylsiloxane containing (meth)acryloyl groups is preferable from the viewpoint of suppressing bleeding out of the release agent from the cured product. The content of the release agent in the photocurable composition is preferably 0.1 to 1.0 parts by mass with respect to 100 parts by mass as the total amount of the radically polymerizable component and the photopolymerization initiator.

Additives such as silicone surfactants, thickeners, leveling agents, antistatic agents, and antifoaming agents may be further added to the photocurable composition, if necessary. good too. The total content of the additive and solvent in the photocurable composition may be, for example, 0.01 to 10 parts by mass with respect to 100 parts by mass as the total amount of the radically polymerizable component and the photopolymerization initiator. Even when the photocurable composition does not contain a solvent, the photocurable composition has a sufficiently low viscosity suitable for coating.

The viscosity of the photocurable composition at 25° C. is preferably 40 to 1000 mPa·s, more preferably 45 to 500 mPa·s. When the viscosity is within the above range, it is advantageous from the viewpoint of coatability of the photocurable composition and from the viewpoint of transferring the fine shape from the mold to the shaping layer. The viscosity can be adjusted, for example, by adjusting the amount of solvent, the molecular weight of each component, and the like.

The glass transition temperature (Tg) of the cured product of the photocurable composition is heat resistance (for example, when a shaped film is used as an optical sheet, heat resistance to heat from the surrounding environment, and the optical sheet It is preferably 20 to 90 ° C., from the viewpoint of heat resistance against heat dissipation of the display when used in the display) and from the viewpoint of maintaining the adhesion of the shaping layer for a long time under high temperature and high humidity conditions. 90°C is more preferred. As used herein, the glass transition temperature is measured using a dynamic rheometer.

The method for producing the shaped film is not particularly limited, and for example, the shaped film can be produced by the following production method. First, a coating film of the photocurable composition is formed by uniformly applying the photocurable composition to one surface (principal surface) of the substrate. Here, the coating film may be covered with a release film. Next, by curing the coating film by irradiating the coating film with an active energy ray from the substrate side, it is possible to obtain a shaped film in which the cured product of the photocurable composition is laminated on the substrate. can. Here, the light source is not particularly limited as long as it can sufficiently cure the photocurable composition, and a light source generally used for curing the photocurable composition, such as a metal halide lamp. can be used. The irradiation dose of the active energy ray is also not particularly limited as long as it can sufficiently cure the photocurable composition, and may be, for example, 1000 mJ/cm ² .

When the shaping layer consists of two layers as shown in FIG. 2, first, the first shaping layer can be formed on the substrate by the same method as described above. Next, the material for the second shaping layer is uniformly applied to the surface of the first shaping layer to form a coating film, and the coating is cured by a method according to the material for the second shaping layer. Thus, a shaped film in which the substrate, the first shaped layer, and the second shaped layer are laminated in this order can be obtained.

The shaping layer of the shaping film may have a fine structure, and the fine structure can be formed by a known method. For example, in any of the above production methods, the shape of the mold is transferred to the coating film by pressing a mold imitating the shape of the fine structure against the coating film before or simultaneously with the curing of the coating film. be able to. After curing, the coating becomes a shaping layer having a microstructure. The shape of the microstructure is appropriately designed according to the use of the shaped film.

Since the shaped film according to the above aspects of the present disclosure has excellent optical properties, it can be used, for example, as a prism sheet used for backlights of liquid crystal display devices, etc., as a lenticular lens sheet used for stereoscopic photography and projection screens, and as a condenser for projectors. It can be used for Fresnel lens sheets used for lenses and the like, or diffraction gratings used for color filters. In addition, the shaping film maintains the adhesion of the shaping layer even under high-temperature and high-humidity conditions, and also has excellent heat resistance. In addition, it can be suitably used as an optical sheet used for an in-vehicle display.

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

<Raw materials>
Table 1 shows the raw materials used to prepare the photocurable compositions in the following examples.

A1-3 in Table 1 were obtained as follows. 167.4 g of pentaerythritol tetraacrylate (Aronix M305: manufactured by Toagosei Co., Ltd.), 0.1 g of methoquinone, and 0.1 g of dibutyltin dilaurate were placed in a 300 mL flask, stirred uniformly, and heated to 75°C. After thermal stabilization at 75° C., 28.8 g of isophorone diisocyanate was added in 24 portions (1.2 g per portion) at intervals of 5 minutes. After the addition was complete, the reaction was completed by incubating at 75° C. for 4 hours. After completion of the reaction, pentaerythritol tetraacrylate was added, and the resulting A1-3 was confirmed to have a viscosity of 45 to 65 Pa·s at 25°C. The obtained A1-3 was a polyfunctional urethane acrylate having an alicyclic structure and no PC structure.

In Table 1, the weight average molecular weight Mw is a value converted from a calibration curve using standard polystyrene by the GPC method. The measurement conditions of the GPC method are as follows.
・ Apparatus: HLC-8320GPC manufactured by Tosoh Corporation (with built-in RI detector)
・Detector: RI (differential refractometer)
・Solvent: pure first class THF (tetrahydrofuran)
・Guard column: TSK-guardcolumn SuperMP (HZ)-H (1 piece)
・Guard column size: 4.6 mm (ID) x 20 mm
・ Column: TSK-GELSuperMultipore HZ-H manufactured by Tosoh Corporation (3 connected), column size: 4.6 mm (ID) × 150 mm
・Temperature: 40℃
・ Sample concentration: 0.01 g / 5 mL
・Injection volume: 10 μL
・Flow rate: 0.35mL/min

<Preparation of photocurable composition>
To 100 parts by mass of the radically polymerizable component in the blending ratio shown in Table 2, the other components in the amounts (parts by mass) shown in Table 3 were blended, and stirred at 60 ° C. for 1 hour, Examples 1 to 11 and Uniform photocurable compositions of Comparative Examples 1 to 4 were obtained. Numerical values in Tables 2 and 3 are parts by mass.

The viscosity of each photocurable composition was measured at 25° C. using a digital viscometer RE80R manufactured by Toki Sangyo Co., Ltd.

<Preparation of sample for evaluation of adhesion and pencil hardness>
Examples 1 to 11 and Comparative Example 1 were applied on a PC film having a thickness of 100 μm (manufactured by Mitsubishi Gas Chemical Co., Ltd., product name: Iupilon (registered trademark) Film FE-2000) so that the thickness of the cured product was 30 μm. Each of the photocurable compositions of 1 to 4 was uniformly applied. The formed coating film of the photocurable composition is covered with a release film having a thickness of 50 μm (manufactured by Fujimori Kogyo Co., Ltd., product name: Film Binah (registered trademark) BD), and is exposed from the PC film side using a metal halide lamp. The coating film was cured by irradiating with ultraviolet rays of 1000 mJ/cm ² .

<Preparation of sample for glass transition temperature evaluation>
Each of the photocurable compositions of Examples 1 to 11 and Comparative Examples 1 to 4 was uniformly applied onto a glass plate so that the thickness of the cured product was 100 μm. The formed photocurable composition layer is covered with a 50 μm thick release film (film binder BD), and a metal halide lamp is used to irradiate the coating film with ultraviolet rays of 1000 mJ/cm ² from the PC film side. Cured.

<Evaluation>
(1) Evaluation of Adhesion after Pressure Cooker Test A sample for evaluation of adhesion was cut to prepare a test piece having a length of 10 cm and a width of 5 cm (imprint layer (hardened product) thickness: 30 μm). Using a pressure cooker (PC-242SIII manufactured by Hirayama Seisakusho Co., Ltd.), the test piece was treated for a certain period of time under conditions of a temperature of 121° C., a pressure of 0.2 MPa, and a humidity of 100% RH (pressure cooker test, hereinafter abbreviated as PCT). A test piece was taken out from the pressure cooker every 25 hours, its appearance was observed, and the adhesion of the cured product (imprint layer) to the PC film (substrate) was evaluated. Adhesion was evaluated by a cross-cut peeling test according to JIS K 5600-5-6:1999. Specifically, first, a 10 mm×10 mm section in the test piece was cut with a cutter knife at intervals of 1 mm in a grid pattern. Cellophane tape (manufactured by Nichiban Co., Ltd., Cellotape (registered trademark)) was pressed against the cut portion, and the tape was peeled off at an angle of 45° by holding the edge of the tape. Observing the test piece, if the cured product is not peeled off from the substrate at any cut portion, it is determined that the cured product is “adhering”, and the cured product is peeled off from the substrate starting from the cut portion. When there was a place where there was a sticking point, the cured product was determined to be "not in close contact". PCT was repeated until the cured product was determined to be "not in close contact", and the time during which the cured product remained in close contact with the substrate was recorded. When the cured product had not already adhered 25 hours after the start of PCT, the time during which the adhered state was maintained was recorded as 0 hour. A test piece that maintains close contact for 50 hours or more from the start of PCT can be evaluated as maintaining the adhesion of the imprinting layer to the substrate for a long time even under high temperature and high humidity conditions. .

(2) Haze measurement The haze of the shaped layer (cured product) before PCT and 25 hours after the start of PCT of the test piece in (1) was measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd., model number: HGM-2). ), and the amount of change ΔHz in haze before and after the test was calculated. Specimens with a ΔHz between 0 and 1.5 can be rated as having excellent optical properties.

(3) Measurement of glass transition temperature A sample for glass transition temperature evaluation was cut to prepare a test piece having a length of 25 mm and a width of 10 mm. Using a dynamic viscoelasticity measuring device (manufactured by SII Nanotechnology Co., Ltd., model number: DMS6100), in "tensile sine wave mode", frequency 1 Hz, strain amplitude 0.05%, heating rate 3 ° C./min The maximum value (glass transition temperature) of the loss tangent (tan δ) of the test piece was measured under the following conditions.

(4) Measurement of Pencil Hardness The pencil hardness of the imprinting layer (cured product) in the sample for adhesion evaluation was measured according to JIS K 5600-5-4:1999. A pencil was applied to the main surface of the shaping layer at an angle of 45°, and the surface of the shaping layer was scratched while applying a load of 200 g. This was repeated 5 times with pencils of different hardnesses, and the hardest pencil was recorded among the pencils that did not leave scratches on the imprinting layer 4 or more times out of 5 times. A sample having a pencil hardness of 3B or more can be evaluated as having high hardness.

Table 4 shows the results of the above evaluation and measurement. In Table 4, the ratio of each component represents the blending amount (% by mass) based on the total amount of the radically polymerizable component. The shaped films of Examples 1 to 11, which comprise the cured product of the photocurable composition containing the combination of the components (A1) and (A2) as the shaping layer, are even after long-term severe temperature and humidity tests. , the high adhesion of the shaping layer and the excellent haze of the shaping layer were maintained. In addition, since the shaping films of Examples 1 to 11 have a shaping layer with high hardness, it is possible to maintain an excellent appearance. On the other hand, in the shaping films of Comparative Examples 1, 2 and 4, the adhesion of the shaping layer was remarkably lowered by the test under severe temperature and humidity conditions. Also, the shaping layer in the shaping film of Comparative Example 3 did not have sufficient hardness.

DESCRIPTION OF SYMBOLS 1, 4... Shaping layer, 2... 1st shaping layer, 3... 2nd shaping layer, 5... Base material, 10, 20... Shaping film.

Claims (20)

A shaping film comprising a substrate and a shaping layer laminated on the substrate,
The shaping layer comprises (A) a cured product of a photocurable composition containing a radically polymerizable component,
The (A) radically polymerizable component is
(A1) a urethane acrylate having two or more (meth)acryloyl groups;
(A2) a nitrogen-containing monofunctional (meth) acrylic monomer;
(A3) and an ethylene oxide-modified bisphenol A di(meth)acrylate represented by the following general formula (1) ,
The content of the (A3) ethylene oxide-modified bisphenol A di(meth)acrylate in the photocurable composition is 0.1 to 15% by mass based on the total amount of the radically polymerizable component (A). the film.

[In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n and m represent positive integers selected so that n+m=20-40. ] The shaped film according to claim 1, wherein the (A) radically polymerizable component further contains (A4) an alicyclic monofunctional (meth)acrylic monomer. 3. The shaped film according to claim 2 , wherein the (A4) alicyclic monofunctional (meth)acrylic monomer has a dicyclopentadiene skeleton. The excipient according to any one of claims 1 to 3 , wherein the (A) radically polymerizable component further comprises (A5) a polyfunctional (meth)acrylic monomer having two or more (meth)acryloyl groups. the film. The shaped film according to any one of claims 1 to 4 , wherein the (A1) urethane acrylate has a polycarbonate structure. The shaped film according to any one of claims 1 to 5 , wherein the photocurable composition further contains (B) a photopolymerization initiator. The shaped film according to any one of claims 1 to 6 , wherein the photocurable composition further contains (C) a phenolic antioxidant containing a structure represented by the following general formula (2): .

[In the formula, R ³ represents a tert-butyl group or a methyl group. ] The shaped film according to any one of claims 1 to 7 , wherein the photocurable composition further contains (D) a light stabilizer. Any one of claims 1 to 8 , wherein the content of the (A1) urethane acrylate in the photocurable composition is 0.1 to 50% by mass based on the total amount of the (A) radically polymerizable component. The shaped film described in . The content of the (A4) alicyclic monofunctional (meth) acrylic monomer in the photocurable composition is 30 to 75% by mass based on the total amount of the (A) radically polymerizable component, claim 2 or 3. The shaped film according to 3. The shaped film according to any one of claims 1 to 10 , wherein the substrate is a polycarbonate film. (A) A photocurable composition containing a radically polymerizable component,
The (A) radically polymerizable component is
(A1) a urethane acrylate having two or more (meth)acryloyl groups;
(A2) a nitrogen-containing monofunctional (meth) acrylic monomer;
(A3) and an ethylene oxide-modified bisphenol A di(meth)acrylate represented by the following general formula (1) ,
The content of the (A3) ethylene oxide-modified bisphenol A di(meth)acrylate in the photocurable composition is 0.1 to 15% by mass based on the total amount of the (A) radically polymerizable component. mold composition.

[In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and n and m represent positive integers selected so that n+m=20-40. ] 13. The photocurable composition according to claim 12 , wherein the (A) radically polymerizable component further contains (A4) an alicyclic monofunctional (meth)acrylic monomer. 14. The photocurable composition according to claim 13 , wherein the (A4) alicyclic monofunctional (meth)acrylic monomer has a dicyclopentadiene skeleton. The (A) radically polymerizable component further comprises (A5) a polyfunctional (meth) acrylic monomer having two or more (meth) acryloyl groups, photocuring according to any one of claims 12 to 14 . mold composition. The photocurable composition according to any one of claims 12 to 15 , wherein the (A1) urethane acrylate has a polycarbonate structure. (B) The photocurable composition according to any one of claims 12 to 16 , further comprising a photopolymerization initiator. The photocurable composition according to any one of claims 12 to 17 , further comprising (C) a phenolic antioxidant containing a structure represented by the following general formula (2).

[In the formula, R ³ represents a tert-butyl group or a methyl group. ] The photocurable composition according to any one of claims 12 to 18 , further comprising (D) a light stabilizer. The photocurable composition according to any one of claims 12 to 19 , which has a viscosity at 25°C of 40 to 1000 mPa·s.

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