TWI774814B - Shaped film and photocurable composition - Google Patents

Abstract

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

Description

Shaped film and photocurable composition

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

With the rapid development of display technologies such as liquid crystal display devices, the demand for optical sheets (optical films) used therein for those having new functions and higher quality is also increasing. As such an optical sheet, for example, a lens sheet used for backlights of liquid crystal display devices, etc., a lenticular lens sheet used for a 3D photograph, a projection screen, etc., a lens sheet for an overhead projector, etc. Fresnel lens sheets used in condenser lenses, etc., diffraction gratings used in color filters, etc., shaped films for lighting used in game machines, toys, home appliances, etc. . Such an optical sheet is also called a shaping film, and generally includes a base material and a shaping layer laminated on the base material. A fine shape is transferred to the shaping layer by a mold or the like, and desired optical properties are imparted.

With regard to the optical sheet, for example, the surface and side surfaces of the shaping layer such as the top portion of the fine structure may be deformed or chipped due to impact or vibration during production, and may be worn. The abrasion of such an optical sheet causes unevenness on the display surface of the display device and reduces the display performance. In order to improve such a problem, various proposals have been made regarding the material of the shaping layer (for example, refer to Patent Document 1). [Prior Art Document] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2011-21114

[The problem to be solved by the invention]

In recent years, the use of optical sheets in in-vehicle liquid crystal display devices has been increasing, and an optical sheet which is not only difficult to wear but also has excellent durability in a high temperature and high humidity environment is required. However, in the optical sheet disclosed in Patent Document 1, the adhesiveness of the shaping layer to the base material may decrease in an environment of high temperature and high humidity. An object of the present invention is to provide a shaped film including 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 to provide a shaped film for producing the shaped film light-hardening composition.

[Means of Solving Problems]

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

The said shaped film contains (A1) urethane acrylate having two or more (meth)acryloyl groups as (A) a radically polymerizable component, whereby the cured product (ie, shaped layer) can The adhesion of the material is greatly enhanced. Furthermore, by combining the component (A1) and the component (A2), the shaping layer can maintain the adhesiveness to the base material for a long period of time even under high temperature and high humidity conditions where the adhesive force tends to decrease. In addition, the hardness of the hardened material (ie, the shaping layer) increases. By containing the (A2) nitrogen-containing monofunctional (meth)acrylic monomer as a radically polymerizable component, the adhesiveness of the cured product to the base material can be improved in terms of physical and mechanical aspects. In addition, the hardness of the hardened product increases. The shaping film includes a shaping layer with high hardness, and can maintain the adhesion of the shaping layer to the substrate for a long time under high temperature and high humidity conditions, wherein, the shaping film includes a shaping layer having a The cured product of the photocurable composition of the combination of the above (A1) component and (A2) component.

The (A) radically polymerizable component may further include (A3) 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 to 40]

By including such a component, the shrinkage of the photocurable composition during curing is alleviated, and therefore, even if the photocurable composition is cured by light irradiation and high temperature treatment, the cured product can be maintained on the base material for a long time. of tightness. 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 include (A4) an alicyclic monofunctional (meth)acrylic monomer. By including such a component, the shrinkage of the photocurable composition during curing is alleviated, and therefore, even if the photocurable composition is cured by light irradiation and high temperature treatment, the cured product can be maintained on the base material for a long time. of tightness.

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

The (A) radically polymerizable component may further include (A5) a polyfunctional (meth)acrylic monomer having two or more (meth)acryloyl groups. By including such a component, the hardness of the shaping layer becomes higher, and the adhesion of the shaping layer to the base material can be maintained for a longer period of time under high temperature and high humidity conditions.

The (A1) urethane acrylate may also have a polycarbonate structure. Since urethane acrylate has a polycarbonate structure, the adhesiveness of the shaping layer to the base material becomes higher.

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，R³ 表示第三丁基或甲基] （C）酚系抗氧化劑具有如下效果：藉由抑制硬化物的熱氧化劣化來提高硬化物的耐熱黃變性、賦形層對基材的密接性及高分子的壽命等長期可靠性。The photocurable composition may further contain (C) a phenolic antioxidant containing a structure represented by the following general formula (2). [hua 2]

[wherein, R ³ represents a tertiary butyl group or a methyl group] (C) The phenolic antioxidant has the following effects: by suppressing the thermal oxidative deterioration of the cured product, the heat-resistant yellowing property of the cured product is improved, and the forming layer has the effect on the base material. long-term reliability such as adhesion and polymer life.

The photocurable composition may further contain (D) a light stabilizer. (D) The light stabilizer is useful for obtaining more excellent adhesion, hardness, and light stability of the shaping layer.

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

The content of the (A3) ethylene oxide-modified bisphenol A di(meth)acrylate in the photocurable composition may be based on the total amount of the (A) radically polymerizable components. It is 0.1 mass % - 20 mass %. When the content of ethylene oxide-modified bisphenol A di(meth)acrylate is equal to or greater than the lower limit value, more suitable flexibility can be imparted in order to obtain excellent adhesiveness, and photohardening can be further eased. shrinkage of the type composition upon hardening. Moreover, when content of ethylene oxide modified bisphenol A di(meth)acrylate is below the said upper limit, the glass transition temperature of hardened|cured material can be maintained at a fixed value or more. When the Tg of the cured product is a certain value or more, the decrease in adhesion due to molecular motion of the cured product under high temperature conditions can be suppressed.

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

The substrate can also be a polycarbonate film. The shaped layer of the shaped film of the aspect of the present disclosure exhibits excellent adhesiveness even if the base material is a polycarbonate film.

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

[式中，R¹ 及R² 分別獨立地表示氫原子或甲基，n及m表示以成為n+m=20～40的方式所選擇的正整數]The (A) radically polymerizable component may further include (A3) ethylene oxide-modified bisphenol A di(meth)acrylate represented by the following general formula (1). [hua 3]

[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 to 40]

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

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

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

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

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

[式中，R³ 表示第三丁基或甲基]The photocurable composition may further contain (C) a phenolic antioxidant containing a structure represented by the following general formula (2). [hua 4]

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

[Effect of invention]

According to the present invention, it is possible to provide a shaping layer comprising a high hardness and capable of being used for a long time (for example, under high temperature and high humidity conditions (for example, the temperature is above 85°C and the humidity is above 85% Relative Humidity, RH)). , 50 hours or more) a shaped film that maintains the adhesion of the shaped layer to the substrate, and a photocurable composition for producing the shaped film. In particular, the shaped film can maintain the adhesiveness of the shaped layer to the base material under high temperature and high humidity conditions for a long time even if the base material is a polycarbonate film.

Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In this specification, the term "(meth)acrylic group" represents a methacrylic group or an acrylic group. 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 includes a cured product of a photocurable composition containing a radically polymerizable component (hereinafter, also simply referred to as "hardening"). An embodiment of the shaped film is schematically shown in FIG. 1 . The shaping film 10 shown in FIG. 1 includes a base material 5 and a shaping layer 1 laminated on the base material 5 , and the shaping layer 1 includes a cured product of a photocurable composition containing a radically polymerizable component. The shaping layer 1 may contain only the hardened|cured material of a photocurable composition. The shaping layer laminates the cured product and the base material so as to be in contact with each other. Therefore, in this specification, high adhesion of the cured product to the base material and high adhesion of the shaping layer to the base material are synonymous. In this specification, "the adhesiveness of the cured product to the base material" is expressed as "the adhesiveness of the cured product", and the "adhesion of the shaping layer to the base material" is expressed as the "adhesion of the shaped layer", respectively. There are also cases where these abbreviations are referred to as "adhesion".

Another embodiment of the shaped film is schematically shown in FIG. 2 . The shaping film 20 shown in FIG. 2 includes a base material 5 and a shaping layer 4 laminated on the base material 5 , and the shaping layer 4 includes a cured product of a photocurable composition containing a radically polymerizable component. More specifically, the shaping layer 4 includes a first shaping layer 2 (also referred to as a primer layer) that is a cured product of the photocurable composition, and a second shaping layer laminated on the first shaping layer 2 Layer 3. 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 on the second shaping layer 3 , and may be a material used for a conventional shaping film. 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, the shaping layer 4 can also be said to include only a cured product of the photocurable composition.

The shaping layer of the present disclosure may also have a fine structure on the surface. For example, the shaping layer 1 in FIG. 1 may also have a fine structure (not shown) on the surface. Similarly, the shaping layer 4 in FIG. 2 , and more precisely, the second shaping layer 3 in FIG. 2 may also have a fine structure (not shown) on the surface. In the present disclosure, since the shaping layer includes a cured product of the photocurable composition, it has high hardness. The shape retention property of the shaping layer which has high hardness becomes favorable. Here, the term "good shape retention" means that the surface and side surfaces of the shaping layer are hardly deformed or chipped. For example, the top of the fine structure arbitrarily formed on the surface of the shaping layer is hardly deformed and chipped, and it is also an example of having good shape retention.

The thicknesses of the shaped layer 1 and the shaped layer 4 may both be 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, the shaping layer tends to be easily shaped (that is, a fine structure is easily formed), and when the shaping layer is thin, the haze of the shaping layer is reduced and the shaping film is excellent in optical properties Propensity. When the thickness of the shaping layer is within the above-mentioned range, it is possible to make the shaping layer easy to shape and the optical properties to coexist at a higher level. As in the embodiment shown in FIG. 2 , when the shaping layer includes two layers, the thickness of the first shaping layer 2 of the cured product containing the photocurable composition may be, for example, 1 μm to 5 μm, and the thickness of the first shaping layer 2 may be, for example, 1 μm to 5 μm. 2. The thickness of the shaping layer 3 can be appropriately designed according to the thickness of the first shaping layer 2.

The substrate can be polycarbonate (PC), polyethylene terephthalate (PET), polyester, cycloolefin polymer (COP), polyimide and other films. Preferably it is a PC film. 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 shaped layer of the shaped film of the aspect of the present disclosure exhibits excellent adhesiveness even if the base material is a PC film. The thickness of the base material is not particularly limited, but is, for example, 10 μm to 125 μm.

The photocurable composition will be described below. The photocurable composition contains (A1) urethane acrylate and (A2) 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 cross-linked polymer. Thereby, the photocurable composition is cured.

(A1) Urethane Acrylate

Urethane acrylate (also referred to as "(A1) component") has two or more (meth)acryloyl groups. By including such urethane acrylate, the adhesion of the cured product to the base material is greatly enhanced. Furthermore, by combining with the below-mentioned (A2) component, even under the conditions of high temperature and high humidity in which the adhesive force tends to decrease, the shaping layer can maintain the adhesiveness to the base material for a long time. In addition, when the photocurable composition contains urethane acrylate, the hardness of the cured product is improved. The urethane acrylate is obtained by reacting a monofunctional (meth)acrylic monomer having a hydroxyl group with a polyurethane chain which is a polycondensate of a polyol and a polyisocyanate, for example.

As a polyhydric alcohol used as a raw material of urethane acrylate, diols, such as polycarbonate diol, polyester diol, polyether diol, polycaprolactone diol, are mentioned, for example. These polyols may be used alone or in combination of two or more. In general, urethane acrylates obtained using polycarbonate diols, polyester diols, polyether diols, or polycaprolactone diols are referred to as polycarbonate acrylate urethanes, Polyester acrylate urethane, polyether acrylate urethane, or polycaprolactone acrylate urethane.

Examples of the polyisocyanate used as a raw material of urethane acrylate include tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. , tetramethyl xylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane Diisocyanates such as diisocyanate, isophenylene diisocyanate, biphenyl diisocyanate, and tetramethylene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

Examples of the monofunctional (meth)acrylic monomer having a hydroxyl group used as a raw material for urethane acrylate include 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate. , 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 1,4-cyclohexanedimethanol mono(meth)acrylic acid ester. These (meth)acrylic-type monomers may be used individually by 1 type, and may use 2 or more types together.

The acrylate urethane is preferably an acrylate urethane having a polycarbonate (PC) structure, and more preferably an acrylate urethane having a PC structure and no alicyclic structure. By using urethane acrylate having a PC structure, the adhesiveness of the shaping layer becomes higher. Moreover, by using the acrylic urethane which does not have an alicyclic structure, the hardened|cured material which has high transparency (that is, small haze) can be obtained.

The weight average molecular weight of the urethane acrylate is not particularly limited, but is preferably 1,000 or more and 30,000 or less, more preferably 2,000 or more and 20,000 or less, and still 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 becomes favorable for roll-to-roll coating, and the photocurable composition has a good viscosity. Tendency to improve coatability. If the weight average molecular weight is 30,000 or less, the amount of diluent monomers that can be used to maintain coatability is small, and therefore, the hardness and adhesiveness of the cured product tend to improve. The weight average molecular weight of urethane acrylate can be adjusted, for example, by the molar ratio of polyol and polyisocyanate, or the molecular weight of these. In the present specification, the weight average molecular weight (Mw) is a value converted from a calibration curve using standard polystyrene by a gel permeation chromatography (Gel Permeation Chromatography, GPC) method.

The number of (meth)acryloyl groups in the urethane acrylate is not particularly limited as long as it has two or more, but preferably six or less, more preferably four or less, and still more preferably three or less. When the number of (meth)acryloyl groups contained in the urethane acrylate is within the above range, the adhesion of the shaping layer to the substrate can be maintained for a longer period of time under high temperature and high humidity conditions .

The content of the urethane acrylate in the photocurable composition may be 0.1% by mass to 90% by mass based on the total amount of the radically polymerizable components. From the viewpoint of maintaining the adhesiveness of the shaping layer for a longer period of time under high temperature and high humidity conditions, the content of the urethane acrylate may be 5% by mass to the total amount of the radically polymerizable components. 90% by mass. From the viewpoint of setting the viscosity of the photocurable composition to a value suitable for forming the shaping layer, the content of the urethane acrylate may be 10% by mass to 70% by mass based on the total amount of the radically polymerizable components. %, 11-50 mass % may be sufficient, and 15-35 mass % may be sufficient. Moreover, content of urethane acrylate may be 0.1 mass % - 50 mass % based on the total amount of radically polymerizable components.

(A2) Nitrogen-containing monofunctional (meth)acrylic monomer Nitrogen-containing monofunctional (meth)acrylic monomer (also referred to as "(A2) component") has only one (meth)acryloyl group and a monofunctional (meth)acrylic monomer having a functional group containing a nitrogen atom. By including such a monofunctional (meth)acrylic monomer, the adhesiveness of the shaping layer to the base material can be improved from a physical point of view and a mechanical point of view. More specifically, by including these components, chemical interaction (physical aspect) occurs between the cured product and the base material, and the anchoring effect (mechanical aspect) of the cured product on the base material is exhibited, so the cured product The adhesion to the substrate is improved. In addition, the hardness of the hardened product is also improved.

Nitrogen-containing monofunctional (meth)acrylic monomers include, for example, (meth)acrylamido, acryl morpholine, (meth)acrylic acid dialkylamino alkyl esters, and derivatives thereof, and more Preferred are (meth)acrylamides and derivatives thereof. The nitrogen-containing monofunctional (meth)acrylic monomer may also be a (meth)acrylamide derivative (including (meth)acrylamide) represented by the following general formula (3a) or general formula (3b). . In the general formula (3a) and the general formula (3b), R is a hydrogen atom or a methyl group. In the general formula (3a), R ¹ and R ² each independently represent a monovalent group containing at least one atom selected from a carbon atom, a hydrogen atom, and an oxygen atom. R ¹ and R ² may each independently be a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, or a hydrogen atom, and in particular, may be a methyl group, an ethyl group, an isopropyl group or a hydroxyethyl group . R ¹ and R ² may each independently be a hydrogen atom or a methyl group. In the general formula (3b), R ³ and R ⁴ each independently represent a divalent group containing at least one atom selected from a carbon atom, a hydrogen atom, and an oxygen atom. R ³ , R ⁴ and nitrogen atom (N) can also form a tetrahydro-1,4-oxazine ring.

[hua 5]

Specific examples of nitrogen-containing monofunctional (meth)acrylic monomers include acrylamide, N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl Acrylamide, N,N-Dimethacrylamide, (Meth)acrylomorpholine, N-Isopropylacrylamide, N,N-Diethylacrylamide, and N-Hydroxyethyl base acrylamide. These nitrogen-containing monofunctional (meth)acrylic monomers may be used alone or in combination of two or more.

The content of the nitrogen-containing monofunctional (meth)acrylic monomer in the photocurable composition may be 5% by mass to 70% by mass, and may be 5% by mass to 40% by mass based on the total amount of radically polymerizable components %, 5.5 mass % - 30 mass % may be sufficient, and 6 mass % - 25 mass % may be sufficient. If the content of the nitrogen-containing monofunctional (meth)acrylic monomer is within the above range, the hardness of the shaping layer can be increased, and under high temperature and high humidity conditions, the shaping layer can be maintained to the base for a longer time. material adhesion. Moreover, when content of a nitrogen-containing monofunctional (meth)acrylic-type monomer is 40 mass % or less, compared with the case where content exceeds 40 mass %, the haze of hardened|cured material can be reduced.

(A3) Ethylene oxide modified bisphenol A di(meth)acrylate photocurable composition may further include modified ethylene oxide (EO) represented by the following general formula (1) Bisphenol A di(meth)acrylate (also referred to as "EO-modified bisphenol A di(meth)acrylate" or "(A3) component") serves as the (A) radically polymerizable component. By including such EO-modified bisphenol A di(meth)acrylate, the glass transition temperature (Tg) of the cured product is moderately improved, whereby the flexibility is moderately improved, and thus the adhesiveness of the cured product is further improved. In addition, the shrinkage at the time of curing the photocurable composition is alleviated, so even if the curing reaction of the photocurable composition proceeds by light irradiation and high temperature treatment, the adhesiveness of the cured product can be maintained.

[式中，R¹ 及R² 分別獨立地表示氫原子或甲基，n及m表示以成為n+m=20～40的方式所選擇的正整數][hua 6]

[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 to 40]

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

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

The content of the EO-modified bisphenol A di(meth)acrylate in the photocurable composition may be 0.1% by mass to 20% by mass, or 5% by mass to 19% by mass based on the total amount of the radically polymerizable components. The mass % may be 10 to 15 mass %. When the content of EO-modified bisphenol A di(meth)acrylate is 0.1 mass % or more, more suitable flexibility is provided in order to obtain excellent adhesiveness, and hardening of the photocurable composition can be further eased contraction of time. When the content of the EO-modified bisphenol A di(meth)acrylate is 20 mass % or less, the Tg of the cured product can be kept at a constant level or more. When the Tg of the cured product is a certain value or more, the decrease in adhesion due to molecular motion of the cured product under high temperature conditions can be suppressed.

(A4) Alicyclic monofunctional (meth)acrylic monomer The photocurable composition may further contain an alicyclic monofunctional (meth)acrylic monomer (also referred to as "(A4) component") as a (A) Radical polymerizable component. The alicyclic monofunctional (meth)acrylic monomer is a monofunctional (meth)acrylic monomer having only one (meth)acryloyl group and having an alicyclic structure. By including such a monofunctional (meth)acrylic monomer, the shrinkage at the time of curing of the photocurable composition is reduced. Therefore, even if the curing reaction of the photocurable composition is performed by light irradiation and high temperature treatment, Adhesion of the cured product can be maintained.

Alicyclic structures include, for example, cyclohexyl skeleton, dicyclopentadiene skeleton, adamantane skeleton, isobornyl skeleton, cycloalkane skeleton (cycloheptane skeleton, cyclooctane skeleton, cyclononane skeleton, cyclodecane skeleton , cycloundecane skeleton, cyclododecane skeleton, etc.), cycloolefin skeleton (cycloheptene skeleton, cyclooctene skeleton, etc.), norbornene skeleton, norbornadiene skeleton, polycyclic skeleton (cubicane skeleton, etc.) , basket alkane skeleton, room alkane skeleton, etc.), spiro skeleton, etc. 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 shaping layer for a longer period of time under high temperature conditions.

The alicyclic monofunctional (meth)acrylic monomer is preferably (meth)acrylate, and specifically, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, ( Adamantyl meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and the like. Among these, from the viewpoint of maintaining the adhesiveness of the shaping layer for a longer period of time under high temperature conditions, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, or (meth)acrylate are preferred. base) dicyclopentenyloxyethyl acrylate. These may be used individually by 1 type, and may use 2 or more types together.

From the viewpoint of maintaining the adhesiveness of the shaping layer for a longer period of time under high temperature conditions, the alicyclic monofunctional (meth)acrylic type in the photocurable composition is based on the total amount of the radically polymerizable components. The content of the monomer may be 0.1 to 75 mass %, 0.1 to 70 mass %, 40 to 65 mass %, or 45 to 60 mass %. In addition, from the same viewpoint, the content of the alicyclic monofunctional (meth)acrylic monomer may be 30% by mass to 75% by mass, and may be 30% by mass based on the total amount of the photocurable composition. % to 70 mass %, 35 to 65 mass %, 40 to 60 mass %, or 45 to 57 mass %.

(A5) Polyfunctional (meth)acrylic monomer The photocurable composition may further include a polyfunctional (meth)acrylic monomer having two or more (meth)acryloyl groups (also referred to as "( A5) Component") as (A) radically polymerizable component. By including such a polyfunctional (meth)acrylic monomer, the adhesion of the shaping 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 hardened product becomes higher. In addition, (A5) component is a component which does not correspond to neither (A1) nor (A3) component.

Examples of polyfunctional (meth)acrylic monomers include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol. Alcohol di(meth)acrylate, polyethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate (meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxytrimethylacetate, neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, 3 - Methylpentanediol di(meth)acrylate, bisdiethylene glycol phthalate α,ω-di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trihydroxy Methyl ethane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri- (Acryloyloxyethyl)isocyanurate, tris(methacryloyloxyethyl)isocyanurate, dipentaerythritol penta(meth)acrylate, di-trimethylolpropane tetraacrylic acid ester, dipentaerythritol monohydroxypenta (meth)acrylate, polyglycerol polyacrylate, and alkylene oxide modified polyfunctional (methyl) modified with ethylene oxide or propylene oxide. ) acrylates, and caprolactone-modified polyfunctional (meth)acrylates obtained by modifying these caprolactones. These polyfunctional (meth)acrylic monomers may be used alone or in combination of two or more. Among these, polyethylene glycol di(meth)acrylate is preferable.

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

The photocurable composition may further contain (A) radically polymerizable components other than the above-mentioned (A1) components to (A5) components. (A) radically polymerizable components other than (A1) component - (A5) component, diluent monomers, such as tetrahydrofurfuryl acrylate and acrylate o-phenylphenoxyethyl, are mentioned, for example. The content of the radical polymerizable components other than the components (A1) to (A5) may be 90% by mass or less, 0.1% by mass to 90% by mass, based on the total amount of the (A) radically polymerizable components. 0.5 mass % - 80 mass %, 1 mass % - 75 mass %, and 1 mass % - 50 mass % may be sufficient.

(B) Photopolymerization Initiator In order to efficiently harden the photocurable composition by photoradical polymerization, the photocurable composition may further contain a photopolymerization initiator (also referred to as "(B) Element"). The photopolymerization initiator is not particularly limited as long as it is a compound that starts radical polymerization when irradiated with active energy rays. Examples of active energy rays include ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. As the photopolymerization initiator, benzophenone-based photopolymerization initiators, anthraquinone-based photopolymerization initiators, benzyl-based photopolymerization initiators, perylene salt-based photopolymerization initiators, heavyweight Photopolymerization initiators such as azonium salt-based photopolymerization initiators, onium salt-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators. The photopolymerization initiator may also be a photopolymerization initiator that starts polymerization by extracting hydrogen in the molecule.

Specific examples of the photopolymerization initiator include benzophenone, 4-methylbenzophenone, N,N,N',N'-tetramethyl-4,4'-diaminobenzophenone Ketone (Michler's ketone), N,N,N',N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminodi Benzophenone, α-hydroxyisobutylphenone, 2-ethylanthraquinone, tert-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone Quinone, 3-chloro-2-methylanthraquinone, 1,2-benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thiaxanthone, 2- Chlorothiathanone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl-1-benzene Aromatic ketone compounds such as benzoin-1-one; benzoin compounds such as benzoin, methyl benzoin, ethyl benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin phenyl ether and other benzoin ether compounds; benzoin, benzene Benzil compounds such as azodimethyl ketal; aromatic ketone compounds such as 2,2-diethoxyacetophenone; β-(acridin-9-yl)(meth)acrylic acid ester compounds, 9 - Acridine compounds such as phenyl acridine, 9-pyridyl acridine, 1,7-diacridyl heptane; 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2 -(o-Chlorophenyl)-4,5-bis(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-bis(p-methoxyphenyl)-4,5-diphenylimidazole dimer Methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methylmercapto Phenyl)-4,5-diphenylimidazole dimer and other 2,4,5-triarylimidazole dimers; 2-benzyl-2-dimethylamino-1-(4-morpholinyl Phenyl)-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propane and other α-aminoalkylphenone compounds; bis( 2,4,6-Trimethylbenzyl)-phenylphosphine oxide and 2,4,6-trimethylbenzyldiphenylphosphine oxide; and oligo(2-hydroxy-2-methyl) base-1-(4-(1-methylvinyl)phenyl)acetone). These compounds may be used alone or in combination of two or more.

The content of the photopolymerization initiator in the photocurable composition may be 0.01 part by mass or more, 0.1 part by mass or more, or 0.5 part by mass or more, and may be 10 parts by mass relative to 100 parts by mass of the radically polymerizable component parts 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 favorable photopolymerization properties 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). This phenolic antioxidant has the effect of improving long-term reliability such as thermal yellowing resistance of the cured product, adhesion of the shaping layer to the base material, and life of the polymer by suppressing the thermal oxidative deterioration of the cured product.

[式中，R³ 表示第三丁基或甲基][hua 7]

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

Preferred examples of phenolic antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodieneethylbis[3-( 3,5-Di-tert-butyl-4-hydroxyphenyl)propionate], n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butyl-benzene yl) propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], hexamethylene bis[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-hydroxyphenyl]methyl}phosphonate and the like. These antioxidants may be used alone or in combination of two or more. Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] is preferred from the viewpoint of obtaining better thermal yellowing resistance and adhesion. , 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.

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

(D) Light stabilizer The light-curable composition may further contain a light stabilizer (ultraviolet absorber) (also referred to as "component (D)"). As the light stabilizer, for example, radical scavengers such as thiol-based compounds, thioether-based compounds, and hindered amine-based compounds, or benzotriazole-based ultraviolet absorbers and hydroxyphenyltriazine (HPT)-based ultraviolet absorbers can be used. and other UV absorbers. These light stabilizers may be used alone or in combination of two or more. Among them, HPT-based ultraviolet rays are preferred from the viewpoint of obtaining excellent adhesion, hardness, and light stability, and from the viewpoint of compatibility with the (meth)acrylic-based monomer contained in the photocurable composition. absorbent.

Examples of HPT-based ultraviolet absorbers include: 85% 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl 15% 1-Methoxy of the reaction product with oxiranes (especially [(alkyloxy)methyl]oxiranes, and the alkyloxy is C10-C16, mainly C12-C13) Alkyl-2-propanol solution (trade name: TINUVIN (registered trademark) 400), 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylene) (Trade name: TINUVIN 405), 2,4-bis[2- Hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine (trade name: TINUVIN 460), TINUVIN (TINUVIN) 477, and Dinubin (TINUVIN) 479 (both are manufactured by BASF (BASF) Japan Co., Ltd.). Among them, TINUVIN 479 is preferred from the viewpoint of obtaining excellent photostability and compatibility with the (meth)acrylic monomer contained in the photocurable composition. Dinubin (TINUVIN) 479 is 4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]benzene-1,3-diol and alkyl= The reaction product of 2-bromopropionate and the alkyl=2-{4-[4,6-bis(biphenyl-4-yl)-1,3,5-triazin-2-yl]-3 -Hydroxyphenoxy}propionate as the main component. The "alkyl" refers to a branched alkyl group having 8 carbon atoms.

From the viewpoint of preventing yellowing of the cured product caused by high temperature, the content of the light stabilizer in the photocurable composition with respect to 100 parts by mass of the total amount of the radically polymerizable component and the photopolymerization initiator It is preferably 0.01 to 10 parts by mass, 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 forming a fine structure in a shaping layer using a mold. The fine structure arbitrarily formed in the shaping layer can be transferred from a mold having a fine shape, for example, to the shaping layer before curing. When the photocurable composition contains a mold release agent, the shaping layer can be easily released from the mold. . The release agent includes, for example, a (meth)acryloyl group-containing polyether-modified polydimethylsiloxane or a (meth)acryloyl group-free polyether-modified polydimethylsiloxane. Among them, a polyether-modified polydimethylsiloxane containing a (meth)acryloyl group is preferable from the viewpoint of suppressing the oozing of the release agent from the cured product. The content of the mold release agent in the photocurable composition is preferably 0.1 part by mass to 1.0 part by mass relative to 100 parts by mass of the total of the radically polymerizable component and the photopolymerization initiator.

Additives such as silicone-based surfactants, tackifiers, leveling agents, antistatic agents, and antifoaming agents, as well as solvents, may be further added to the photocurable composition if necessary. The total content of additives and solvents in the photocurable composition may be, for example, 0.01 to 10 parts by mass relative to 100 parts by mass of the total of the radically polymerizable component and the photopolymerization initiator. Furthermore, when the photocurable composition does not contain a solvent, the viscosity of the photocurable composition has a sufficiently low viscosity suitable for coating.

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

From the viewpoint of heat resistance (for example, heat resistance to heat from the surrounding environment when the shaped film is used as an optical sheet, and heat resistance to heat dissipation of the display when the optical sheet is used for a display) and at high temperatures and From the viewpoint of maintaining the adhesiveness of the shaping layer for a long time under high humidity conditions, the glass transition temperature (Tg) of the cured product of the photocurable composition is preferably 20°C to 90°C, more preferably 40°C to 90°C . In this specification, the glass transition temperature is measured using a dynamic viscoelasticity measuring apparatus.

The manufacturing method of the said shaped film is not specifically limited, For example, the said shaped film can be manufactured by the following manufacturing method. First, a coating film of the photocurable composition is formed by uniformly coating the photocurable composition on one side (main surface) of the base material. Here, the coating film may be covered with a release film. Then, active energy rays are irradiated to the coating film from the side of the base material to harden the coating film, whereby a shaped film in which the cured product of the photocurable composition is laminated on the base material can be obtained. 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 a photocurable composition such as a metal halide lamp can be used. The irradiation amount of the active energy ray is not particularly limited as long as it is an amount that can sufficiently harden the photocurable composition, and may be, for example, 1000 mJ/cm ² .

When the shaping layer includes 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. Then, the material of the second shaping layer is uniformly coated on the surface of the first shaping layer to form a coating film, and is cured by a method corresponding to the material of the second shaping layer, thereby obtaining A shaped film in which the first shaped layer and the second shaped layer are laminated in this order.

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

The shaped film of the aspect of the present disclosure has excellent optical properties, and therefore, can be used, for example, for a lens sheet used in a backlight of a liquid crystal display device, etc., a lenticular lens sheet used in a 3D photograph, a projection screen, and the like, a film for a projector, etc. Frenanet lenses used in condenser lenses, etc., or diffraction gratings used in color filters. In addition, the shaping film maintains the adhesiveness of the shaping layer even under high temperature and high humidity conditions, and also has excellent heat resistance, so it can be used as an optical sheet other than an optical sheet used in game machines, toys, home appliances, and the like. Optical sheets used in in-vehicle monitors should be used appropriately. [Example]

Hereinafter, the present invention will be further specifically described with reference to Examples. However, the present invention is not limited to these Examples.

<Raw material> Table 1 shows the raw material used in order to prepare a photocurable composition in the following examples.

[Table 1]

A1-3 in Table 1 was obtained as follows. 167.4 g of pentaerythritol tetraacrylate (Aronix M305: manufactured by Toagosei Co., Ltd.), 0.1 g of methoxyphenol, and 0.1 g of dibutyltin dilaurate were added to a 300 mL flask, and the mixture was uniformly stirred. and heated to 75°C. After thermal stabilization at 75° C., 28.8 g of isophorone diisocyanate was added at 5-minute intervals in 24 times (1.2 g at a time). After the addition was completed, the reaction was completed by holding at 75°C for 4 hours. After completion of the reaction, pentaerythritol tetraacrylate was charged, and the viscosity at 25° C. of the obtained A1-3 was confirmed to be 45 Pa·s to 65 Pa·s. The obtained A1-3 is a polyfunctional acrylic urethane which has an alicyclic structure and does not have a 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.・Device: HLC-8320GPC (built-in refractive index (RI) detector) manufactured by Tosoh Co., Ltd. ・Detector: RI (differential refractometer) ・Solvent: pure grade 1 tetrahydrofuran (THF) ) Guard column: TSK-guardcolumn Super (Super) MP (HZ)-H (1 piece) Guard column size: 4.6 mm (ID) × 20 mm Column: Tosoh (Tosoh) ) TSK-GEL Super Multipore HZ-H (3 connections) manufactured by Co., Ltd., column size: 4.6 mm (ID) × 150 mm Temperature: 40°C Sample concentration: 0.01 g/5 mL Injection volume: 10 μL Flow rate: 0.35 mL/min

<Preparation of photocurable composition> The other components in the amounts (parts by mass) shown in Table 3 were blended with respect to 100 parts by mass of the radically polymerizable components in the blending ratios shown in Table 2, and stirred at 60° C. for 1 hours, the uniform photocurable compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were obtained. Numerical values in Table 2 and Table 3 are parts by mass.

[Table 2]

[table 3]

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 Adhesion and Pencil Hardness Evaluation> PC film (trade name: Iupilon (registered trademark) film by Mitsubishi Gas Chemical Co., Ltd. made by Mitsubishi Gas Chemical Co., Ltd.) with a thickness of 100 μm FE-2000), the photocurable compositions of Examples 1 to 11 and Comparative Examples 1 to 4 were uniformly coated so that the thickness of the cured product was 30 μm. The formed coating film of the photocurable composition was covered with a release film (trade name: FILMBYNA (registered trademark) BD, manufactured by Fujimori Kogyo Co., Ltd.) with a thickness of 50 μm, and a metal The halide lamp irradiated ultraviolet rays of 1000 mJ/cm ² from the PC film side, thereby curing the coating film.

<Preparation of samples for glass transition temperature evaluation> The photocurable types of Examples 1 to 11 and Comparative Examples 1 to 4 were uniformly coated on a glass plate so that the thickness of the cured product was 100 μm. composition. The layer of the photocurable composition formed was covered with a release film (FILMBYNA BD) with a thickness of 50 μm, and 1000 mJ/cm ² of ultraviolet rays were irradiated from the PC film side using a metal halide lamp. , thereby hardening the coating film.

<Evaluation> (1) Evaluation of Adhesion after Pressure Cooker Test A sample for evaluation of adhesion was cut to prepare a test piece with a length of 10 cm and a width of 5 cm (thickness of the shaping layer (hardened product): 30 μm) . Using a pressure cooker (PC-242SIII manufactured by Hirayama Seisakusho Co., Ltd.) under the conditions of temperature 121°C, pressure 0.2 MPa, and humidity 100% RH, the test piece was treated for a certain period of time (Pressure Cooker Test, hereinafter abbreviated as PCT) . The test piece was taken out from the pressure cooker every 25 hours, the external appearance was observed, and the adhesiveness of the cured product (shape layer) to the PC film (substrate) was evaluated. Adhesion was evaluated by the cross-cut peel test according to the specification of Japanese Industrial Standard (JIS) K 5600-5-6:1999. Specifically, first, the test piece was formed into a checkerboard shape by using a dicing blade to give knife marks at intervals of 1 mm to blocks of 10 mm×10 mm. A cellophane tape (Cellotape (registered trademark) manufactured by Nichiban Co., Ltd.) was pressed against the cut portion, and the tape was peeled off at an angle of 45° with the end of the tape. The test piece was observed, and when the cured product did not peel off from the base material in any of the knife marks, it was judged that the cured product was "adhered", and when there was a portion where the cured product peeled off from the base with the knife mark as a starting point, The hardened material was judged to be "not in close contact". PCT was repeatedly performed until it was determined that the cured product was "not in close contact", and the time in which the state of the cured product in close contact with the base material was maintained was recorded. When the cured product was not in close contact after 25 hours from the start of PCT, the time for which the adhered state was maintained was recorded as 0 hours. The test piece maintained in the state of being in close contact with each other for 50 hours or more from the PCT can be evaluated as maintaining the adhesion of the shaping layer to the base material for a long period of time even under high temperature and high humidity conditions.

(2) Measurement of haze Using a haze meter (Model: HGM-2, manufactured by Suga Testing Machine Co., Ltd.), the test piece in (1) was shaped before PCT and 25 hours after the start of PCT. The haze of the layer (hardened product) was measured, and the amount of change ΔHz in the haze before and after the test was calculated. A test piece having ΔHz of 0 to 1.5 can be evaluated as having excellent optical properties.

(3) Measurement of glass transition temperature The sample for glass transition temperature evaluation was cut, and a test piece having a length of 25 mm and a width of 10 mm was prepared. A dynamic viscoelasticity measuring device (Model: DMS6100 manufactured by SII Nano Technology Co., Ltd.) was used in the "stretching sine wave mode" at a frequency of 1 Hz, a strain amplitude of 0.05%, and a heating rate of 3°C/min. The maximum value (glass transition temperature) of the loss tangent (tanδ) of the test piece was measured under the same conditions.

(4) Measurement of pencil hardness According to the specification of JIS K 5600-5-4:1999, the pencil hardness of the shaping|molding layer (hardening degree) in the sample for adhesion evaluation was measured. The surface of the shaping layer was scribed while applying a load of 200 g with a pencil at an angle of 45° with respect to the main surface of the shaping layer. Each of the above operations was repeated 5 times with pencils with different hardnesses, and among the hardnesses of the pencils that did not leave scratches on the shaping layer 4 times or more of the 5 times, the hardest was recorded. A sample having a pencil hardness of 3 B or more can be evaluated as having high hardness.

The results of the above evaluation and measurement are shown in Table 4. In Table 4, the ratio of each component shows the compounding quantity (mass %) based on the total amount of radically polymerizable components. Tests of the shaped films of Examples 1 to 11 having a hardened product of a photocurable composition containing a combination of the (A1) component and the (A2) component as the shaped layer under severe temperature and humidity for a long time After that, the high adhesiveness of the shaping layer and the excellent haze of the shaping layer were also maintained. In addition, since the shaped films of Examples 1 to 11 include shaped layers with high hardness, excellent appearance can be maintained. On the other hand, with respect to the shaped films of Comparative Example 1, Comparative Example 2, and Comparative Example 4, the adhesiveness of the shaped layer was significantly decreased by the test under severe temperature and humidity. In addition, the shaped layer in the shaped film of Comparative Example 3 did not have sufficient hardness.

[Table 4]

1. 4‧‧‧Shaping layer 2‧‧‧First shaping layer 3‧‧‧Second shaping layer 5‧‧‧Substrate 10, 20‧‧‧Shaping film

FIG. 1 is a schematic cross-sectional view showing an embodiment of a shaped film. FIG. 2 is a schematic cross-sectional view showing an embodiment of a shaped film.

1‧‧‧Shaping layer

5‧‧‧Substrate

10‧‧‧Shaping film

Claims (21)

A shaping film comprising a base material and a shaping layer laminated on the base material, wherein the shaping layer includes a photocurable composition containing (A) a radically polymerizable component. A cured product, wherein the (A) radically polymerizable component includes (A1) urethane acrylate having two or more (meth)acryloyl groups, and (A2) nitrogen-containing monofunctional (meth)acrylic acid A monomer, the (A) radically polymerizable component further contains: (A3) 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 to 40. The shaped film according to claim 1, wherein the (A) radically polymerizable component further contains (A4) an alicyclic monofunctional (meth)acrylic monomer. The shaped film according to claim 2, wherein the (A4) alicyclic monofunctional (meth)acrylic monomer has a dicyclopentadiene skeleton. The shaped film according to any one of Claims 1 to 3, wherein the (A) radically polymerizable component further comprises: (A5) having two or more (meth)acrylonitrile based multifunctional (meth)acrylic monomers. The shaped film according to any one of claims 1 to 3, wherein the (A1) urethane acrylate has a polycarbonate structure. The shaped film according to any one of Claims 1 to 3, wherein the photocurable composition further contains (B) a photopolymerization initiator. The shaped film according to any one of claims 1 to 3, wherein the photocurable composition further contains (C) a phenol having a structure represented by the following general formula (2) antioxidant,

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 3, wherein the photocurable composition further contains (D) a light stabilizer. The shaped film according to any one of Claims 1 to 3, wherein, based on the total amount of the (A) radically polymerizable components, all the components in the photocurable composition The content of the (A1) urethane acrylate is 0.1% by mass to 50% by mass. The shaped film according to claim 1, wherein the (A3) ethylene oxide in the photocurable composition is based on the total amount of the (A) radically polymerizable component. The content of the modified bisphenol A di(meth)acrylate is 0.1% by mass to 20% by mass. The shaped film according to claim 2 or claim 3, wherein the (A4) in the photocurable composition is based on the total amount of the (A) radically polymerizable component. Content of an alicyclic monofunctional (meth)acrylic-type monomer is 30 mass % - 75 mass %. The shaped film according to any one of claims 1 to 3, wherein the substrate is a polycarbonate film. A photocurable composition comprising (A) a radically polymerizable component, wherein the (A) radically polymerizable component comprises: (A1) having two or more (meth)propylenes Acrylic urethane of an acyl group, and (A2) a nitrogen-containing monofunctional (meth)acrylic monomer, the (A) radically polymerizable component further comprises: (A3) the following general formula (1) represented by ethylene oxide modified bisphenol A di(meth)acrylate,

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 to 40. The photocurable composition according to claim 13, wherein the (A) radically polymerizable component further contains (A4) an alicyclic monofunctional (meth)acrylic monomer. The photocurable composition according to claim 14, wherein the (A4) alicyclic monofunctional (meth)acrylic monomer has a dicyclopentadiene skeleton. The photocurable composition according to any one of claims 13 to 15, wherein the (A) radically polymerizable component further comprises: (A5) having two or more (methyl groups) Acryloyl polyfunctional (meth)acrylic monomer. The photocurable composition according to any one of Claims 13 to 15, wherein the (A1) urethane acrylate has a polycarbonate structure. The photocurable composition according to any one of Claims 13 to 15, further comprising (B) a photopolymerization initiator. The photocurable composition according to any one of Claims 13 to 15, further comprising (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 according to any one of claims 13 to 15, further comprising (D) a light stabilizer. The photocurable composition according to any one of the 13th to 15th items in the scope of the application, whose viscosity at 25°C is 40mPa. s~1000mPa. s.

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