WO2023166823A1

WO2023166823A1 - Composition for forming cured film, curing agent, self-supporting film, and method for producing cured film

Info

Publication number: WO2023166823A1
Application number: PCT/JP2022/047026
Authority: WO
Inventors: 祐七島
Original assignee: リンテック株式会社
Priority date: 2022-03-01
Filing date: 2022-12-21
Publication date: 2023-09-07
Also published as: TW202340289A; JP2023127390A

Abstract

This composition for forming a cured film contains: an ethylene carbonate-containing acrylic monomer (A) having an ethylene carbonate structure represented by formula (1); and an active energy ray-curable compound (B) having a reactive group. The composition for forming a cured film can use carbon dioxide as a raw material for production, and can also be used to form a self-supporting film.

Description

Cured film-forming composition, cured film, self-supporting film, and method for producing cured film

The present invention relates to a composition for forming a cured film, a cured film, a self-supporting film, and a method for producing a cured film.

Conventionally, cured films obtained by curing curable compositions have been used in various fields and various products. For example, various displays such as liquid crystal displays (LCD) and organic EL displays (OELD), especially displays used as touch panels, are often provided with a cured film as a hard coat layer to prevent scratches. .

For example, Patent Document 1 describes, as a curable composition for forming a cured film (hard coat layer) as described above, an N-vinyl compound (A), a dialkylaminoalkyl (meth)acrylate (B1) and/or a dialkyl A compound (B) which is an aminoalkyl (meth)acrylamide (B2), a monoester (C1) of (meth)acrylic acid and an alcohol having 2 to 30 carbon atoms and/or (meth)acrylic acid and 5 carbon atoms It proposes an active energy ray-curable composition containing a compound (C) which is a monoamidated product (C2) with a monoamine of ∼30, a polyfunctional acrylate (D), and a photopolymerization initiator (E). .

JP 2020-196825 A

By the way, in recent years, along with the growing demand for building a recycling-based society, gases such as carbon dioxide, methane, and carbon monoxide are attracting attention as sustainable carbon raw materials. For example, it has been reported that an aliphatic polycarbonate having only aliphatic (non-aromatic) groups in the main chain can be produced by copolymerizing carbon dioxide and epoxide, and chemical products using gases such as carbon dioxide as raw materials and its manufacturing technology.

　Since carbon dioxide is said to cause global warming, the effective use of carbon dioxide emitted from factories in the process of manufacturing various materials is useful for environmental protection. It is even more desirable if carbon dioxide can be effectively used for the production of cured films.

The present invention has been made in view of such circumstances, and aims to provide a cured film-forming composition, a cured film, a self-supporting film, and a method for producing a cured film, which can use carbon dioxide as a production raw material. aim.

In order to achieve the above object, first, the present invention provides the following formula (1)

and an active energy ray-curable compound (B) having a reactive group. (Invention 1).

The composition for forming a cured film according to the above invention (Invention 1) can be produced using carbon dioxide as a production raw material, and therefore can effectively utilize carbon dioxide. Further, the cured film obtained by curing the cured film-forming composition by irradiation with active energy rays is a polymer of the active energy ray-curable compound (B) and the ethylene carbonate-containing acrylic monomer (A) and the active energy ray-curable Due to the three-dimensional network structure of the copolymer with the compound (B) and the higher-order structure due to the interaction between ethylene carbonates, the cohesive force is high and the coating strength is high.

In the above invention (invention 1), the ethylene carbonate-containing acrylic monomer (A) is preferably a compound represented by the following formula (2) or (3) (invention 2).

(In the formula, n represents an integer of 0 or more.)

(In the formula, n represents an integer of 0 or more.)

The cured film-forming composition according to the above inventions (inventions 1 and 2) preferably contains a photopolymerization initiator (C) (invention 3).

In the above inventions (Inventions 1 to 3), it is preferable that the number of reactive groups in the active energy ray-curable compound (B) is 2 or more (Invention 4).

In the above inventions (Inventions 1 to 4), the active energy ray-curable compound (B) preferably has an alkylene glycol chain (Invention 5).

In the above invention (Invention 5), the active energy ray-curable compound (B) has a (meth)acryloyl group, and the alkylene glycol chain is bonded to each of the (meth)acryloyl groups. (Invention 6).

In the above inventions (inventions 5 and 6), the number of repeating units of alkylene glycol in the alkylene glycol chain is preferably 1 or more and 20 or less (invention 7).

The cured film-forming compositions according to the above inventions (Inventions 1 to 7) are preferably solvent-free (Invention 8).

Secondly, the present invention provides a cured film (Invention 9) obtained by curing the cured film-forming composition (Inventions 1 to 8).

Thirdly, the present invention provides a self-supporting film (invention 10) comprising the cured film (invention 9). As used herein, the term "self-supporting membrane" refers to a membrane that is strong enough to be handled independently without being damaged and that can maintain its shape without a support.

In the fourth aspect of the present invention, the cured film-forming composition (inventions 1 to 8) is applied to a first sheet, a second sheet is laminated on the coating film of the cured film-forming composition, and the second sheet is laminated on the coating film of the cured film-forming composition. A method for producing a cured film, comprising irradiating an active energy ray through the first sheet or the second sheet to cure the cured film-forming composition to form a cured film (Invention 11 ).

According to the present invention, it is possible to provide a composition for forming a cured film, a cured film, a self-supporting film, and a method for producing a cured film that can use carbon dioxide as a production raw material.

Embodiments of the present invention will be described below.
[Composition for forming cured film]
The cured film-forming composition according to one embodiment of the present invention (hereinafter sometimes referred to as “cured film-forming composition X”) is represented by the following formula (1)

Contains an ethylene carbonate-containing acrylic monomer (A) having an ethylene carbonate structure shown in and an active energy ray-curable compound (B) having a reactive group, preferably further containing a photopolymerization initiator (C) .

Ethylene carbonate-containing acrylic monomer (A), as disclosed in JP-A-2006-335971, by introducing a carbonate group by adding CO ₂ to the epoxy group of (meth)acrylate having an epoxy group can be manufactured. That is, the cured film-forming composition X according to the present embodiment using the ethylene carbonate-containing acrylic monomer (A), and the cured film and self-supporting film obtained by curing the cured film-forming composition X contain carbon dioxide. can be produced as a production raw material, and therefore effective utilization of carbon dioxide can be achieved. In this specification, (meth)acrylate means both acrylate and methacrylate. The same applies to other similar terms.

When the cured film-forming composition X according to the present embodiment is cured by irradiation with active energy rays, the active energy ray-curable compounds (B) having reactive groups react with each other and polymerize. It also reacts with the ethylene carbonate-containing acrylic monomer (A) and the active energy ray-curable compound (B) for copolymerization. It is believed that these polymers are entangled with each other to form a three-dimensional network structure. Further, the ethylene carbonate structure of the ethylene carbonate-containing acrylic monomer (A) remains as it is after curing, and this ethylene carbonate structure is characterized by strong interaction between ethylene carbonates. Therefore, a higher-order structure is formed by interaction between the above-mentioned three-dimensional network structure and ethylene carbonate, and a cured film containing the higher-order structure has high cohesion and exhibits high film strength.

1. Components of cured film-forming composition (1) Ethylene carbonate-containing acrylic monomer (A)
The ethylene carbonate-containing acrylic monomer (A) is not particularly limited as long as it contains an ethylene carbonate structure and has a (meth)acryloyl group (structure). Preferred examples of the ethylene carbonate-containing acrylic monomer (A) include (meth)acrylic acid esters having a structure in which an organic group having an ethylene carbonate structure and a (meth)acryloyloxy group are bonded. Examples of such (meth)acrylic acid esters include the following formula (2)

Acrylic acid ester represented by, or the following formula (3)

The methacrylic acid ester represented by is mentioned. In both formulas (2) and (3), n represents an integer of 0 or more. Among the (meth)acrylic acid esters represented by the above formulas (2) and (3), a (meth)acrylic acid ester in which n is 1 or more is preferable, and a (meth)acrylic acid ester in which n is 2 or more is preferred. When n is 1 or more, the ethylene carbonate group is present at a relatively distant position from the polymer, increasing the probability that the ethylene carbonate structures present in the resulting cured film overlap with each other. As a result, the stacking interaction between the ethylene carbonate structures works, the cohesive force becomes stronger, and the film strength of the resulting cured film becomes higher. The upper limit of n is not particularly limited, but from the viewpoint of polymerizability, it is preferably 10 or less, more preferably 6 or less, particularly preferably 4 or less, and further preferably 3 or less. is preferred. Among these, from the viewpoint of favorable mechanical properties of the resulting cured film, (meth)acrylic acid esters where n = 1 are preferred, and in particular, methacrylic acid (2-oxo- 1,3-dioxolan-4-yl)methyl is preferred. In addition, the ethylene carbonate-containing monomer may be used alone or in combination of two or more.

The cured film-forming composition X according to the present embodiment may contain one type of the ethylene carbonate-containing acrylic monomer (A) described above, or may contain two or more types. . Moreover, the composition X for forming a cured film according to the present embodiment may contain another acrylic monomer together with the ethylene carbonate-containing acrylic monomer (A) described above.

(2) Active energy ray-curable compound (B)
The active energy ray-curable compound (B) having a reactive group is not particularly limited as long as it polymerizes and cures via the reactive group when irradiated with an active energy ray.

The number of reactive groups of the active energy ray-curable compound (B) may be 1 or more, but preferably 2 or more. When the number of reactive groups is 2 or more, the reactivity is increased, and a three-dimensional network structure with high density is formed when the active energy ray-curable compound (B) is cured. Higher coating strength. From the above viewpoint, the number of reactive groups in the active energy ray-curable compound (B) is more preferably 2 or more, particularly preferably 3 or more, and further preferably 4 or more. On the other hand, the upper limit of the number of reactive groups in the active energy ray-curable compound (B) is not particularly limited, but from the viewpoint of curing shrinkage suppression, it is preferably 100 or less, more preferably 50 or less, and particularly 30. It is preferably 12 or less, more preferably 12 or less.

The active energy ray-curable compound (B) preferably has an alkylene glycol chain in addition to the reactive group. Since the alkylene glycol chain is highly flexible, brittleness is alleviated by including an appropriate amount of the active energy ray-curable compound (B) having an alkylene glycol chain, and the resulting cured film tends to be a self-supporting film with desired strength. . Further, when the active energy ray-curable compound (B) has an alkylene glycol chain, the resulting cured film shrinks on the opposite surface side when moisture such as water droplets comes into contact with one surface, and dries. It can be a self-supporting film with a unique property of returning to its original state when moisture is removed.

The conventional cured film disclosed in Patent Document 1 and the like mentioned above is premised on being formed by applying a curable composition to a substrate such as a plastic film and curing the composition. However, if the cured film itself can become a self-supporting film as described above, no substrate is required, and productivity can be improved and costs can be reduced.

When the active energy ray-curable compound (B) has 2 or more reactive groups and has an alkylene glycol chain, the alkylene glycol chain functions as a spacer between a plurality of reactive groups. As a result, the resulting cured film has a relatively low storage modulus and is excellent in flexibility while maintaining high film strength.

The number of alkylene glycol repeating units in the alkylene glycol chain is preferably 1 or more, more preferably 2 or more, particularly preferably 5 or more, and further preferably 10 or more. This makes it possible to sufficiently ensure the flexibility of the cured film. The number of repeating units of the alkylene glycol is preferably 20 or less, more preferably 18 or less, particularly preferably 15 or less, and further preferably 14 or less. Thereby, the strength of the film can be sufficiently maintained.

Examples of the alkylene in the alkylene glycol chain include ethylene, propylene, and butylene, among which ethylene or propylene is preferred, and ethylene is particularly preferred. That is, the alkylene glycol chain is particularly preferably an ethylene glycol chain. Specific examples of the active energy ray-curable compound (B) having an alkylene glycol chain include bifunctional acrylates such as polyethylene glycol diacrylate and tetrafunctional acrylates such as ethoxylated pentaerythritol tetraacrylate.

Specific examples of the active energy ray-curable compound (B) preferably include polyfunctional (meth)acrylate monomers, (meth)acrylate prepolymers, etc. Among them, polyfunctional (meth)acrylate monomers are particularly preferred. preferable. A polyfunctional (meth)acrylate-based monomer and a (meth)acrylate-based prepolymer may be used alone, or both may be used in combination.

Examples of polyfunctional (meth)acrylate monomers include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, (Meth)acrylates, neopentylglycol hydroxypivalate di(meth)acrylate, dicyclopentanyl di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate (meth)acrylates, ethylene oxide-modified phosphoric acid di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, ethylene oxide isocyanurate-modified di(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate ) acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tris(acryloxy Ethyl)isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, etc. Functional (meth)acrylates may be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(Meth)acrylate-based prepolymers include, for example, polyester acrylate-based, epoxy acrylate-based, urethane acrylate-based, and polyol acrylate-based prepolymers.

When the active energy ray-curable compound (B) is a polyfunctional (meth)acrylate-based monomer, it is preferable that each (meth)acryloyl group has an alkylene glycol chain bonded thereto. Particularly preferred active energy ray-curable compounds (B) include hexafunctional acrylates represented by the following formula (4).

... (4)
(Wherein, m, n, p, q, r and s each represent an integer of 0 or more and may be independently the same or different.)

The active energy ray-curable compound (B) represented by the above formula (4) has high reactivity and satisfactorily exhibits the spacer function of the alkylene glycol chain, so that a highly flexible cured film can be obtained.

The preferred ranges of m, n, p, q, r and s in the above formula (4) are as described above as the number of alkylene glycol repeating units in the alkylene glycol chain.

The content of the active energy ray-curable compound (B) in the cured film-forming composition X is preferably 5 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the ethylene carbonate-containing acrylic monomer (A). It is more preferably 20 parts by mass or more, and more preferably 30 parts by mass or more. In addition, the content of the active energy ray-curable compound (B) is preferably 90 parts by mass or less and 80 parts by mass or less with respect to 100 parts by mass of the (meth)acrylate polymer (A). is more preferably 75 parts by mass or less, and more preferably 70 parts by mass or less. When the content of the active energy ray-curable compound (B) is within the above range, a cured film having high film strength can be effectively obtained. Moreover, when the active energy ray-curable compound (B) has an alkylene glycol chain, it is possible to effectively obtain a self-supporting film having good mechanical properties.

(3) Photopolymerization Initiator When ultraviolet light is used to cure the cured film-forming composition according to the present embodiment, the cured film-forming composition X preferably contains a photopolymerization initiator (C). By containing the photopolymerization initiator (C), the ethylene carbonate-containing acrylic monomer (A) and the active energy ray-curable compound (B) can be efficiently polymerized, and the polymerization curing time and the irradiation amount of ultraviolet rays can be reduced. can be reduced.

Examples of such photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylaminobenzophenone, dichloro Benzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4- Diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo[2-hydroxy-2-methyl-1[4-(1-methylvinyl)phenyl]propanone], 2,4,6- and trimethylbenzoyl-diphenyl-phosphine oxide. These may be used alone or in combination of two or more.

The content of the photopolymerization initiator (C) in the cured film-forming composition X is preferably 1 part by mass or more, particularly 2 parts by mass, with respect to 100 parts by mass of the active energy ray-curable compound (B). parts by mass or more, and more preferably 3 parts by mass or more. The content of the photopolymerization initiator (C) is preferably 20 parts by mass or less, particularly preferably 15 parts by mass or less, relative to 100 parts by mass of the active energy ray-curable compound (B). , and more preferably 10 parts by mass or less.

(4) Various Additives The cured film-forming composition X may optionally contain various additives such as colorants, flame retardants, plasticizers, antistatic agents, lubricants, fillers, ultraviolet absorbers, light stabilizers, and the like. may contain.

The cured film-forming composition X may or may not contain a diluent solvent. Since the composition X for forming a cured film contains the components described above as main components, it can be applied by a normal coating method to form a coating film without using a diluent solvent. Since the composition X for forming a cured film does not contain a diluent solvent, it does not release a volatile organic compound during the formation of a cured film. Therefore, in addition to efficient use of carbon dioxide, it is more helpful for environmental protection.

2. Preparation of Cured Film-Forming Composition The ethylene carbonate-containing acrylic monomer (A) is produced by introducing a carbonate group by adding CO ₂ to the epoxy group of a (meth)acrylate having an epoxy group, as described above. be able to. The cured film-forming composition X is prepared by mixing an ethylene carbonate-containing acrylic monomer (A) and an active energy ray-curable compound (B), and optionally adding a photopolymerization initiator (C) and additives. can be prepared by

The viscosity of the cured film-forming composition X thus prepared is usually preferably 10 mPa·S ⁻¹ or more at a shear rate of 10 S ⁻¹ , particularly preferably 100 mPa·S ⁻¹ or more. , and more preferably 200 mPa·S ⁻¹ or more. Further, it is preferably 15000 mPa·S ⁻¹ or less, particularly preferably 10000 mPa·S ⁻¹ or less, further preferably 5000 mPa·S ⁻¹ or less. This makes it easy to form a cured film having excellent coatability and a desired film thickness.

[Cured film]
A cured film according to one embodiment of the present invention is formed by curing the composition for forming a cured film according to the above-described embodiment. Preferably, it is formed by irradiating the coating film of the composition X for forming a cured film with an active energy ray to cure the composition X for forming a cured film.

The thickness of the cured film according to the present embodiment is appropriately set according to its intended use, but is usually preferably 0.1 μm or more and 300 μm or less. When the cured film according to the present embodiment is a hard coat layer, the thickness is usually preferably 0.1 µm or more, more preferably 1 µm or more, and particularly preferably 5 µm or more. Also, the thickness is preferably 20 μm or less, more preferably 15 μm or less. When the cured film according to this embodiment is a hard coat layer, it is preferable that the cured film according to this embodiment is laminated on various substrates.

The cured film according to this embodiment is also preferably a self-supporting film. In the case of a self-supporting film, since it exists by itself without being damaged and can be handled, there is no need for a substrate or the like, and productivity can be improved and costs can be reduced. When the cured film according to the present embodiment is a self-supporting film, the thickness of the cured film is preferably 10 μm or more, more preferably 25 μm or more. Also, the thickness is preferably 300 μm or less, more preferably 200 μm or less, particularly preferably 150 μm or less, further preferably 100 μm or less.

1. Physical Properties of Cured Film (1) Gel Fraction The gel fraction of the cured film according to the present embodiment is preferably 70% or more, more preferably 75% or more, and particularly preferably 80% or more. Preferably, it is 85% or more. In addition, the gel fraction is preferably 100% or less, more preferably 99% or less, particularly preferably 98.5% or less, and further preferably 98.0% or less. preferable. In addition, the method for measuring the gel fraction of the cured film in the present specification is as described in the test examples described later.

(2) Tensile strength The tensile strength at 23 ° C. of the cured film according to the present embodiment is appropriately set according to the purpose of use, but it is usually preferably 5 MPa or more, more preferably 10 MPa or more. It is preferably 30 MPa or more, and more preferably 50 MPa or more. Further, the tensile strength is preferably 1500 MPa or less, more preferably 1000 MPa or less, particularly preferably 800 MPa or less, further preferably 600 MPa or less. The method for measuring the tensile strength of the cured film in this specification is as described in the test examples described later.

(3) Breaking elongation rate The breaking elongation rate at 23°C of the cured film according to the present embodiment is appropriately set according to its intended use, but is usually preferably 1% or more, and 3% or more. more preferably 5% or more, and more preferably 8% or more. The elongation at break is preferably 100% or less, more preferably 80% or less, particularly preferably 60% or less, and further preferably 50% or less. The method for measuring the elongation at break of the cured film in this specification is as described in the test examples described later.

(4) Storage elastic modulus The storage elastic modulus E′(30) at 30° C. of the cured film according to the present embodiment is appropriately set according to its intended use, but is usually 0.1 GPa or more. It is preferably 0.15 GPa or more, more preferably 0.20 GPa or more, and further preferably 0.25 GPa or more. The storage modulus E'(30) is preferably 10 GPa or less, more preferably 9 GPa or less, particularly preferably 8 GPa or less, and further preferably 7 GPa or less. The method for measuring the storage elastic modulus E' of the cured film in the present specification is as described in the test examples described later.

The storage elastic modulus E′(100) at 100° C. of the cured film according to the present embodiment is appropriately set according to its intended use, but is usually preferably 0.05 GPa or more, and 0.10 GPa or more. It is more preferably 0.15 GPa or more, and more preferably 0.20 GPa or more. In addition, the storage modulus E′(100) is preferably 6.0 GPa or less, more preferably 5.5 GPa or less, particularly preferably 5.0 GPa or less, and further 4.5 GPa. The following are preferable.

(5) Pencil hardness The pencil hardness of the cured film according to the present embodiment is appropriately set according to its intended use, but is usually preferably 6B or more, particularly preferably 5B or more, and further is preferably 4B or more. The pencil hardness is preferably 7H or less, particularly preferably 6H or less, and more preferably 5H or less. In addition, the method for measuring the pencil hardness is as shown in the test examples described later.

(6) Total light transmittance The total light transmittance of the cured film according to the present embodiment is appropriately set according to its intended use, but is usually preferably 90% or more, and 91.0% or more. is more preferably 91.5% or more, and more preferably 92.0% or more. Although the upper limit of the total light transmittance is not particularly limited, it is usually 100% or less, preferably 99.9% or less, particularly preferably 99.5% or less, and further 99.0%. The following are preferable. The total light transmittance in this specification is a value measured according to JIS K7361-1:1997.

(7) Haze value The haze value of the cured film according to the present embodiment is appropriately set according to its intended use, but is usually preferably 5% or less, more preferably 4% or less. , particularly preferably 3% or less, more preferably 2% or less. Although the lower limit of the haze value is not particularly limited, it is usually 0% or more, preferably 0.05% or more, particularly preferably 0.10% or more, and further preferably 0.15% or more. Preferably. In addition, the haze value in this specification is a value measured according to JIS K7136:2000.

(8) Surface resistance value The surface resistance value of the cured film according to the present embodiment is appropriately set according to its intended use, but is usually 1.0 × 10 ¹⁰ Ω / sq or more, 1.0 × 10 ¹⁶ Ω/sq or less. Incidentally, the method for measuring the surface resistance value in the present specification is as shown in the test examples described later.

(9) Flexibility When the cured film according to the present embodiment is formed to have a width of 25 mm, a length of 100 mm, and a thickness of 50 μm, and is bent at 23° C. for 10 seconds, problems such as breakage and cracks do not occur. The minimum bending diameter (diameter) is preferably 10 mm or less, more preferably 8 mm or less, particularly preferably 6 mm or less, further preferably 4 mm or less. This makes it excellent in flexibility and suitable for bending applications. The method for measuring the minimum bending diameter in this specification is as shown in the test examples described later.

2. Method for Producing Cured Film The cured film according to the present embodiment can be formed by irradiating the coating film of the composition for forming a cured film according to the above-described embodiment with an active energy ray to cure the coating film. preferable. Specifically, the cured film-forming composition X is applied to a first sheet, the second sheet is laminated on the resulting coating film of the cured film-forming composition X, and the first sheet or the second sheet is laminated. It is preferable to irradiate the active energy ray through the sheet to cure the cured film-forming composition to form a cured film (hereinafter referred to as the first sheet/coating film of the cured film-forming composition/second The laminated structure of the sheets may be referred to as a "gap laminated structure").

When applying the composition X for forming a cured film, it may be applied without using a solvent. As a method for applying the cured film-forming composition X, for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.

The first sheet and the second sheet are not particularly limited as long as at least one of them transmits active energy rays and can be peeled off from the cured film after forming the cured film. Such sheets include, for example, woven fabrics or non-woven fabrics using fibers such as rayon, acrylic, polyester; papers such as fine paper, glassine paper, impregnated paper, coated paper; metal foils such as aluminum and copper; , foams such as polyethylene foam; polyester films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyurethane films, polyethylene films, polypropylene films, cellulose films such as triacetyl cellulose, polyvinyl chloride films, polyvinylidene chloride films , polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, acrylic resin film, norbornene-based resin film, cycloolefin resin film, etc.; can be done. The plastic film may be uniaxially or biaxially oriented.

In addition, the coating film contact surface of the composition X for forming a cured film in the above sheet may be subjected to a release treatment. Examples of release agents used in the release treatment include alkyd-based, silicone-based, fluorine-based, unsaturated polyester-based, polyolefin-based, and wax-based release agents. Of the first sheet and the second sheet, one sheet may be a heavy release type release sheet with a large release force, and the other sheet may be a light release type release sheet with a small release force.

Although the thickness of the first sheet and the second sheet is not particularly limited, it is usually about 10-200 μm, preferably about 30-100 μm.

The active energy ray that irradiates the coating film of the composition X for forming a cured film refers to an electromagnetic wave or charged particle beam that has an energy quantum, and specifically includes ultraviolet rays and electron beams. Among active energy rays, ultraviolet rays are particularly preferable because they are easy to handle.

Ultraviolet irradiation can be performed by a high-pressure mercury lamp, a fusion H lamp, a xenon lamp, an LED lamp, or the ^like . It is preferably on the order of cm ² . The amount of light is preferably 50 to 10000 mJ/cm ² , more preferably 200 to 7000 mJ/cm ² and particularly preferably 500 to 3000 mJ/cm ² . On the other hand, electron beam irradiation can be performed by an electron beam accelerator or the like, and the electron beam irradiation dose is preferably about 10 to 1000 krad.

As described above, when the coating film of the cured film-forming composition X sandwiched between the first sheet and the second sheet is irradiated with an active energy ray, the cured film-forming composition X undergoes oxygen inhibition. Cures well without Moreover, by using the first sheet and the second sheet, a cured film having a desired thickness and surface roughness can be formed. However, the present invention is not limited to this, and active energy rays can be applied in an inert gas atmosphere without using the second sheet.

3. Use of Cured Film Since the cured film according to the present embodiment has scratch resistance, it can be used, for example, as a hard coat layer or a primer layer for various purposes such as optical use and decorative use. For example, in a laminated film having a substrate layer and a hard coat layer, the hard coat layer can be formed from the cured film according to the present embodiment. The type of the substrate layer is not particularly limited, and for example, various synthetic resin films can be used as the substrate layer. In addition, the self-supporting membrane according to the present embodiment can be applied, for example, to water treatment membranes such as reverse osmosis membranes and filtration membranes, or gas separation membranes such as carbon dioxide, oxygen, nitrogen, and hydrogen. . Furthermore, it can be used as a film base material for various purposes because of its characteristics as a transparent high-strength material.

The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiment is meant to include all design changes and equivalents that fall within the technical scope of the present invention.

Although the present invention will be described in more detail with reference to examples and the like, the scope of the present invention is not limited to these examples and the like.

[Example 1]
1. Preparation of cured film-forming composition As the ethylene carbonate-containing acrylic monomer (A), 70 parts by mass of an ethylene carbonate-containing acrylic monomer in which n is 2 in the above formula (3), and an active energy ray-curable compound (B) , 30 parts by mass of a hexafunctional acrylate (B1) in which m, n, p, q, r and s are 10 in the above formula (4), and benzophenone and 1-hydroxycyclohexyl as a photopolymerization initiator (C) 5 parts by mass of a mixture of phenyl ketone at a mass ratio of 1:1 was mixed and sufficiently stirred to obtain a composition for forming a cured film. The viscosity was 210 mPa·S ^-1 .

2. Formation of cured film (self-supporting film) The obtained composition for forming a cured film was applied to a heavy release type release sheet (manufactured by Lintec Corporation, product name “SP-PET752150”) obtained by releasing one side of a polyethylene terephthalate film with a silicone release agent. ) was applied to the release-treated surface.

Then, on the coated film of the cured film-forming composition on the heavy release release sheet coated above, a light release release sheet (manufactured by Lintec Co., Ltd., product name: "SP-PET381130") was laminated so that the release-treated surface of the light release type release sheet was in contact with the coating film.

Subsequently, an ultraviolet irradiation device (manufactured by Eyegraphics, product name “Eyegrantage ECS-401GX”) was applied to the coating film with a gap lamination structure through a light release type release sheet under the following conditions. was irradiated to cure the coating film to form a cured film (self-supporting film). The thickness of the resulting cured film (self-supporting film) was 50 μm. The thickness of the cured film is a value measured in accordance with JIS K7130 using a constant pressure thickness gauge (manufactured by Teclock, product name "PG-02").
[Ultraviolet irradiation conditions]
・Light source: High pressure mercury lamp ・Lamp power: 2 kW
・Conveyor speed: 4.23m/min
・Illuminance: 200mW/ ^cm2
・Light intensity: 600 mJ/cm ²

[Examples 2-3, Comparative Examples 1-2]
A composition for forming a cured film was prepared in the same manner as in Example 1, except that the amounts of the ethylene carbonate-containing acrylic monomer (A) and the active energy ray-curable compound (B) were changed as shown in Table 1. Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

[Example 4]
As the active energy ray-curable compound (B), the same as in Example 1 except that a hexafunctional acrylate (B2) in which m, n, p, q, r and s are each 1 in the above formula (4) is used. to prepare a composition for forming a cured film. Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

[Examples 5 to 6, Comparative Example 3]
A composition for forming a cured film was prepared in the same manner as in Example 4, except that the amounts of the ethylene carbonate-containing acrylic monomer (A) and the active energy ray-curable compound (B) were changed as shown in Table 1. Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

[Example 7]
A composition for forming a cured film was prepared in the same manner as in Example 1, except that dipentaerythritol hexaacrylate (DPHA) (B3) was used as the active energy ray-curable compound (B). Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

[Examples 8 to 9, Comparative Example 4]
A composition for forming a cured film was prepared in the same manner as in Example 7, except that the amounts of the ethylene carbonate-containing acrylic monomer (A) and the active energy ray-curable compound (B) were changed as shown in Table 1. Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

[Example 10]
A composition for forming a cured film was prepared in the same manner as in Example 1, except that polyethylene glycol diacrylate (B4) represented by the following formula (5) was used as the active energy ray-curable compound (B). Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

... (5)
(n=14)

[Examples 11 to 12, Comparative Example 5]
A composition for forming a cured film was prepared in the same manner as in Example 10, except that the amounts of the ethylene carbonate-containing acrylic monomer (A) and the active energy ray-curable compound (B) were changed as shown in Table 1. Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

[Example 13]
A composition for forming a cured film was prepared in the same manner as in Example 1 except that an ethoxylated pentaerythritol tetraacrylate (B5) represented by the following formula (6) was used as the active energy ray-curable compound (B). Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

... (6)
R = _-CH2 - _CH2 -O-
(a+b+c+d=35)

[Examples 14 to 15, Comparative Example 6]
A composition for forming a cured film was prepared in the same manner as in Example 10, except that the amounts of the ethylene carbonate-containing acrylic monomer (A) and the active energy ray-curable compound (B) were changed as shown in Table 1. Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

[Example 16]
A composition for forming a cured film in the same manner as in Example 1, except that a polyester urethane acrylate (B6; manufactured by Shin-Nakamura Chemical Co., Ltd., product name "UA-4400") is used as the active energy ray-curable compound (B). prepared the product. Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

[Comparative Example 7]
38 parts by mass of methyl methacrylate (MMA) and, as the active energy ray-curable compound (B), a hexafunctional acrylate (B1) in which m, n, p, q, r and s are each 10 in the above formula (4) 62 parts by mass and 5 parts by mass of a mixture of benzophenone and 1-hydroxycyclohexylphenyl ketone at a mass ratio of 1:1 as a photopolymerization initiator (C) are mixed and sufficiently stirred to form a cured film. A composition for Then, a cured film was formed in the same manner as in Example 1 using the cured film-forming composition.

[Example 17]
As the ethylene carbonate-containing acrylic monomer (A), 70 parts by mass of the ethylene carbonate-containing acrylic monomer in which n is 2 in the above formula (3), and as the active energy ray-curable compound (B), in the above formula (4) 30 parts by mass of a hexafunctional acrylate (B1) in which m, n, p, q, r and s are each 10, and benzophenone and 1-hydroxycyclohexylphenyl ketone as a photopolymerization initiator (C) at a mass ratio of 1:1 (manufactured by BASF Europe Ltd., product name "OMUNIRAD500") and 5 parts by weight of the mixture was diluted with propylene glycol monomethyl ether to prepare a cured film-forming composition having a solid content concentration of 30% by weight.

On the surface of the primer layer of a polyethylene terephthalate film with a single-sided primer layer (substrate layer; manufactured by Toyobo Co., Ltd., product name "Cosmo Shine A4160", thickness: 50 μm), the above composition for forming a cured film was applied using a Meyer bar. It was applied and dried at 80° C. for 1 minute. Thereafter, the coating film was cured by irradiating ultraviolet rays in a nitrogen stream in the same manner as in Example 1 to form a cured film (hard coat layer) having a thickness of 5 μm. In this manner, a laminate film composed of a cured film (hard coat layer)/base material layer was obtained.

[Examples 18 to 25, Comparative Examples 8 to 10]
A composition for forming a cured film was prepared in the same manner as in Example 17, except that the amount of the ethylene carbonate-containing acrylic monomer (A) and the type and amount of the active energy ray-curable compound (B) were changed as shown in Table 3. prepared the product. Then, using the cured film-forming composition, a cured film (hard coat layer) was formed in the same manner as in Example 17 to obtain a laminated film.

[Test Example 1] (Calculation of CO ₂ fixed amount)
From the amount of the ethylene carbonate-containing acrylic monomer (A) in the cured film-forming compositions prepared in Examples and Comparative Examples, the amount (mass ratio) of carbon _dioxide used (fixed) in the cured film was It was calculated as a conversion amount. Specifically, the molecular weight of CO ₂ (=44) was divided by the molecular weight of the ethylene carbonate-containing acrylic monomer (A) (=158) and expressed as a percentage. The results are shown in Tables 2 and 4.

[Test Example 2] (Evaluation of self-supporting film)
The light release type release sheet and the heavy release type release sheet were sequentially peeled off from the laminate composed of the light release type release sheet/cured film/heavy release type release sheet prepared in Examples and Comparative Examples. The toughness and brittleness of the obtained cured film alone were checked by tactile test, visual observation or microscope, and cutting processing was performed in the vertical direction with respect to the plane of the cured film alone using a cutter, and the cut surface was observed. Evaluation as a self-supporting film was performed based on the following criteria. Table 2 shows the results.
A: No change in appearance, toughness was exhibited, and workability was also excellent.
B... Showed toughness and was workable.
C: Workable, but highly brittle.
D: Cracks occurred during curing, peeling, or cutting.

[Test Example 3] (Measurement of gel fraction)
The cured films prepared in Examples and Comparative Examples were cut into a size of 80 mm×80 mm, and the mass was calculated. Let the mass at this time be M1. Next, the cured film was immersed in ethyl acetate at room temperature (23° C.) for 24 hours. After that, the cured film was taken out, air-dried for 24 hours under an environment of a temperature of 23° C. and a relative humidity of 50%, and further dried in an oven of 80° C. for 12 hours. After drying, the mass was weighed with a precision balance. Let the mass at this time be M2. A gel fraction (%) is represented by (M2/M1)×100. From this, the gel fraction of the cured film was derived. Table 2 shows the results.

[Test Example 4] (Tensile test)
The cured films prepared in Examples and Comparative Examples were cut into a size of 15 mm×140 mm, and this was used as a test piece. The test piece was measured for tensile strength (MPa) and elongation at break (%) at 23°C in accordance with JIS K7127:1999. Specifically, the above test piece is set to a chuck distance of 100 mm with a tensile tester (manufactured by Shimadzu Corporation, product name "Autograph AG-IS 500N"), and then a tensile test is performed at a speed of 200 mm / min. was performed, and the tensile strength (MPa) and elongation at break (%) were measured. Table 2 shows the results.

[Test Example 5] (Measurement of storage modulus)
For the cured films prepared in Examples and Comparative Examples, a dynamic viscoelasticity measuring instrument (manufactured by TA Instruments, product name "DMA Q800") was used, with a frequency of 10 Hz, an amplitude of 5 µm, and a heating rate of 3. The viscoelasticity in the tensile mode was measured when the temperature was raised from 25°C to 150°C at a rate of °C/min. From the viscoelasticity measurement results, the storage elastic modulus (E') (MPa) of the cured film at 30°C and 100°C was read. Table 2 shows the results.

[Test Example 6] (Measurement of pencil hardness)
For the surface of the cured film prepared in Examples and Comparative Examples, according to JIS K5600-5-4, using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd., product name "No. 553-M"), a pencil Hardness was measured. Measurement conditions were a load of 750 g and a scratching speed of 0.5 mm/sec. The results are shown in Tables 2 and 4.

[Test Example 7] (Measurement of total light transmittance)
For the cured films prepared in Examples and Comparative Examples, according to JIS K7361-1: 1997, a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SH-7000") was used to measure total light transmittance (%). was measured. Table 2 shows the results.

[Test Example 8] (Measurement of haze value)
The haze values (%) of the cured films prepared in Examples and Comparative Examples were measured according to JIS K7136:2000 using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SH-7000"). Table 2 shows the results.

[Test Example 9] (Measurement of surface resistance)
For the surfaces of the cured films prepared in Examples and Comparative Examples, a resistivity meter (Mitsubishi Chemical Analytic Tech, Hiresta UP MCP-HT450 type) was used to measure surface resistance (Ω/sq) according to JIS K6911. was measured. Table 2 shows the results.

[Test Example 10] (Evaluation of Flexibility)
The cured films and laminated films prepared in Examples and Comparative Examples were subjected to a mandrel test according to JIS K5600-5-1 (1999) using a cylindrical mandrel bending tester (manufactured by Cortec). In the laminated film, the mandrel test was conducted with the cured film (hard coat layer) of the laminated film facing outward. The diameter of the mandrel with the smallest diameter (minimum mandrel diameter; mmφ) among the mandrels that did not cause defects such as breakage, cracks, discoloration, etc. in the cured film or hard coat layer was determined, and the value was used as the evaluation of flexibility. The results are shown in Tables 2 and 4.

[Test Example 11] (Scratch resistance test)
The cured film (hard coat layer) side surface of the laminated films produced in Examples 17 to 25 and Comparative Examples 8 to 10 was rubbed back and forth 10 times at 50 mm with a load of 250 g/cm ² using #0000 steel wool. Ta. The surface of the cured film (hard coat layer) was visually observed under a three-wavelength fluorescent lamp, and the scratch resistance was evaluated according to the following criteria. Table 4 shows the results.
O: There was no damage at all.
Δ: About 1 to 2 scratches were observed.
x: There were many scratches.

[Test Example 12] (Evaluation of Shrinkability)
A few water droplets were dropped on one surface of the cured films prepared in Examples and Comparative Examples to confirm the state of the cured film (self-supporting film). Next, the cured film was dried, and the state of the cured film (self-supporting film) at that time was confirmed. Based on these results, the presence or absence of shrinkability was evaluated according to the following criteria. Table 2 shows the results.
Existence: A phenomenon was observed in which the surface opposite to the surface on which water droplets were dropped was shrunk, and returned to its original shape when dried.
None: No phenomenon of shrinking was observed even when water droplets were dropped.

As can be seen from Tables 2 and 4, the cured films and laminated films prepared in Examples were capable of fixing a predetermined amount of carbon dioxide, and had physical properties that could be used for various purposes. .

The composition for forming a cured film, the cured film, the self-supporting film, and the method for producing a cured film according to the present invention can fix carbon dioxide and are useful for environmental protection.

Claims

Formula (1) below

An ethylene carbonate-containing acrylic monomer (A) having an ethylene carbonate structure shown in
A composition for forming a cured film, comprising an active energy ray-curable compound (B) having a reactive group.
2. The composition for forming a cured film according to claim 1, wherein the ethylene carbonate-containing acrylic monomer (A) is a compound represented by the following formula (2) or (3).

(In the formula, n represents an integer of 0 or more.)

(In the formula, n represents an integer of 0 or more.)
The composition for forming a cured film according to claim 1, characterized by containing a photopolymerization initiator (C).
The composition for forming a cured film according to claim 1, wherein the active energy ray-curable compound (B) has 2 or more reactive groups.
The composition for forming a cured film according to claim 1, wherein the active energy ray-curable compound (B) has an alkylene glycol chain.
6. The active energy ray-curable compound (B) has a (meth)acryloyl group, and the alkylene glycol chain is bonded to each of the (meth)acryloyl groups. A composition for forming a cured film as described above.
The composition for forming a cured film according to claim 5, wherein the number of repeating units of alkylene glycol in the alkylene glycol chain is 1 or more and 20 or less.
The composition for forming a cured film according to claim 1, which is solvent-free.
A cured film obtained by curing the composition for forming a cured film according to any one of claims 1 to 8.
A self-supporting film made of the cured film according to claim 9.
Applying the cured film-forming composition according to any one of claims 1 to 8 to the first sheet,
Laminating a second sheet on the coating film of the cured film-forming composition,
A method for producing a cured film, comprising irradiating an active energy ray through the first sheet or the second sheet to cure the cured film-forming composition to form a cured film.