TW202330689A - Active energy ray-curable composition and cured product and article thereof which comprises polyfunctional urethane (meth)acrylate - Google Patents

Abstract

This invention relates to an active energy ray-curable composition; a cured product of the active energy ray-curable composition; and an article. The active energy ray-curable composition comprises polyfunctional urethane (meth)acrylate (A). The polyfunctional urethane (meth)acrylate (A) is represented by general formula (1) or general formula (2), wherein the article is characterized by having a coating film containing a cured product.

Description

Active energy ray curable composition, its cured product, and article

The present invention relates to an active energy ray curable composition, cured product and article.

In recent years, high anti-fog properties to prevent fogging have been required for automotive headlights, virtual reality (VR) displays, and the like. The so-called fogging here is a phenomenon caused by diffuse reflection of light caused by water droplets adhering to the surface. As an anti-fog method for preventing fogging, a method of reducing the contact angle of water, a method of absorbing water adhering to the surface, and a method of imparting water repellency to the surface to repel water are generally known. Among them, the method of reducing the contact angle of water is often used because it is simple and has good anti-fog performance.

As a method of reducing the contact angle of water, an attempt has been made to form an antifogging coating film by coating an antifogging resin composition on the surface of glass or plastic as a substrate. However, in antifogging resin compositions, the surfactant bleeds out due to long-term use, which may cause a decrease in antifogging properties or a deterioration in the appearance of the coating film. Therefore, a highly heat-resistant anti-fogging resin composition that can withstand long-term use has been demanded. Therefore, as an antifogging resin composition excellent in antifogging properties, antifogging durability, and abrasion resistance, there is known an ethoxy-modified diacrylate, a hydrophilic An ultraviolet curable antifog composition comprising a functional monomer, a polar diluent solvent, and a photopolymerization initiator (for example, refer to Patent Document 1). In addition, Patent Document 2 discloses an active energy ray containing a radical polymerizable compound, a water-soluble leveling agent, and a photopolymerization initiator in a predetermined content as an antifogging resin composition having both water resistance and water resistance. Hardening type anti-fog coating composition.

[Prior art literature] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2005-239832 [Patent Document 2] Japanese Patent Laid-Open No. 2015-229680

[Problem to be Solved by the Invention] However, in the inventions described in Patent Document 1 and Patent Document 2, studies on heat-resistant adhesiveness at a high temperature of 100 degrees or higher and yellowing after a heat resistance test have not been conducted, and the inventions described in Patent Document 1 and Patent Document 2 The heat resistance cannot be sufficiently expressed without degrading the anti-fog property.

The present invention is made in view of the above problems, and aims to provide an active energy ray-curable composition and a cured product that can form a cured coating film that prevents the reduction in anti-fogging properties and adhesiveness after high-temperature heating and does not damage the appearance. and items.

[Technical means to solve the problem] As a result of studies conducted by the inventors of the present invention, it was found that polyfunctional urethane (methyl) containing four or more (meth)acryl groups in the molecule and a structure derived from polyalkylene glycol The active energy ray-curable composition of acrylate (A) can solve the said problem, and completed this invention.

That is, the present invention provides the following inventions. [1] An active energy ray-curable composition containing a polyfunctional urethane (meth)acrylate (A) represented by the following general formula (1) or (2).

[chemical 1]

[Chem 2]

In the formula, X represents a structure derived from polyalkylene glycol, and Y ₁ to Y ₄ are independently selected from the following general formula (3), general formula (4) and general formula (5), the formula (1 ) and the compound represented by formula (2) contains at least one group represented by formula (3) or formula (4), α and β represent structures derived from isocyanate compounds, and multiple α or β in the formula can be the same as each other or It may be different, and the average repetition number n1 is an integer of 1-10.

[Chem 3]

In the formula, R ₁ to R ₅ independently represent a hydrogen atom or a methyl group, * is a bond, and the oxygen adjacent to any one of Y ₁ to Y ₄ in formula (1) or formula (2) Atoms bond.

[chemical 4]

In the formula, R ₆ to R ₈ each independently represent a hydrogen atom or a methyl group, * is a bond, and the oxygen adjacent to any one of Y ₁ to Y ₄ in formula (1) or formula (2) Atoms bond.

[chemical 5]

In the formula, R ₉ represents a hydrogen atom or a methyl group, R ₁₀ represents an alkylene group with 2 to 10 carbons, * is a bond, and is adjacent to Y ₁ to Y in formula (1) or formula (2). Any one of ₄ is bonded to an oxygen atom. [2] The active energy ray-curable composition according to [1], wherein the number average molecular weight of X in the general formula (1) or (2) is 250 to 1500. [3] The active energy ray-curable composition according to [1] or [2], wherein α in the general formula (1) is a structure derived from a diisocyanate compound having an alicyclic structure. [4] The active energy ray-curable composition according to [1] or [2], wherein β in the general formula (2) is derived from a biuret-type or isocyanurate-type isocyanate compound. structure. [5] The active energy ray-curing composition according to any one of [1] to [4], wherein the average repetition number n1 in the general formula (1) or (2) is 1 to 3. [6] The active energy ray-curable composition according to any one of [1] to [5], which contains a polyfunctional compound having a polycarbonate polyol-derived structure represented by the following general formula (6): Urethane (meth)acrylate (B).

[chemical 6]

In the formula, Z represents a structure derived from polycarbonate polyol, Y ₅ to Y ₆ are independently selected from general formula (3), general formula (4) and general formula (5), and γ represents a structure derived from isocyanate compound The structure of the formula, a plurality of γ in the formula may be the same or different, and the average number of repetitions n2 is an integer of 1-10. [7] The active energy ray-curable composition according to [6], wherein the content of the polyfunctional urethane (meth)acrylate (A) is 15 parts by mass relative to 100 parts by mass of resin solids It is the range of 5-90 mass parts, and content of polyfunctional urethane (meth)acrylate (B) is the range of 5-60 mass parts with respect to 100 mass parts of resin solid content. [8] The active energy ray-curing composition according to any one of [1] to [7], further comprising a surfactant (C). [9] The active energy ray-curing composition according to [8], wherein the surfactant (C) contains a salt represented by the following general formula (7).

[chemical 7]

In the formula, R ₂₁ and R ₂₂ independently represent any one of an alkyl group, a cycloalkyl group, an alkenyl group, and an alkyl group modified with an alkylene oxide with a carbon number of 4 to 22, and A represents lithium, sodium, any of potassium. [10] A cured product of an active energy ray-curable composition, which is a cured product of the active energy ray-curable composition according to any one of [1] to [9]. [11] An article having a coating film comprising the cured product according to [10].

[Effect of the invention] The active energy ray-curable composition of the present invention can form a cured coating film which has excellent anti-fogging properties, prevents the reduction in anti-fogging properties and adhesiveness after high-temperature heating, and does not spoil the appearance. The cured coating film exhibits excellent anti-fogging properties even when exposed to a high-temperature environment, so the active energy ray-curable composition of the present invention can be preferably used as a hard coat layer of a resin material for automobiles or displays. .

In this specification, the compound represented by formula (1) is referred to as "compound (1)", and the same applies to compounds represented by other formulas. In addition, "acrylate" and "methacrylate" are collectively referred to as "(meth)acrylate", and "(meth)acryl" and "acryl" are collectively referred to as "(meth)acryl". base". The said urethane (meth)acrylate (A) is called "(A) component", and the same applies to other compound (B) component - (C) component.

＜Active energy ray curable composition＞ The active energy ray-curable composition of the present invention (hereinafter sometimes simply referred to as "composition") contains (A) component as an essential component and optionally contains any one or more of (B) to (C) components. As an evaluation method of the present invention, the anti-fogging property and base material adhesiveness after high-temperature heating of the coating film after curing the composition were tested. When the above-mentioned test results are excellent, the anti-fogging property and the adhesiveness are not easily lowered even in a high-temperature environment. Furthermore, the change in appearance including yellowing and whitening of the cured coating film after high-temperature heating was also observed, and the less the change in appearance, the less damaged the appearance.

[(A) Ingredients] The component (A) is a polyfunctional urethane (meth)acrylate compound having four or more (meth)acryl groups and a polyalkylene glycol-derived structure in a molecule. In this specification, the polyalkylene glycol-derived structure refers to a structure obtained by removing a terminal hydrogen atom from the polyalkylene glycol. Generally, in order to exhibit anti-fogging properties, it is necessary to lower the surface tension of water droplets adhering to the surface of the substrate to form a clean water film. Therefore, in order to impart hydrophilicity to the substrate surface, a structure derived from polyalkylene glycols such as polyethylene glycol and polypropylene glycol is introduced into the component (A). Furthermore, when the component (A) contains four or more (meth)acryloyl groups, the rigidity is improved, and an anti-fogging coating film that is less likely to deteriorate even in a high-temperature environment can be obtained. Specifically, the component (A) is preferably a compound represented by the general formula (1) or the general formula (2), and more preferably a compound represented by the formula (1).

[chemical 1]

[Chem 2]

In the formula (1), X represents a structure derived from polyalkylene glycol, and Y ₁ to Y ₂ are independently selected from the following general formula (3), general formula (4) and general formula (5) Among them, the compound represented by formula (1) contains at least one group represented by formula (3) or formula (4), α represents a structure derived from an isocyanate compound, and multiple α in the formula can be the same or different from each other, and the average The repetition number n1 is an integer of 1-10. The average number of repeats in this specification means the average obtained by dividing the total number of repeats by the number of molecules contained in the composition when there are a plurality of molecules with different repeat numbers in the composition. The value is rounded off below the decimal point of the value. In the formula (2), X represents a structure derived from polyalkylene glycol, and Y ₁ to Y ₄ are each independently selected from the following general formula (3), general formula (4) and general formula (5) Among them, β represents a structure derived from an isocyanate compound, and a plurality of β in the formula may be the same as or different from each other, and the average repetition number n1 is an integer of 1-10. The average number of repeats in this specification means the average obtained by dividing the total number of repeats by the number of molecules contained in the composition when there are a plurality of molecules with different repeat numbers in the composition. The value is rounded off below the decimal point of the value.

[Chem 3]

In the formula (3), R ₁ to R ₅ independently represent a hydrogen atom or a methyl group, * is a bonding bond, and are adjacent to Y ₁ to Y ₄ in formula (1) or formula (2). Either oxygen atom is bonded.

[chemical 4]

In the formula (4), R ₆ to R ₈ independently represent a hydrogen atom or a methyl group, * is a bonding bond, and are adjacent to Y ₁ to Y ₄ in formula (1) or formula (2). Either oxygen atom is bonded.

[chemical 5]

In the formula (5), R ₉ represents a hydrogen atom or a methyl group, R ₁₀ represents an alkylene group with 2 to 10 carbons, * is a bond, and is adjacent to the formula (1) or formula (2) Any one of Y ₁ to Y ₄ is bonded to an oxygen atom.

Examples of X in the compound (1) or compound (2) include structures derived from polyalkylene glycols such as polyethylene glycol and polypropylene glycol, as raw materials for compound (1) or compound (2). , preferably polyethylene glycol, polypropylene glycol, or a copolymer of polyethylene glycol and polypropylene glycol, particularly preferably polyethylene glycol. The number average molecular weight of the polyalkylene glycol which is a raw material of compound (1) or compound (2) is preferably in the range of 100 to 10,000, more preferably in the range of 150 to 2,500, particularly preferably in the range of 250 to 1,500 . By setting it as the number average molecular weight in the said range, suitable hydrophilicity can be provided to the surface of a base material, and the cured coating film which is excellent in anti-fogging property even after high-temperature heating, and an appearance is hard to deteriorate can be obtained.

Examples of commercially available polyalkylene glycols used as a raw material for the compound (1) or compound (2) include the "PEG" series (PEG-200, PEG- 400, PEG-600, PEG-1000, PEG-2000, PEG-4000, etc.), Sanyo Chemical Industry Co., Ltd.'s product name "NEWPOL (registered trademark)" PP series (PP-200, PP-400, PP-600, PP-1000, PP-2000, etc.), each grade of Mitsubishi Chemical Corporation's trade name "PTMG" (PTMG-650, PTMG-1000, PTMG-2000, etc.), etc.

α in the compound (1) and β in the compound (2) are structures derived from isocyanate compounds. The term "isocyanate compound" in this specification means a compound having one or more isocyanate groups in the molecule and all polymers thereof, and the term "structure derived from an isocyanate compound" means that all isocyanate is removed from the isocyanate compound. base position. Therefore, compound (1) or compound (2) is synthesize|combined using an isocyanate compound as a raw material.

Examples of isocyanate compounds include aromatic isocyanates such as diphenylmethane diisocyanate and toluene diisocyanate; 1,6-hexamethylene diisocyanate, 1,4-butane diisocyanate, 2,2,4-tris Aliphatic isocyanate such as methylhexamethylene diisocyanate, 2,4,4-trimethylhexexylene diisocyanate, lysine diisocyanate, lysine triisocyanate; isophorone diisocyanate, 4, 4'-methylene bis(cyclohexyl isocyanate), 1,3-bis(isocyanate)cyclohexane, norbornane diisocyanate, hydrogenated xylene diisocyanate, 2-methyl-1,3- Alicyclic isocyanate compounds such as cyclohexyl diisocyanate and 2-methyl-1,5-cyclohexyl diisocyanate, and the like. Alternatively, dimers or trimers of these isocyanate compounds (isocyanurate, biuret, allophanate, etc.) may also be used. In the present invention, as the compound (1), among isocyanate compounds, aliphatic isocyanates and alicyclic isocyanates are more preferred, alicyclic diisocyanates are particularly preferred, and among alicyclic diisocyanates, 4, 4'-methylene bis(cyclohexyl isocyanate), norbornane diisocyanate. Since the compound (1) has a structure derived from an alicyclic diisocyanate, a particularly rigid cured coating film can be formed, and thus a decrease in adhesion and a deterioration in appearance after high-temperature heating can be further prevented. Among the isocyanate compounds, the compound (2) is more preferably a trimer of aliphatic isocyanate and alicyclic isocyanate, particularly preferably a trimer of aliphatic diisocyanate, among which 1,5-pentane Diisocyanate, isocyanurate body and biuret body of 1,6-hexamethylene diisocyanate, more preferably 1,5-pentamethylene diisocyanate, isocyanurate body of 1,6-hexamethylene diisocyanate Cyanurate body. Since the compound (2) has an aliphatic-derived trimer structure, especially a cyclic structure, a particularly rigid cured coating film can be formed, and thus the decrease in adhesion and the deterioration in appearance after high-temperature heating can be further prevented.

The group represented by the above formula (3) is a structure derived from dipentaerythritol penta(meth)acrylate. The "structure derived from dipentaerythritol penta(meth)acrylate" in this specification substantially means a site where a hydroxyl group is removed from dipentaerythritol penta(meth)acrylate. Therefore, dipentaerythritol penta(meth)acrylate can be used as a raw material of compound (1) or compound (2).

Examples of commercially available dipentaerythritol penta(meth)acrylates include various products under the trade name "Aronix (registered trademark)" manufactured by Toagosei Co., Ltd. (M-400, M-403, M-404, M-405, M-406, etc.) etc.

The group represented by the above formula (4) is a structure derived from pentaerythritol tri(meth)acrylate. The "structure derived from pentaerythritol tri(meth)acrylate" in this specification substantially means a site in which a hydroxyl group is removed from pentaerythritol tri(meth)acrylate. Therefore, pentaerythritol tri(meth)acrylate can be used as a raw material of compound (1) or compound (2).

Commercially available pentaerythritol tri(meth)acrylates include various products under the trade name "Aronix (registered trademark)" manufactured by Toagosei Co., Ltd. (M-306, M-305, M-303, M -452, M-450, etc.), etc.

The group represented by the said formula (5) is a structure derived from the mono(meth)acrylate containing a hydroxyl group. Here, the "structure derived from a hydroxyl group-containing mono(meth)acrylate" essentially means a site where a hydroxyl group is removed from a hydroxyl group-containing mono(meth)acrylate. Therefore, a hydroxyl group-containing mono(meth)acrylate can be used as a raw material for compound (1) or compound (2).

Specific examples of hydroxyl-containing mono(meth)acrylates include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate , 4-Hydroxybutyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy mono(meth)acrylate (for example, products manufactured by Daicel Corporation) name "Placcel (registered trademark) FA-2D", etc.), polycarbonate-modified hydroxy mono(meth)acrylate (for example, Daicel's trade name "sea (HEMAC)” (registered trademark), etc.), polyethylene glycol or polypropylene glycol-modified hydroxy mono(meth)acrylate (for example, the product name “Blemmer” (registered trademark) manufactured by NOF Corporation Trademark) AE-200", "Blemmer (registered trademark) AP-400", etc.), etc.

As mentioned above, compound (1) preferably contains at least one group represented by formula (3) or formula (4). Therefore, compared with the case where all of Y ₁ to Y ₄ are groups represented by formula (5), the number of (meth)acryloyl groups in the molecule increases, so compound (1) or compound (2) The degree of crosslinking increases, and an anti-fogging coating film that is less likely to deteriorate even in a high-temperature environment can be obtained.

As mentioned above, compound (1) preferably contains at least one group represented by formula (4) or formula (5). Thus, compared with the case where all of Y ₁ to Y ₄ are groups represented by formula (3), the number of (meth)acryloyl groups in the molecule decreases, so the degree of crosslinking of compound (2) decreases, Improves anti-fog performance.

Furthermore, the average repetition number n1 in compound (1) and compound (2) is preferably in the range of 1-10, more preferably in the range of 1-6, particularly preferably in the range of 1-3. By setting it as these ranges, the cured coating film which has antifogging property and base-material adhesiveness can be formed without impairing an external appearance even after high-temperature heating.

In view of the above, the composition of the present invention is particularly preferably in which the component (A) is the compound (1) and the amount of X is Polyethylene glycol with an average molecular weight of 250-1500, at least one of _Y1 and _Y2 is a group represented by formula (3) or formula (4), and α is derived from norbornane diisocyanate or 4,4' - A compound having a methylene bis(cyclohexyl isocyanate) structure, wherein the average repeat number n1 is in the range of 1-3. Compound (2) is particularly preferred, and the number average molecular weight of X is polyethylene glycol of 250-1500, Y ₁ to Y ₄ are groups represented by formula (4) or formula (5), and β is derived from 1 , The compound having the structure of an isocyanurate body obtained by trimerizing 5-pentane diisocyanate and 1,6-hexamethylene diisocyanate has an average repeat number n1 in the range of 1-3. However, even when using compound (1) or compound (2) in which Y ₁ , Y ₂ , X, α, and n1 are different, the problem of the present invention can be solved, so it is not particularly limited to this.

(A) A component may be used individually by 1 type, or may use it in combination of 2 or more types.

The content of the component (A) is preferably in the range of 15 to 100 parts by mass, more preferably in the range of 25 to 90 parts by mass, with respect to 100 parts by mass of the resin solid content of the composition of the present invention, especially Preferably, it is the range of 40 mass parts - 80 mass parts. By setting it as these ranges, it has excellent antifogging property, prevents the fall of antifogging property and base-material adhesiveness after high-temperature heating, and can form the cured coating film which does not spoil an external appearance. In addition, the resin solid content in this specification means the total amount of the compound which has a polymerizable functional group.

[(B) Ingredients] (B) A component is a polyfunctional urethane (meth)acrylate compound (B) which has a structure derived from a polycarbonate polyol represented by formula (6). In this invention, by using (A) component and (B) component together, the fall of the antifogging property and base-material adhesiveness after high-temperature heating can be suppressed further.

[chemical 6]

In the formula, Z represents a structure derived from polycarbonate polyols, Y ₅ to Y ₆ are independently selected from the general formula (3), general formula (4) and general formula (5), and γ represents a structure derived from In the structure of the isocyanate compound, a plurality of γ in the formula may be the same or different, and the average repetition number n2 is an integer of 1-10. The structure derived from the polycarbonate polyol in this specification means the site|part which removed the terminal hydrogen atom from the polycarbonate polyol.

The structure derived from polycarbonate polyol contained in compound (6) is derived from polycarbonate polyol, and the polycarbonate polyol is obtained by having a linear alkyl structure, branched alkyl structure, polyether diol structure, and any one of the caprolactone diol structure polyol and carbonate ester exchange reaction and synthesis.

Specific examples of polyhydric alcohols having a linear alkyl structure include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol , 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, etc. Specific examples of polyhydric alcohols having a branched alkyl structure include: 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2-methanol Base-1,8-octanediol, etc. Among these polyols, polyhydric alcohols having a straight-chain alkyl structure are more preferable from the viewpoint of substrate adhesion and appearance after high-temperature heating of the composition, and among them, 1,5-pentanediol, 1 , 6-hexanediol, and 1,9-nonanediol, most preferably 1,6-hexanediol and 1,5-pentanediol.

As specific examples of carbonates, ethylene carbonate, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, carbonic acid diphenyl ester, etc.

As a raw material of the compound (6), commercially available polycarbonate polyols can also be used. Concretely, for example, various products of Ube Industries Co., Ltd.'s product name "ETERNACOLL" (registered trademark) series (UH-50, UH-100, UH-200, UH-300, PH- 50, PH-100, PH-200, PH-300, UC-100, UM-90, UHC50-100, UP-50, UP-100 and UP-200, etc.), Mitsubishi Chemical Corporation's trade name "Benny BENEBiOL" (registered trademark) grades (NL1010DB, NL2010DB, NL3010DB, NL1005B, NL2005B, NL1030B, HS0830B, HS0840B, HS0840B, HS0850H, etc.), Kuraray's product name "Kuraray Multi Alcohol (Kuraray polyol)" brands (C-590, C-1090 and C-2090, etc.), etc.

The number average molecular weight of these polycarbonate polyols is preferably in the range of 100 to 3500, more preferably It is in the range of 200 to 2500, particularly preferably in the range of 300 to 1500.

γ in the compound (6) represents a structure derived from an isocyanate compound. Therefore, compound (6) is synthesized using an isocyanate compound as a raw material.

Examples of isocyanate compounds include aromatic isocyanates such as diphenylmethane diisocyanate and toluene diisocyanate; 1,6-hexamethylene diisocyanate, 1,4-butane diisocyanate, 2,2,4-tris Aliphatic isocyanate such as methylhexamethylene diisocyanate, 2,4,4-trimethylhexexylene diisocyanate, lysine diisocyanate, lysine triisocyanate; isophorone diisocyanate, 4, 4'-methylene bis(cyclohexyl isocyanate), 1,3-bis(isocyanate)cyclohexane, norbornane diisocyanate, hydrogenated xylene diisocyanate, 2-methyl-1,3- Alicyclic isocyanates such as cyclohexyl diisocyanate and 2-methyl-1,5-cyclohexyl diisocyanate, and the like. Alternatively, dimers or trimers of these isocyanates (isocyanurate, biuret, allophanate, etc.) may also be used. In the present invention, among the isocyanate compounds, aliphatic isocyanate and alicyclic isocyanate are more preferred, alicyclic diisocyanate is particularly preferred, and among alicyclic diisocyanates, isophorone diisocyanate or 4, 4'-methylene bis(cyclohexyl isocyanate). Since the compound (6) has a structure derived from an alicyclic diisocyanate, a particularly rigid cured coating film can be formed, and thus a decrease in substrate adhesion and a deterioration in appearance after high-temperature heating can be further prevented.

Y ₅ and Y ₆ in compound (6) are groups represented by any one of formula (3) to formula (5). Therefore, any one or more of dipentaerythritol penta(meth)acrylate, pentaerythritol tri(meth)acrylate, and hydroxyl group-containing mono(meth)acrylate can be used as a raw material of compound (6).

As commercially available products of dipentaerythritol penta(meth)acrylate, various products (M-400, M-403, M-404) under the trade name "Aronix" (registered trademark) manufactured by Toagosei Co., Ltd. are listed, for example. , M-405, M-406, etc.) etc. Examples of commercially available pentaerythritol tri(meth)acrylates include various products under the trade name "Aronix" (registered trademark) manufactured by Toagosei Co., Ltd. (M-306, M-305, M-303, M-452, M-450, etc.), etc.

Specific examples of hydroxyl-containing mono(meth)acrylates include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate , 4-Hydroxybutyl (meth)acrylate, 2-Hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy mono(meth)acrylate (for example, products manufactured by Daicel Corporation) name "Placcel (registered trademark) FA-2D", etc.), polycarbonate-modified hydroxyl mono(meth)acrylate (for example, Daicel's trade name "sea (HEMAC)” (registered trademark), etc.), polyethylene glycol or polypropylene glycol-modified hydroxy mono(meth)acrylate (for example, the product name “Blemmer” (registered trademark) manufactured by NOF Corporation Trademark) AE-200", "Blemmer (registered trademark) AP-400", etc.), etc.

At least one of Y ₅ and Y ₆ of compound (6) is more preferably formula (4) or formula (5), particularly preferably Y ₅ and Y ₆ , both of which are formula (4) or formula (5), Y Both ₅ and Y ₆ are optimally represented by formula (5). This reduces curing shrinkage and improves substrate adhesion.

Furthermore, the average repetition number n2 in compound (6) is preferably in the range of 1-10, more preferably in the range of 1-6, and particularly preferably in the range of 1-3. By setting it as these ranges, the cured coating film which has antifogging property and base-material adhesiveness can be formed without impairing an external appearance even after high-temperature heating.

From the above, it is particularly preferable that the composition of the present invention is composed of compound (6) and Z is derived from As a structure of polycarbonate polyol which is a reaction product of 1,6-hexanediol, 1,5-pentanediol, and carbonate, Y ₅ and Y ₆ are groups represented by formula (5), and γ is In the compound derived from the structure of isophorone diisocyanate or 4,4'-methylene bis(cyclohexyl isocyanate), the average repetition number n2 is in the range of 1-3. However, even when using compound (6) in which Y ₅ , Y ₆ , Z, γ, and n2 are different, the subject of the present invention can be solved, and it is not particularly limited thereto.

The (B) component can also use a commercial item from a viewpoint of easy acquisition, for example, the brand name "UV-3310B" by Mitsubishi Chemical Corporation etc. can be used.

(B) A component may be used individually by 1 type, or may use it in combination of 2 or more types.

When the composition of the present invention contains the component (B), the content of the component (B) is preferably in the range of 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the resin solid content of the composition, more preferably It is in the range of 10 to 50 parts by mass, particularly preferably in the range of 20 to 40 parts by mass. By setting it as these ranges, it has excellent antifogging property, prevents the fall of antifogging property and base-material adhesiveness after high-temperature heating, and can form the cured coating film which does not spoil an external appearance.

The mass ratio [(A)/(B)] of component (A) to component (B) in the composition is preferably in the range of 0.1/1 to 20/1, more preferably in the range of 0.3/1 to 10/1 , particularly preferably in the range of 1/1 to 4/1. By setting it as these ranges, the fall of the anti-fogging property and base material adhesiveness after high-temperature heating, and the deterioration of an external appearance can be prevented further.

[(C) Component] (C) The component is a surfactant selected from anionic surfactants, cationic surfactants, and nonionic surfactants, and may be a single component or a combination of multiple components. In the present invention, by adding the component (C), more suitable hydrophilicity can be imparted to the surface of the base material, and the decrease in the anti-fog property after high-temperature heating can be further suppressed.

As the anionic surfactant, all conventionally known anionic surfactants can be used, for example: fatty acid salts such as sodium oleate and potassium oleate; higher alcohol sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate ; Sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate and other alkylbenzene sulfonates and alkylnaphthalene sulfonates; Sulfosuccinate, dialkyl phosphate, polyoxyethylene alkyl phenyl ether sulfate and other polyoxyethylene sulfate; perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl Fluorine-containing anionic surfactants such as phosphate esters, etc. Among them, dialkyl sulfosuccinates and dialkyl phosphates are preferable in terms of excellent anti-fog performance.

As the cationic surfactant, all conventionally known cationic surfactants can be used, for example, ethanolamines, laurylamine acetate, triethanolamine monoformate, stearamide ethyl diethylamine Amine salts such as acetate; Alkyl trimethyl ammonium salts such as lauryl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride; Dilauryl dimethyl ammonium chloride, distearyl dimethyl ammonium Dialkyl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride and other dialkyl dimethyl ammonium salts; perfluoroalkyl trimethyl ammonium salts and other fluorine-containing Cationic surfactants, etc. Among these, alkyltrimethylammonium salts and dialkyldimethylammonium salts are preferable in terms of excellent anti-fog performance.

As the nonionic surfactant, all conventionally known surfactants can be used, for example, polyoxyethylene higher alcohol ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; polyoxyethylene octylphenol , polyoxyethylene nonylphenol and other polyoxyethylene alkyl aryl ethers; polyoxyethylene glycol monostearate and other polyoxyethylene acyl esters; polypropylene glycol ethylene oxide adducts, polyoxyethylene Polyoxyethylene sorbitan fatty acid esters such as sorbitan monolaurate and polyoxyethylene sorbitan monostearate; phosphoric acid esters such as alkyl phosphate and polyoxyethylene alkyl ether phosphate; sugar esters Classes, cellulose ethers; perfluoroalkyl ethylene oxide, perfluoroalkyl ethylene oxide adducts, oligomers with perfluoroalkyl and hydrophilic groups, perfluoroalkyl and lipophilic Fluorine-containing nonionic surfactants such as oligomers with perfluoroalkyl groups, oligomers with hydrophilic groups, and lipophilic groups. Among these, polyoxyethylene higher alcohol ethers and polyoxyalkylene higher alcohol ethers are preferable in terms of excellent anti-fog performance.

(C) The component is not particularly limited, but among the above, from the viewpoint of anti-fogging properties, it is preferable to include at least an anionic surfactant, and it is particularly preferable to include an anionic surfactant represented by the following general formula (7). Represents dialkyl sulfosuccinate or dienyl sulfosuccinate.

[chemical 7]

In the formula, R ₂₁ and R ₂₂ each independently represent any one of an alkyl group, an alkenyl group, a cycloalkyl group, and an alkyl group modified with an alkylene oxide having a carbon number of 4 to 22. The term "alkyl group" in this specification refers to a group obtained by removing one arbitrary hydrogen atom from a straight-chain alkane or a branched alkane. In the formula, A represents any one of lithium, sodium and potassium, particularly preferably sodium.

From the viewpoint of suppressing a decrease in anti-fogging properties, the compounding amount of the component (C) is preferably 0.5 parts by mass or more, particularly preferably 1 part by mass, based on 100 parts by mass of the solid content of the active energy ray-curable composition. servings or more.

In addition, the active energy ray-curable composition of the present invention may contain a photopolymerization initiator.

[Photopolymerization Initiator] As the photopolymerization initiator, for example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxy Ethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-di Phenylethane-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-Trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, etc.

These photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, particularly preferably 1 to 5 parts by mass. When the content of the photopolymerization initiator is 0.1 parts by mass or more, the curing reaction proceeds favorably and a cured product having high hardness can be obtained, which is preferable. On the other hand, when content of a photoinitiator is 10 mass parts or less, yellowing etc. will not generate|occur|produce easily, and since the hardened|cured material which has high transparency can be obtained, it is preferable.

In addition, the active energy ray-curable composition of the present invention may contain a solvent. By including a vehicle, the viscosity of the composition can be adjusted.

[solvent] Examples of the solvent include alcohol solvents such as methanol, ethanol, 1-propanol, tert-butanol, and diacetone alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, carbitol, cellosolve and other alcohol ether solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketone solvents; methyl acetate, ethyl acetate, Ester solvents such as butyl acetate; aromatic solvents such as toluene, xylene, dibutyl hydroxytoluene, etc.

These solvents may be used alone or in combination of two or more.

The content of the solvent is preferably from 0 to 300 parts by mass, more preferably from 0 to 100 parts by mass, based on 100 parts by mass of solid content of the active energy ray-curable composition. When content of the said solvent is 300 mass parts or less, it is easy to control film thickness, and it is preferable. In addition, when the content of the solvent is 10 parts by mass or more, various coating methods such as spray coating and flow coating can be used, which is preferable.

Furthermore, the active energy ray-curable composition of this invention may contain other additives as needed.

[other ingredients] Typical examples of other components include reactive compounds, various resins, fillers, ultraviolet absorbers, and leveling agents. In addition, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, catalysts, surfactants other than component (C), stabilizers, flow regulators, coupling agents, dyes, rheology control agents, Antioxidants, plasticizers, etc.

As a reactive compound, the compound which has a double bond, such as a (meth)acrylate compound other than (A) component - (C)component, and a vinyl group, can also be mix|blended. Examples of the (meth)acryl-based compound include monofunctional (meth)acrylates and polyfunctional (meth)acrylates.

Examples of monofunctional (meth)acrylates include: acrylmorpholine, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone modified Hydroxy(meth)acrylate (for example, the trade name "Placcel" manufactured by Daicel Co., Ltd.), phthalic anhydride or succinic anhydride with hydroxyalkyl(meth)acrylate ester reactant, mono(meth)acrylate of polyester diol obtained from succinic acid and ethylene glycol, mono(meth)acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene Glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-(meth)acryloxypropyl (meth)acrylate, acrylamide, dimethyl Acrylamide, diethylacrylamide, amino (meth)acrylate, (meth)acrylate containing sulfonic acid group or ionic group such as quaternary ammonium salt, (meth)acrylic acid of various epoxy esters Additions etc.

Examples of polyfunctional (meth)acrylates include: 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol Di(meth)acrylate, Neopentyl glycol di(meth)acrylate, Glyceryl tri(meth)acrylate modified by ethylene oxide, Glyceryl tri(meth)acrylate modified by propylene oxide Acrylates, trimethylolpropane tri(meth)acrylate, hydroxyvaleric acid modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate modified by ethylene oxide base) acrylate, trimethylolpropane tri(meth)acrylate modified by propylene oxide, phosphate tri(meth)acrylate modified by ethylene oxide, pentaerythritol ethoxy tetra(methyl) ) acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate Dipentaerythritol hexa(meth)acrylate, tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate ester, tripentaerythritol octa(meth)acrylate, pentaerythritol tetra(meth)acrylate modified by ethylene oxide, pentaerythritol tetra(meth)acrylate modified by propylene oxide, Modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate modified by propylene oxide, urethane (methyl) obtained by reacting isocyanate compound and alcohol compound ) acrylate compound, polyester (meth)acrylate compound synthesized by condensation reaction of polyhydric alcohol, (meth)acrylic acid and polyfunctional carboxylic acid, bisphenol type epoxy resin or novolak type epoxy resin Epoxy (meth)acrylate compounds synthesized by addition reaction with (meth)acrylic acid, etc.

In addition, a liquid organic polymer can also be used for viscosity adjustment. The so-called liquid organic polymers are liquid organic polymers that do not directly participate in the hardening reaction, for example, carboxyl group-containing polymer modified products (Flowlen (Flowlen) G-900, NC-500: co-prosperity Chemical Industry Co., Ltd.), acrylic polymer (Flowlen (Flowlen) WK-20: manufactured by Kyoei Chemical Industry Co., Ltd.), amine salt of specially modified phosphoric acid ester (HIPLAAD (registered trademark) ED-251 : manufactured by Kusumoto Chemical Co., Ltd.), modified acrylic block copolymer (DISPERBYK (registered trademark) 2000: manufactured by BYK-Chemie), etc.

As various resins, thermosetting resins or thermoplastic resins can be used.

A thermosetting resin is a resin that is substantially insoluble and can be changed to infusibility when hardened by means such as heating, radiation, or a catalyst. As a specific example, a thermosetting resin is a resin that is substantially insoluble and can be changed to infusibility when hardened by means such as heating, radiation, or a catalyst. Specific examples thereof include phenolic resins, urea resins, melamine resins, benzoguanamine resins, alkyd resins, unsaturated polyester resins, vinyl ester resins, diallyl terephthalate resins, epoxy resin, silicone resin, urethane resin, furan resin, ketone resin, xylene resin, thermosetting polyimide resin, benzoxazine resin, active ester resin, aniline resin, cyanate resin, Styrene-maleic anhydride (Styrene-Maleic Anhydride, SMA) resin, etc. These thermosetting resins may be used alone or in combination of two or more.

The term "thermoplastic resin" refers to a resin that can be melt-molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (Acrylonitrile Butadiene Styrene, ABS) resin, acrylonitrile- Styrene (Acrylonitrile Styrene, AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, acetic acid Cellulose resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, Polycarbonate resin, polyamide resin, polyphenylene sulfide resin, polyether imide resin, polyether imide resin, polyacrylate resin, thermoplastic polyimide resin, polyamide imide resin, polyether ether Ketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndiotactic polystyrene resin, cyclic polyolefin resin, etc. These thermoplastic resins may be used alone or in combination of two or more. As a filler, for example, silica may be compounded for the purpose of improving hard coat properties. The silica is not limited, and known fine silica particles such as powdered silica or colloidal silica can be used. Examples of commercially available powdery silica fine particles include the product name "Aerosil (registered trademark)" series (50, 200, etc.) manufactured by Aerosil Corporation of Japan, AGC's product name "Sildex" series (H31, H32, H51, H52, H121, H122, etc.), Tosoh Silica Corporation's product name "E220A" or "E220" , the trade name "SYLYSIA (registered trademark) 470" manufactured by Fuji Silysia Chemical Co., Ltd., the trade name "SG Flake" manufactured by Nippon Plate Glass Co., Ltd., etc. In addition, examples of commercially available colloidal silica include "methanol silica sol", "IPA-ST", "MEK-ST", "PGM-ST", "NBA -ST", "XBA-ST", "DMAC-ST", "ST-UP", "ST-OUP", "ST-20", "ST-40", "ST-C", "ST-N ", "ST-O", "ST-50", "ST-OL" and so on.

Silica Reactive silica can also be used. Examples of reactive silica include reactive compound-modified silica. Examples of the reactive compound include a reactive silane coupling agent having a hydrophobic group, a compound having a (meth)acryl group, a compound having a maleimide group, and a compound having a glycidyl group. Commercially available powdery silica modified with a compound having a (meth)acryloyl group includes the product name "Aerosil (registered)" manufactured by Aerosil Corporation of Japan. Trademark) RM50", "Aerosil (registered trademark) R711", etc., as commercially available colloidal silica modified with a compound having a (meth)acryl group, Nissan Chemical Industry Co., Ltd. The manufactured product names are "MIBK-SD", "MIBK-SD-L", "MIBK-AC-2140Z", "MEK-AC-2140Z", etc. In addition, as reactive silica, silica obtained by adding acrylic acid after modifying glycidyl groups such as 3-glycidoxypropyltrimethoxysilane, or silica having Silica modified by the carbamate reaction of 3-isocyanatopropyltriethoxysilane with hydroxyl and (meth)acryl compounds.

The shape of the silica fine particles is not particularly limited, and spherical, hollow, porous, rod-like, plate-like, fibrous or indeterminate silica fine particles can be used. For example, as commercially available hollow silica fine particles, a product name "Silinax" (registered trademark) manufactured by Nippon Steel Mining Co., Ltd. or the like can be used. In addition, the primary particle diameter is preferably in the range of 5 nm to 200 nm. When it is 5 nm or more, the dispersion of the inorganic fine particles in the composition becomes sufficient, and when it is 200 nm or less, sufficient strength of the cured product can be maintained. The compounded amount of silica is preferably 0.05 mass % to 60 mass % in 100 mass % of the composition.

Examples of fillers other than silica include inorganic fillers and organic fillers. The shape of the filler is not limited, and examples thereof include particulate, plate-like, and fibrous fillers. Examples of fillers excellent in heat resistance include alumina, magnesia, titanium dioxide, and zirconia, and fillers excellent in thermal conductivity include boron nitride, aluminum nitride, alumina, titanium oxide, magnesium oxide, zinc oxide, Silicon oxide, etc.; as fillers with excellent conductivity, metal fillers and/or metal coatings using single metals or alloys (such as iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.) Filler; as a filler with excellent barrier properties, it is mica, clay, kaolinite, talc, zeolite, wollastonite, montmorillonite and other minerals or potassium titanate, magnesium sulfate, sepiolite, vermiculite, aluminum borate, carbonic acid Calcium, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide; fillers with high refractive index, barium titanate, zirconium oxide, titanium oxide, etc.; fillers showing photocatalytic properties, titanium, cerium, zinc, copper , aluminum, tin, indium, phosphorus, carbon, sulfur, ruthenium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead and other photocatalyst metals, complexes of the metals, their oxides, etc.; As fillers excellent in wear resistance, metals such as alumina, zirconia, and magnesia, and their composites and oxides, etc.; as fillers excellent in electrical conductivity, metals such as silver and copper, tin oxide, indium oxide, etc. and the like; and fillers excellent in shielding ultraviolet rays include titanium oxide, zinc oxide, and the like. These inorganic fine particles may be used alone or in combination, as long as they are appropriately selected according to the application. In addition, the inorganic fine particles have various properties other than the properties listed in the examples, so it is only necessary to select them appropriately according to the application.

Examples of inorganic fibers include carbon fibers, activated carbon fibers, graphite fibers, tungsten carbide fibers, ceramic fibers, and natural fibers in addition to inorganic fibers such as carbon (carbon) fibers, glass fibers, boron fibers, alumina fibers, and silicon carbide fibers. , basalt and other mineral fibers, boron nitride fibers, boron carbide fibers and metal fibers, etc. Examples of the metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

Examples of organic fibers include polybenzobisazole, polyaramide, poly p-phenylene benzo-oxazole (PBO), polyphenylene sulfide, polyester, acrylic, Synthetic fibers of resin materials such as polyamide, polyolefin, polyvinyl alcohol, and polyarylate, or natural fibers such as cellulose, pulp, cotton, wool, and silk, and regenerated fibers such as proteins, polypeptides, and alginic acid, etc.

The blending amount of the filler is preferably 0% by mass to 60% by mass in 100% by mass of the composition.

Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, benzotriazine-based, cyclic imide ester-based, cyanoacrylate-based, polymer-type ultraviolet absorbers, and the like.

In the composition of the present invention, a photostabilizer may be used in combination for the purpose of improving light resistance. As a light stabilizer, hindered amine light stabilizer (hindered amine light stabilizer, HALS) etc. are mentioned.

Various surface modifiers may be added to the composition of the present invention for the purpose of improving leveling at the time of coating, or improving the sliding properties of a cured film to improve scratch resistance, and the like. As the surface modifying agent, various additives that are marketed under the names of surface conditioner, leveling agent, smoothness imparting agent, antifouling agent, etc. and modify surface physical properties can be used. Among these, silicone-based surface modifiers and fluorine-based surface modifiers are preferable. Specifically, silicone-based polymers and oligomers having silicone chains and polyalkylene oxide chains, silicone-based polymers and oligomers having silicone chains and polyester chains, perfluoroalkane Fluorine-based polymers and oligomers with polyalkylene oxide chains, fluorine-based polymers and oligomers with perfluoroalkyl ether chains and polyalkylene oxide chains, etc. It is sufficient to use more than one of these. A substance containing a (meth)acryloyl group in the molecule can be used for the purpose of improving the durability of the slidability and the like. Specific surface modifiers include: EBECRYL (registered trademark) 350 (manufactured by Daicel-Ornex), BYK-333 (BYK -Chemie Japan), BYK-377 (manufactured by BYK-Chemie Japan), BYK-378 (manufactured by BYK-Chemie Japan), BYK-UV3500 (manufactured by BYK-Chemie Japan) BYK-Chemie Japan), BYK-UV3505 (BYK-Chemie Japan), BYK-UV3576 (BYK-Chemie Japan), BYK- UV3535 (manufactured by BYK-Chemie Japan), Megaface (registered trademark) RS-75 (manufactured by DIC), Megaface (registered trademark) ) RS-76-E (manufactured by DIC), Megaface (registered trademark) RS-72-K (manufactured by DIC), Megaface ( Registered trademark) RS-76-NS (manufactured by DIC), Megaface (registered trademark) RS-90 (manufactured by DIC), Megaface ( Registered trademark) RS-91 (manufactured by DIC), Megaface (registered trademark) RS-55 (manufactured by DIC), Optool (registered trademark ) DAC-HP (manufactured by Daikin Corporation), ZX-058-A (manufactured by T&K TOKA), ZX-201 (manufactured by T&K TOKA), ZX-202 (manufactured by T&K TOKA), ZX-212 (manufactured by T&K TOKA), ZX -214-A (manufactured by T&K TOKA), X-22-164AS (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164A (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164B (manufactured by Shin-Etsu Chemical Co., Ltd.), X -22-164C (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-164E (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-174DX (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

The active energy ray-curable composition of the present invention can be preferably used as a cured coating film that imparts anti-fogging properties to a base material by applying it to at least one surface of various materials and then irradiating it with active energy rays. The cured coating film containing the composition of the present invention suppresses the reduction of the anti-fogging property and substrate adhesion in a high-temperature environment, and does not damage the appearance, so it is used as a coating for long-term use in a severe high-temperature and high-humidity environment or outdoors. The anti-fog coating film of the material exerts an excellent effect.

＜Hardened objects, articles＞ (Structural materials) The article of the present invention has a coating film comprising a cured product of the active energy ray-curable composition of the present invention, and a substrate. The substrate is not particularly limited, and can be appropriately selected according to the application, for example, plastic, glass, wood, metal, metal oxide, paper, silicon or modified silicon, etc., can also be a substrate obtained by joining different raw materials. material. The shape of the substrate is also not particularly limited, and may be any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape with curvature on the entire surface or a part thereof. In addition, the hardness, thickness, and the like of the base material are also not limited.

The plastic substrate is not particularly limited as long as it contains a resin, and for example, the above-mentioned thermosetting resin or thermoplastic resin may be used. The mechanical material may be a single resin or a substrate in which multiple resins are mixed, and may have a single layer or a laminated structure of two or more layers. In addition, these plastic substrates can be reinforced with fibers (Fiber Reinforced Polymer (FRP)).

In addition, the substrate may also contain known antistatic agents, antifogging agents, antiblocking agents, ultraviolet absorbers, antioxidants, pigments, organic fillers, inorganic fillers, optical Stabilizers, crystal nucleating agents, lubricants and other known additives.

The article of the present invention may further have a second base material on the base material and the cured coating film. The material of the second substrate is not particularly limited, and examples include glass, wood, metal, metal oxide, plastic, paper, silicon, or modified silicon, or a substrate obtained by bonding different materials. The shape of the substrate is not particularly limited, and may be any shape according to the purpose, such as a flat plate, a sheet, or a three-dimensional shape in which the entire surface or a part thereof has curvature. In addition, the hardness, thickness, and the like of the base material are also not limited.

Since the cured coating film of the present invention has high adhesion to plastics and inorganic substances, it can also be preferably used as an interlayer material of dissimilar materials. Especially preferred is the case where the base material is plastic and the second base material is an inorganic layer. Examples of inorganic layers include quartz, sapphire, glass, optical films, ceramic materials, inorganic oxides, vapor-deposited films (chemical vapor deposition (Chemical Vapor Deposition, CVD), physical vapor deposition (Physical Vapor Deposition, PVD) , sputtering), magnetic film, reflective film, Ni, Cu, Cr, Fe, stainless steel and other metals, paper, spin on glass (Spin On Glass, SOG), spin on carbon (Spin On Carbon, SOC), polyester- Plastic layer such as polycarbonate-polyimide, thin film transistor (Thin Film Transistor, TFT) array substrate, plasma display panel (Plasma Display Panel, PDP) electrode plate, indium tin oxide (Indium Tin Oxide, ITO) or metal Conductive substrates, insulating substrates, silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon and other silicon-based substrates.

(Manufacturing method) The article of the present invention is obtained by coating the surface of a substrate with the composition of the present invention and then curing it. Coating to the base material can be carried out by directly applying the composition to the base material or by forming the composition directly on the base material and curing it. In the case of direct coating, the coating method is not particularly limited, and examples thereof include spray coating, spin coating, dipping, roll coating, blade coating, doctor roll, doctor blade, and curtain coating. , Slit coating method, screen printing method, inkjet method, etc. When performing direct molding, in-die molding, insert molding, vacuum forming, extrusion lamination molding, press molding, etc. are mentioned. In addition, the article of the present invention can also be obtained by laminating a cured product of the composition on a substrate. In the case of laminating a cured product of the composition, a semi-cured cured product may be laminated on a substrate and then completely cured, or a fully cured cured product may be laminated on a substrate.

Since the composition of the present invention contains a compound having a polymerizable unsaturated group, it can be cured by irradiating active energy rays. The active energy rays include ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Among these, ultraviolet rays (Ultraviolet, UV) are preferable in terms of curability and convenience. Lamp, electrodeless lamp (fusion lamp), chemical lamp, black light lamp, mercury-xenon lamp, short-arc lamp, helium-cadmium laser, argon laser, sunlight, light-emitting diode (light-emitting diode, LED) lamp, etc. A cured coating film or a cured product can be obtained by irradiating the coated or shaped composition with ultraviolet rays having a wavelength of about 180 nm to 400 nm using these. The irradiation amount of ultraviolet rays can be appropriately selected according to the type and amount of the photopolymerization initiator to be used. Here, when ultraviolet rays are used as active energy rays, examples of devices for irradiating the ultraviolet rays include low-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide

(use) The cured product of the composition of the present application has excellent anti-fogging properties and heat resistance, so it can be suitably used for helmet visors, face shields, and goggles in relation to safety gear, and can be suitably used in relation to automobiles for headlights, Windshield, glass, rearview mirror, video camera, canopy, roof, cockpit instrument, etc. In addition, it is also suitable for various mirrors, lamps, digital signage, head-up displays, virtual reality (VR) displays, global positioning system (global positioning system) , GPS) navigation devices, electronic control panels, food freezer boxes, business freezers, binoculars, surveillance cameras, surgical cameras, sunglasses, glasses, automotive glass for preventing scattering or window glass or mirrors or display cases Anti-fog film for anti-fogging, partitions for infectious diseases, monitor covers, sensor covers, etc. [Example]

Hereinafter, although an Example and a comparative example are used and this invention is demonstrated more concretely, this invention is not limited to the following aspect. In addition, in the present Examples, "parts" and "%" are based on mass unless otherwise specified.

(Synthesis Example 1: Synthesis of Urethane Acrylate Compound (A-1)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "Desmodur H" (94.14 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Base hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heat up to 70°C, and add pentaerythritol triacrylate (trade name "Aronix" manufactured by Dongya Gosei Co., Ltd.) in batches for 1 hour. ) M-306", containing about 30% by mass of pentaerythritol tetraacrylate) (199.74 parts by mass) and "PEG-200" (55.28 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-1) (containing about 17.2% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 2: Synthesis of Urethane Acrylate Compound (A-2)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "Desmodur (Desmodur) H" (24.52 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (52.03 parts by mass) and "PEG-4000S" (272.62 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-2) (containing about 4.2% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 3: Synthesis of Urethane Acrylate Compound (A-3)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "Desmodur (Desmodur) H" (116.65 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (123.75 parts by mass) and "HEA" (40.27 parts by mass) manufactured by Osaka Organic Chemical Industry Co., Ltd. and "PEG-200" (68.50 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-3) (containing about 10.6% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 4: Synthesis of Urethane Acrylate Compound (A-4)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "Desmodur H" (74.25 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "MIRAMER (MIRAMER) M500" manufactured by MIWON Company in batches for 1 hour (231.31 parts by mass) and "PEG-200" (43.60 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, it reacted at 80 degreeC until the infrared absorption spectrum of 2250 cm ^-1 which shows an isocyanate group disappeared, and obtained the urethane acrylate compound (A-4).

(Synthesis Example 5: Synthesis of Urethane Acrylate Compound (A-5)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, "Duronide" manufactured by Asahi Kasei Co., Ltd. (Duranate) 24A-100" (138.99 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxyterephthalene Phenol (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (184.63 parts by mass) manufactured by Toagosei Co., Ltd. in batches for 1 hour and "PEG-200" (24.55 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-5) (containing about 15.9% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 6: Synthesis of Urethane Acrylate Compound (A-6)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "Desmodur H" (80.68 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (171.60 parts by mass) and "PEG-400" (96.69 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-6) (containing about 14.7% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 7: Synthesis of Urethane Acrylate Compound (A-7)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "Desmodur H" (57.49 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated to 70°C, and put into "Aronix (Aronix) M-306" (121.98 parts by mass) and "PEG-1000" (169.69 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-7) (containing about 10.5% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 8: Synthesis of Urethane Acrylate Compound (A-8)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "Desmodur H" (39.31 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (83.40 parts by mass) and "PEG-2000" (226.45 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-8) (containing about 7.0% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 9: Synthesis of Urethane Acrylate Compound (A-9)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "IPDI" (72.16 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxyhydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into “Aronix (Aronix) M-306” (115.85 parts by mass) manufactured by Toagosei Co., Ltd. and Sanyo Chemical Industry Co., Ltd. "PEG-1000" (161.16 parts by mass) manufactured by the company. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, and the urethane acrylate compound (A-9) (containing about 10% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 10: Synthesis of Urethane Acrylate Compound (A-10)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "Desmodur W" (82.14 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (111.67 parts by mass) and "PEG-1000" (155.35 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-10) (containing about 9.6% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 11: Synthesis of Urethane Acrylate Compound (A-11)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, "Take Naite (Takenate) 600” (64.74 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxyterephthalene Phenol (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (118.95 parts by mass) manufactured by Toagosei Co., Ltd. in batches for 1 hour and "PEG-1000" (165.47 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-11) (containing about 10.2% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 12: Synthesis of Urethane Acrylate Compound (A-12)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, "NBDI" manufactured by Mitsui Chemicals Co., Ltd. was placed. (67.96 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxyhydroquinone (0.07 parts by mass), Dibutyltin diacetate (0.07 parts by mass), raised to 70°C, and put into "Aronix (Aronix) M-306" (117.60 parts by mass) manufactured by Toagosei Co., Ltd. and "Aronix" manufactured by Sanyo Chemical Industry Co., Ltd. PEG-1000" (163.60 parts by mass). After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-12) (containing about 10.1% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 13: Synthesis of Urethane Acrylate Compound (A-13)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "Desmodur (Desmodur) W" (104.74 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and added in batches to "HEA" (46.33 parts by mass) manufactured by Osaka Organic Chemical Industry Co., Ltd. and Sanyo Chemical Industry Co., Ltd. "PEG-1000" (198.09 parts by mass) manufactured by Kogyo Co., Ltd. After charging, it reacted at 80 degreeC until the infrared absorption spectrum of 2250 cm ^-1 which shows an isocyanate group disappeared, and the urethane acrylate compound (A-13) was obtained.

(Synthesis Example 14: Synthesis of Urethane Acrylate Compound (A-14)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "Desmodur W" (119.26 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (108.09 parts by mass) and "PEG-400" (121.81 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-14) (containing about 9.3% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 15: Synthesis of Urethane Acrylate Compound (A-15)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "Desmodur W" (123.43 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated to 70°C, and put into "Aronix (Aronix) M-306" (83.90 parts by mass) and "PEG-400" (141.82 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, and the urethane acrylate compound (A-15) (containing about 7.2% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 16: Synthesis of Urethane Acrylate Compound (A-16)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "Desmodur W" (127.91 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (57.96 parts by mass) and "PEG-400" (163.29 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, and the urethane acrylate compound (A-16) (containing about 5.0% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 17: Synthesis of Urethane Acrylate Compound (A-17)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "Desmodur W" (78.85 parts by mass), isobutyl acetate (150 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.70 parts by mass), methoxy Hydroquinone (0.07 parts by mass), dibutyltin diacetate (0.07 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (71.47 parts by mass) and "PEG-1000" (198.84 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-17) (containing about 6.1% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 18: Synthesis of Urethane Acrylate Compound (B-1)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "IPDI" (188.55 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.00 parts by mass), methoxyhydroquinone (0.10 parts by mass), dibutyltin diacetate (0.10 parts by mass), heated to 70°C, and put in batches of "HEA" (98.49 parts by mass) manufactured by Osaka Organic Chemical Industry Co., Ltd. and "ETERNACOLL UH-50" manufactured by Ube Industries, Ltd. ( 211.77 parts by mass). After charging, it reacted at 80 degreeC until the infrared absorption spectrum of 2250 cm ^-1 which shows an isocyanate group disappeared, and obtained the urethane acrylate compound (B-1).

(Synthesis Example 19: Synthesis of Urethane Acrylate Compound (B-2)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "IPDI" (83.61 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.00 parts by mass), methoxyhydroquinone (0.10 parts by mass), dibutyltin diacetate (0.10 parts by mass), heated to 70°C, and put in batches of "HEA" (43.68 parts by mass) manufactured by Osaka Organic Chemical Industry Co., Ltd. and "ETERNACOLL UH-200" manufactured by Ube Industries, Ltd. ( 371.51 parts by mass). After charging, it reacted at 80 degreeC until the infrared absorption spectrum of 2250 cm ^-1 which shows an isocyanate group disappeared, and obtained the urethane acrylate compound (B-2).

(Synthesis Example 20: Synthesis of Urethane Acrylate Compound (B-3)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "IPDI" (60.31 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.00 parts by mass), methoxyhydroquinone (0.10 parts by mass), dibutyltin diacetate (0.10 parts by mass), heated to 70°C, and put in batches of "HEA" (31.51 parts by mass) manufactured by Osaka Organic Chemical Industry Co., Ltd. and "ETERNACOLL UH-300" manufactured by Ube Industries, Ltd. ( 406.98 parts by mass). After charging, it reacted at 80 degreeC until the infrared absorption spectrum of 2250 cm ^-1 which shows an isocyanate group disappeared, and obtained the urethane acrylate compound (B-3).

(Synthesis Example 21: Synthesis of Urethane Acrylate Compound (B-4)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "IPDI" (189.11 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.00 parts by mass), methoxyhydroquinone (0.10 parts by mass), dibutyltin diacetate (0.10 parts by mass), heated up to 70°C, and put in batches of "HEA" (98.79 parts by mass) manufactured by Osaka Organic Chemical Industry Co., Ltd. and "ETERNACOLL PH-50" manufactured by Ube Industries, Ltd. ( 210.90 parts by mass). After charging, it reacted at 80 degreeC until the infrared absorption spectrum of 2250 cm ^-1 which shows an isocyanate group disappeared, and obtained the urethane acrylate compound (B-4).

(Synthesis Example 22: Synthesis of Urethane Acrylate Compound (B-5)) Into a 1-liter flask including a stirrer, a gas inlet tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "IPDI" (133.85 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.00 parts by mass), methoxyhydroquinone (0.10 parts by mass), dibutyltin diacetate (0.10 parts by mass), heated to 70°C, and put in batches of "HEA" (69.92 parts by mass) manufactured by Osaka Organic Chemical Industry Co., Ltd. and "ETERNACOLL PH-100" manufactured by Ube Industries, Ltd. ( 295.03 parts by mass). After charging, it reacted at 80 degreeC until the infrared absorption spectrum of 2250 cm ^-1 which shows an isocyanate group disappeared, and obtained the urethane acrylate compound (B-5).

(Synthesis Example 23: Synthesis of Urethane Acrylate Compound (B-6)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "IPDI" (132.95 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.00 parts by mass), methoxyhydroquinone (0.10 parts by mass), dibutyltin diacetate (0.10 parts by mass), raised the temperature to 70°C, and put in batches "HEA" (69.45 parts by mass) manufactured by Osaka Organic Chemical Industry Co., Ltd. and "Kuraray polyol" manufactured by Kuraray Co., Ltd. C-1090" (296.40 parts by mass). After charging, it reacted at 80 degreeC until the infrared absorption spectrum of 2250 cm ^-1 which shows an isocyanate group disappears, and the urethane acrylate compound (B-6) was obtained.

(Synthesis Example 24: Synthesis of Urethane Acrylate Compound (B-7)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was added Covestro (Covestro) Co., Ltd. "Desmodur W" (118.03 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.00 parts by mass), methoxyhydroquinone (0.10 parts by mass) , dibutyltin diacetate (0.10 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (160.46 parts by mass) manufactured by Toagosei Co., Ltd. "ETERNACOLL PH-100" (220.31 parts by mass). After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ⁻¹ indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (B-7) (containing about 9.6% by mass of pentaerythritol tetraacrylate).

(Synthesis Example 25: Synthesis of Urethane Acrylate Compound (B-8)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, was placed Covestro (Covestro) Co., Ltd. "Desmodur W" (150.75 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.00 parts by mass), methoxyhydroquinone (0.10 parts by mass) , dibutyltin diacetate (0.10 parts by mass), heated up to 70°C, and put into "HEA" (66.68 parts by mass) manufactured by Osaka Organic Chemical Industry Co., Ltd. and "Etnaco" ( ETERNACOLL) PH-100" (281.37 parts by mass). After charging, it reacted at 80 degreeC until the infrared absorption spectrum of 2250 cm ^-1 which shows an isocyanate group disappears, and the urethane acrylate compound (B-8) was obtained.

(Synthesis Example 26: Synthesis of Urethane Acrylate Compound (A-18)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, "Duronide" manufactured by Asahi Kasei Co., Ltd. (Duranate)” 24A-100 (178.72 parts by mass), isobutyl acetate (180.4 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.80 parts by mass), methoxyterephthalene Phenol (0.08 parts by mass), dibutyltin diacetate (0.08 parts by mass), the temperature was raised to 70°C, and 2-hydroxyethyl acrylate (77.60 parts by mass) and "PEG-1000" manufactured by Sanyo Chemical Industry Co., Ltd. were added in batches for 1 hour "(164.61 parts by mass). After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, and the urethane acrylate compound (A-18) (containing about 0.0% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 27: Synthesis of Urethane Acrylate Compound (A-19)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, "Droneide" manufactured by Asahi Kasei Co., Ltd. (Duranate) 24A-100” (178.72 parts by mass), isobutyl acetate (214.75 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.00 parts by mass), methoxyterephthalene Phenol (0.10 parts by mass), dibutyltin diacetate (0.10 parts by mass), the temperature was raised to 70°C, and 2-hydroxyethyl acrylate (38.80 parts by mass) and "Onix ( "Aronix) M-306" (118.96 parts by mass) and "PEG-1000" (164.61 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, thereby obtaining the urethane acrylate compound (A-19) (containing about 7.1% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 28: Synthesis of Urethane Acrylate Compound (A-20)) Into a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, "Dronide" manufactured by Asahi Kasei Co., Ltd. (Duranate) 24A-100" (178.72 parts by mass), isobutyl acetate (249.11 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.10 parts by mass), methoxyterephthalene Phenol (0.11 parts by mass), dibutyltin diacetate (0.11 parts by mass), heated up to 70°C, and put into "Aronix (Aronix) M-306" (237.91 parts by mass) manufactured by Toagosei Co., Ltd. in batches for 1 hour and "PEG-1000" (164.61 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, and the urethane acrylate compound (A-20) (containing about 12.3% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 29: Synthesis of Urethane Acrylate Compound (A-21)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, put Sumika Bayer Urethane (Sumika Bayer Urethane) "Sumidur N3300" (isocyanurate structure of hexamethylene diisocyanate) (192.66 parts by mass), isobutyl acetate (186.4 parts by mass), 2,6-di-tert-butyl-4-methylphenol (0.90 parts by mass), methoxyhydroquinone (0.09 parts by mass), dibutyltin diacetate (0.09 parts by mass), heated to 70 ° C, for 2-Hydroxyethyl acrylate (77.60 parts by mass) and "PEG-1000" (164.61 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. were added in batches for 1 hour. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, and the urethane acrylate compound (A-21) (containing about 0.0% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 30: Synthesis of Urethane Acrylate Compound (A-22)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, put Sumika Bayer Urethane (Sumika Bayer Urethane) "Sumidur N3300" (isocyanurate structure of hexamethylene diisocyanate) (192.66 parts by mass), isobutyl acetate (220.73 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.00 parts by mass), methoxyhydroquinone (0.10 parts by mass), dibutyltin diacetate (0.10 parts by mass), heated to 70°C for 2-Hydroxyethyl acrylate (38.80 parts by mass) and "Aronix M-306" (118.96 parts by mass) manufactured by Toagosei Co., Ltd. and "PEG-1000" manufactured by Sanyo Chemical Industry Co., Ltd. were added in batches for 1 hour (164.61 parts by mass). After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, and the urethane acrylate compound (A-22) (containing about 6.9% by mass in the solid content pentaerythritol tetraacrylate).

(Synthesis Example 31: Synthesis of Urethane Acrylate Compound (A-23)) In a 1-liter flask including a stirrer, a gas introduction tube, a condenser, and a thermometer, put Sumika Bayer Urethane (Sumika Bayer Urethane) "Sumidur N3300" (isocyanurate structure of hexamethylene diisocyanate) (192.66 parts by mass), isobutyl acetate (255.08 parts by mass), 2,6-di-tert-butyl-4-methylphenol (1.20 parts by mass), methoxyhydroquinone (0.12 parts by mass), dibutyltin diacetate (0.12 parts by mass), heated to 70°C for "Aronix M-306" (237.91 parts by mass) manufactured by Toagosei Co., Ltd. and "PEG-1000" (164.61 parts by mass) manufactured by Sanyo Chemical Industry Co., Ltd. were added in batches for 1 hour. After charging, the reaction was carried out at 80°C until the infrared absorption spectrum at 2250 cm ^-1 indicating the isocyanate group disappeared, and the urethane acrylate compound (A-23) (containing about 12.0% by mass in the solid content pentaerythritol tetraacrylate).

In the following examples and comparative examples, compound (A-1) to compound (A-23) were used as component (A) and compound (B-1) to compound (B-8) were used as component (B) . Their detailed structures are shown in Table 1. In addition, α or β or γ, X or Z, Y ₁ to Y ₆ , n1 or n2 in Table 1 correspond to the symbols in formula (1) to formula (2) and formula (6), and α or β or γ represents the structure obtained by removing the isocyanate group from the isocyanate compounds in the table, and X or Z represents the structure obtained by removing the terminal hydrogen atoms of the polyethylene glycol or polycarbonate polyol in the table.

[Table 1] compound compound alpha or beta or gamma X or Z _Y1 ～ _Y6 n1 or n2 (A-1) (1) HDI PEG200 Y ₁ : Formula (4) Y ₂ : Formula (4) 1 (A-2) PEG4000 (A-3) PEG200 Y ₁ : Formula (4) Y ₂ : Formula (5) (A-4) Y ₁ : Formula (3) Y ₂ : Formula (3) (A-5) (2) HDI-B Y ₁ ~Y ₄ : All are formula (4) (A-6) (1) HDI PEG400 Y ₁ : Formula (4) Y ₂ : Formula (4) (A-7) PEG1000 (A-8) PEG2000 (A-9) IPDI PEG1000 (A-10) H ₁₂ MDI (A-11) H ₆ XDI (A-12) NBDI (A-13) H ₁₂ MDI Y ₁ : Formula (5) Y ₂ : Formula (5) (A-14) PEG400 Y ₁ : Formula (4) Y ₂ : Formula (4) 2 (A-15) 3 (A-16) 5 (A-17) PEG1000 2 (A-18) (2) HDI-B PEG1000 Y ₁ ～Y ₄ : Equation (5) 1 (A-19) Y ₁ to Y ₂ : Formula (5) Y ₃ to Y ₄ : Formula (4) 1 (A-20) Y ₁ ~Y ₄ : formula (4) 1 (A-21) HDI-N PEG1000 Y ₁ ～Y ₄ : Equation (5) 1 (A-22) Y ₁ to Y ₂ : Formula (5) Y ₃ to Y ₄ : Formula (4) 1 (A-23) Y ₁ ~Y ₄ : Formula (4) 1 (B-1) (6) IPDI UH-50 Y ₅ : Formula (5) Y ₆ : Formula (5) 1 (B-2) UH-200 (B-3) UH-300 (B-4) PH-50 (B-5) PH-100 (B-6) C-1090 (B-7) H ₁₂ MDI PH-100 Y ₅ : Formula (4) Y ₆ : Formula (4) (B-8) Y ₅ : Formula (5) Y ₆ : Formula (5)

The abbreviations shown in the above-mentioned Table 1 represent the following compounds. HDI: Hexamethylene diisocyanate, trade name "Desmodur (Desmodur) H", Covestro (Covestro) Co., Ltd. De (Duranate) 24A-100", manufactured by Asahi Kasei Co., Ltd. HDI-N: isocyanurate type hexamethylene diisocyanate, trade name "Sumidur N3300", Sumika Bayer Urethane (Sumika Bayer Urethane) IPDI: Isophorone diisocyanate, trade name "IPDI", Covestro H ₁₂ MDI: 4,4'-methylene bis(cyclohexyl isocyanate), commercial Name "Desmodur W", manufactured by Covestro Corporation H ₆ XDI: hydrogenated xylene diisocyanate, trade name "Takenate (Takenate) 600", manufactured by Mitsui Chemicals Corporation NBDI: drop Bornane diisocyanate, trade name "NBDI", manufactured by Mitsui Chemicals Co., Ltd. PEG200: Polyethylene glycol, number average molecular weight about 200, trade name "PEG-200", manufactured by Sanyo Chemical Industry Co., Ltd. PEG400: Polyethylene glycol, number average Molecular weight about 400, trade name "PEG-400", manufactured by Sanyo Chemical Industry Co., Ltd. PEG1000: polyethylene glycol, number average molecular weight about 1000, trade name "PEG-1000", manufactured by Sanyo Chemical Industry Co., Ltd. PEG2000: polyethylene glycol, The number average molecular weight is about 2000, the product name is "PEG-2000", manufactured by Sanyo Chemical Industry Co., Ltd. Carbonate diol (reaction product of 1,6-hexanediol and dimethyl carbonate), number average molecular weight: about 500, trade name "ETERNACOLL (ETERNACOLL) UH-50", manufactured by Ube Industries, Ltd. UH -200: Polycarbonate diol (reaction product of 1,6-hexanediol and dimethyl carbonate), number average molecular weight: about 2000, trade name "ETERNACOLL (ETERNACOLL) UH-200", Ube Xing UH-300 manufactured by the company: polycarbonate diol (reaction product of 1,6-hexanediol and dimethyl carbonate), number average molecular weight: about 3000, trade name "ETERNACOLL (ETERNACOLL) UH-300 ", PH-50 manufactured by Ube Industrial Co., Ltd.: polycarbonate diol (reaction product of 1,6-hexanediol, 1,5-pentanediol and carbonate), number average molecular weight: about 500, trade name " ETERNACOLL PH-50", PH-100 manufactured by Ube Industrial Co., Ltd.: polycarbonate diol (reaction product of 1,6-hexanediol, 1,5-pentanediol and carbonate), Number average molecular weight: about 1000, trade name "ETERNACOLL (ETERNACOLL) PH-100", manufactured by Ube Industries, Ltd. C-1090: polycarbonate diol (1,6-hexanediol and 3-methyl- Reaction product of 1,5-pentanediol and carbonate), number average molecular weight: about 1000, trade name "Kuraray polyol (Kuraray polyol) C-1090", manufactured by Kuraray

(Example 1) As a solid content, 100 parts by mass of compound (A-1) (containing about 23.5% by mass of pentaerythritol tetraacrylate), 3 parts by mass of a photopolymerization initiator (Omnirad (Omnirad) 2959 (manufactured by IGM)) 1.5 Parts by mass, Omnirad (Omnirad) 819 (manufactured by IGM) 1.5 parts by mass) were uniformly mixed with propylene glycol monomethyl ether so that the solid content became 40 wt%, thereby preparing an active energy ray-curable composition (1 ).

(Example 2 to Example 52, Comparative Example 1 to Comparative Example 5) Except having changed to the composition of the solid content shown in Table 2 - Table 7, it carried out similarly to Example 1, and obtained the active energy ray curable composition of each example.

[Preparation of evaluation samples] The active energy ray-curable composition of each example was coated on a polycarbonate substrate (trade name "Carbo Glass" (registered trademark) manufactured by AGC Corporation) so that the film thickness became 5 μm. Polished transparent (polish clear) (thickness: 2 mm, area: 10 cm × 10 cm), dried at 80 ° C for 4 minutes, and ultraviolet light was carried out under the conditions of 200 mW/cm ² and 1000 mJ/cm ² using a high-pressure mercury lamp. Irradiation was performed, and the obtained laminated body of the polycarbonate substrate and the cured product was used as a test piece.

[Evaluation of initial anti-fog properties] At a height of 2 cm from the water surface of a warm water bath maintained at 80°C, set the test piece with the coating film facing down, and continuously irradiate the coating film with steam from the warm water bath for 10 seconds. Evaluate whether there is fog at this time. ○: A water film is formed immediately after steam irradiation, and no fogging occurs. △: Instantaneous fogging was confirmed immediately after steam irradiation, and a water film was formed without fogging. ×: No clean water film was formed after steam irradiation, and fogging was confirmed.

[Evaluation of anti-fogging property after high-temperature heating] After leaving the test piece at 120°C for 250 hours, set the test piece at a height of 2 cm from the water surface of a warm water bath kept at 50°C with the coating film facing down, and irradiate the coating film continuously for 60 Seconds of steam from a warm water bath, the time required to form a water film was measured. 60 seconds or less was set as pass. In addition, the case where the water film was not formed after the lapse of a certain time was made into x.

[Evaluation of substrate adhesion after high-temperature heating] The coated panel in which the cured product of the test piece was notched in a 1 mm-wide checkerboard shape of 10×10 was allowed to stand under the condition of 120° C. with a cutting machine. After a certain period of time, cellophane tape ("CT-24" manufactured by Nichiban Co., Ltd.) was attached to the checkerboard-shaped part, and the peeling operation was performed, and the time required for peeling was measured. 200 hours or more were set as pass.

[Evaluation of appearance (yellowness) after high-temperature heating] The smaller the yellowness (YI value) of the test piece is, the more transparent the laminate is, for example, when it is used for the front panel of a display device, it is easy to improve visibility. Therefore, the smaller the yellowness, the more excellent the external appearance was evaluated. Specifically, after allowing the test piece to stand at 120°C for 240 hours, a color difference meter "Color meter" manufactured by Nippon Denshoku Industries Co., Ltd. was used in accordance with Japanese Industrial Standards (JIS) K 7373:2006. ZE6000" measures the yellowness (Yellowness Index (YI) value) of the test piece. After performing the background measurement without the test piece, the optical film was placed on the sample holder, and the transmission measurement was performed to obtain the three stimulus values (X, Y, Z), and calculate the YI value based on the following formula. A YI value of 3 or less was regarded as acceptable. YI=100×(1.2985X-1.1335Z)/Y

[Evaluation of appearance (whitening) after high-temperature heating] After the test piece was left to stand under the condition of 120°C for 250 hours, the cured product was peeled off, the state was checked visually, and the evaluation was performed in the following three steps. ◎: No whitening at all 〇: Partial whitening ×: Full whitening

Active energy ray-curable composition (1) to active energy ray-curable composition (45) obtained in Example 1 to Example 52, and active energy ray-curable composition obtained in Comparative Example 1 to Comparative Example 5 were combined The compositions and evaluation results of the product (C1) to the active energy ray-curable composition (C5) are shown in Tables 2 to 7.

In addition, urethane acrylate compound (A-1) to urethane acrylate compound (A-12) and urethane acrylate compound (A-14) in Table 2 to Table 7 - The compounding quantity of a urethane acrylate compound (A-17) and a urethane acrylate compound (B-7) is a value containing pentaerythritol tetraacrylate. Therefore, the content of the urethane acrylate having a polyethylene glycol structure with respect to 100 parts by mass of the resin solid content in the composition is referred to as "(A) component ratio", and the polycarbonate polycarbonate The content of the urethane acrylate of the alcohol structure was shown in Tables 2 to 6 as "(B) component ratio" in percentage.

[Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 combination (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) compound (A-1) 100 (A-2) 100 (A-3) 100 (A-4) 100 (A-5) 100 (A-6) 100 (A-7) 100 (A-8) 100 (A-9) 100 (A-10) 100 (A-11) 100 Photopolymerization initiator 3 3 3 3 3 3 3 3 3 3 3 (A) Composition ratio [%] 82.8 95.8 89.4 100 84.1 93.0 85.3 89.5 90.0 90.4 89.8 Initial anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 After high temperature heating Anti-fog (s) 50 50 50 60 60 40 40 30 30 30 30 Adhesiveness (h) 200 200 200 200 200 200 200 200 300 300 300 Yellowness YI value 2 2.8 2.5 1.5 1.3 2.5 2 2.1 1.4 1.1 1.4 Appearance (albino) ◎ 〇 ◎ ◎ ◎ 〇 ◎ ◎ ◎ ◎ ◎

[table 3] Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 combination (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) compound (A-12) 100 (A-14) 100 95 95 95 95 95 95 (A-15) 100 (A-16) 100 (A-17) 100 (B-1) 5 (B-2) 5 (B-3) 5 (B-4) 5 (B-5) 5 (B-6) 5 Photopolymerization initiator 3 3 3 3 3 3 3 3 3 3 3 (A) Composition ratio [%] 89.9 90.7 92.8 95.0 93.9 86.2 86.2 86.2 86.2 86.2 86.2 (B) Composition ratio [%] 0 0 0 0 0 5.0 5.0 5.0 5.0 5.0 5.0 Initial anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 After high temperature heating Anti-fog (s) 30 20 20 20 20 20 20 20 20 20 20 Adhesiveness (h) 300 300 300 300 300 450 400 350 450 450 450 Yellowness YI value 1.3 1.2 1.3 1.2 1.1 1.1 1.1 1.6 1.1 1.1 1.6 Appearance (albino) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

[Table 4] Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 combination (twenty three) (twenty four) (25) (26) (27) (28) (29) (30) (31) (32) (33) compound (A-14) 95 95 90 80 70 60 50 20 30 45 80 (B-1) 10 20 30 40 50 60 40 30 (B-7) 5 (B-8) 5 UV-3310B 20 M-3190 30 A-DPH-12E 25 ACMO 20 Surfactant 1 Photopolymerization initiator 3 3 3 3 3 3 3 3 3 3 3 (A) Composition ratio [%] 86.2 86.2 81.6 72.6 63.5 54.4 45.4 18.1 27.2 40.8 72.6 (B) Composition ratio [%] 4.5 5.0 10.0 20.0 30.0 40.0 50.0 60.0 40.0 30.0 20.0 Initial anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 After high temperature heating Anti-fog (s) 20 20 20 20 20 20 40 50 20 20 20 Adhesiveness (h) 450 450 500 700 700 700 700 700 700 700 700 Yellowness YI value 0.8 0.8 1.1 1.1 1.1 1.1 1.1 1.5 1.3 1.1 1.1 Appearance (albino) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

[table 5] Example 34 Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Example 43 Example 44 combination (34) (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) compound (A-14) 80 80 80 80 80 80 80 80 80 80 80 (B-1) 20 20 20 20 20 20 20 20 20 20 20 Surfactant 1 3 1.5 1.5 Surfactant 2 3 Surfactant 3 3 3 1.5 0.5 1 5 10 1.5 Surfactant 4 3 0.5 0.25 Photopolymerization initiator 3 3 3 3 3 3 3 3 3 3 3 (A) Composition ratio [%] 72.6 72.6 72.6 72.6 72.6 72.6 72.6 72.6 72.6 72.6 72.6 (B) Composition ratio [%] 20 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Initial anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 After high temperature heating Anti-fog (s) 10 10 5 10 1 1 10 5 5 5 1 Adhesiveness (h) 700 700 700 700 700 700 700 700 700 700 700 Yellowness YI value 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Appearance (albino) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

[Table 6] Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 Example 51 Example 52 combination (45) (45) (45) (45) (45) (45) (45) (45) compound (A-18) 100 70 (A-19) 100 (A-20) 100 (A-21) 100 70 (A-22) 100 (A-23) 100 (B-1) 30 30 (B-2) (B-3) (B-4) (B-5) (B-6) Photopolymerization initiator 3 3 3 3 3 3 3 3 (A) Composition ratio [%] 100 92.9 87.7 100 93.1 88 70 70 (B) Composition ratio [%] 0 0 0 0 0 0 30 30 Initial anti-fog 〇 〇 〇 〇 〇 〇 〇 〇 After high temperature heating Anti-fog (s) 20 25 30 20 25 30 20 20 Adhesiveness (h) 300 300 300 300 300 300 700 700 Yellowness YI value 1.3 1.3 1.3 1.1 1.1 1.1 1.1 1.1 Appearance (albino) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎

[Table 7] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 combination (C1) (C2) (C3) (C4) (C5) compound (A-13) 80 100 (B-1) 20 100 40 30 M-3190 60 A-DPH-12E 70 Photopolymerization initiator 3 3 3 3 3 (A) Composition ratio [%] 80 100 0 0 0 (B) Composition ratio [%] 20.0 0 100 40.0 30.0 Initial anti-fog 〇 〇 x x x After high temperature heating Anti-fog (s) x x x x x Adhesiveness (h) 200 50 300 300 300 Yellowness YI value 4 4 5 4 4 Appearance (albino) x x 〇 x 〇

The abbreviations shown in Table 2 to Table 7 represent the following compounds.・M3190: Trimethylolpropane EO modified triacrylate, trade name "Miramer M3190", manufactured by MIWON Corporation ・A-DPH-12E: Ethoxylated dipentaerythritol polyacrylic acid Ester, trade name "NK Ester (NK Ester) A-DPH-12E", manufactured by Shin-Nakamura Chemical Co., Ltd. ・ACMO: Acryloylmorpholine, trade name "ACMO (Acryloylmorpholine)", manufactured by KJ Chemical Co., Ltd. ・UV-3310B: Urethane acrylate having a structure derived from polycarbonate polyol, trade name "Ultraviolet (registered trademark) UV-3310B, manufactured by Mitsubishi Chemical Corporation" ・Surfactant 1: Nonionic surfactant, trade name "Noigen XL-40", manufactured by Daiichi Kogyo Pharmaceutical Co. Active agent 3: sodium dioctyl sulfosuccinate, trade name "Aerosol (Aerosol) OT-100", manufactured by Solvay (Solvay), R ₂₁ and R ₂₂ in the general formula (7) are carbon number 8 A compound with a branched alkyl group and A is sodium Surfactant 4: Cetyltrimethylammonium chloride, trade name "Lebon TM-16", manufactured by Sanyo Chemical Industry Co., Ltd. Photopolymerization initiator : Contains 50% each of 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name "Omnirad) 2959", manufactured by IGM Corporation) and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name "Omnirad (Omnirad) 819", manufactured by IGM Corporation) mixture・Solvent: Propylene Glycol Monomethyl Ether

It was confirmed that the cured coating film of the active energy ray-curable composition of the present invention prevents the reduction of the anti-fogging property and substrate adhesion after high-temperature heating, and does not impair the appearance. On the other hand, in Comparative Example 1 and Comparative Example 2 in which the compound (A-13) having less than four (meth)acryl groups in the molecule was used as the component (A), the anti-fogging properties after high-temperature heating were significantly reduced. , and the appearance is also deteriorated. Furthermore, it was confirmed that the antifogging property and adhesiveness of the comparative example 3 - the comparative example 5 which did not contain (A) component also fell similarly, and the external appearance was impaired.

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Claims (11)

An active energy ray-curable composition, containing polyfunctional urethane (meth)acrylate (A) represented by the following general formula (1) or general formula (2); In the formula, X represents a structure derived from polyalkylene glycol, and Y ₁ to Y ₄ are independently selected from the following general formula (3), general formula (4) and general formula (5), the formula (1 ) and the compound represented by formula (2) contains at least one group represented by formula (3) or formula (4), α and β represent structures derived from isocyanate compounds, and multiple α or β in the formula can be the same as each other or Can be different, the average number of repetitions n1 is an integer from 1 to 10, In the formula, R ₁ to R ₅ independently represent a hydrogen atom or a methyl group, * is a bond, and the oxygen adjacent to any one of Y ₁ to Y ₄ in formula (1) or formula (2) atomic bonding, In the formula, R ₆ to R ₈ each independently represent a hydrogen atom or a methyl group, * is a bond, and the oxygen adjacent to any one of Y ₁ to Y ₄ in formula (1) or formula (2) atomic bonding, In the formula, R ₉ represents a hydrogen atom or a methyl group, R ₁₀ represents an alkylene group with 2 to 10 carbons, * is a bond, and is adjacent to Y ₁ to Y in formula (1) or formula (2). Any one of ₄ is bonded to an oxygen atom. The active energy ray-curing composition according to claim 1, wherein the number average molecular weight of X in the general formula (1) or (2) is 250-1500. The active energy ray-curable composition according to claim 1, wherein α in the general formula (1) is a structure derived from a diisocyanate compound having an alicyclic structure. The active energy ray-curable composition according to claim 1, wherein β in the general formula (2) is a structure derived from a biuret-type or isocyanurate-type isocyanate compound. The active energy ray-curing composition according to any one of claim 1 to claim 4, wherein the average repetition number n1 in the general formula (1) or (2) is 1-3. The active energy ray-curable composition according to claim 1, comprising a polyfunctional urethane (meth)acrylate represented by the following general formula (6) having a structure derived from polycarbonate polyol (B); In the formula, Z represents a structure derived from polycarbonate polyols, Y ₅ to Y ₆ are independently selected from the general formula (3), general formula (4) and general formula (5), and γ represents a structure derived from In the structure of the isocyanate compound, a plurality of γ in the formula may be the same or different, and the average repetition number n2 is an integer of 1-10. The active energy ray-curable composition according to claim 6, wherein the content of the polyfunctional urethane (meth)acrylate (A) is 15 parts by mass relative to 100 parts by mass of resin solid content It is the range of -90 mass parts, and content of the said polyfunctional urethane (meth)acrylate (B) is the range of 5-60 mass parts with respect to 100 mass parts of resin solid content. The active energy ray-curing composition according to any one of Claims 1 to 7, further comprising a surfactant (C). The active energy ray-curing composition according to claim 8, wherein the surfactant (C) contains a salt represented by the following general formula (7); In the formula, R ₂₁ and R ₂₂ independently represent any one of an alkyl group, a cycloalkyl group, an alkenyl group, and an alkyl group modified with an alkylene oxide with a carbon number of 4 to 22, and A represents lithium, sodium, any of potassium. A cured product of an active energy ray-curable composition is a cured product of an active energy ray-curable composition according to any one of claim 1 to claim 9. An article having a coating film comprising the cured product according to claim 10.