TW202210542A - Active energy ray curable resin composition, cured film and film excellent in storage stability and can form a cured film having excellent antistatic properties, solvent resistance, and adhesion to a plastic substrate - Google Patents

Abstract

The present invention provides a water-based active energy ray-curable resin composition that is excellent in storage stability and can form a cured film having excellent antistatic properties, solvent resistance, and adhesion to a plastic substrate. The active energy ray-curable resin composition of the present invention includes: polyurethane (meth)acrylate (A), a conductive polymer (B), and water (C); the polyurethane (meth)acrylate (A) is a reactant containing reaction components of hydroxyl-containing (meth)acrylate (a1), polyisocyanate (a2), and hydroxyl-containing polyalkylene glycols (a3).

Description

Active energy ray curable resin composition, cured film and film

The present invention relates to an active energy ray-curable resin composition, a cured film and a film.

Plastic films such as polyester films have been widely used for plate-making films and packaging films, films for optical components, films for semiconductor processing tapes, hot stamping films, and decorative films for plastic molding. However, when the plastic film is wound, unwinded, or processed, static electricity is easily generated, and dust in the atmosphere adheres to cause physical defects (pinholes, etc.) on the surface, or poor running on the processing line. Then, various proposals have been made for the purpose of suppressing the electrification of the plastic film.

As one of such means, a method of applying a coating agent having an antistatic function to the surface of the film can be considered. For antistatic coating agents, in addition to antistatic functions, various properties such as solvent resistance of the film and adhesion between the plastic substrate and the film are generally required. As a conventional antistatic coating agent, for example, a coating agent using a quaternary ammonium salt type cationic compound in an active energy ray-curable resin composition containing (meth)acrylates has been proposed (refer to Patent Document 1). . Moreover, as another antistatic coating agent, the coating agent of conductive polymers, such as poly(thiophene) and poly(aniline), can be considered as an active energy ray-curable resin composition. Since such a coating agent is a conductive polymer that is not easily affected by an external environment such as humidity, it is considered that a sufficient antistatic function can be exhibited regardless of the use environment.

However, depending on the application, the active energy ray-curable resin composition may require lower viscosity, and in this case, methods such as using a large amount of a reactive diluent or using an organic solvent in combination are adopted. However, when a reactive diluent is used in a large amount, the curability is lowered, and sufficient physical properties of the coating film are not easily obtained, and when an organic solvent is used in combination, the risk of air pollution and fire increases.

Then, in recent years, from the viewpoints of workability and safety, there has been an increasing demand for water-based activation of an active energy ray-curable resin composition. For example, Patent Document 2 proposes an active energy ray-curable resin composition that can be dissolved in or dispersed in water to achieve low viscosity. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-315373 [Patent Document 2] Japanese Patent Application Laid-Open No. 11-279242

[Technical problem to be solved by the invention]

As an antistatic coating agent having a good antistatic function and excellent handleability and safety, it is conceivable to use a conductive polymer in a water-based active energy ray-curable resin composition. However, the present inventors conducted research and found that such a coating agent has a problem of insufficient stability during storage (storage stability) because the dispersibility of (meth)acrylates and conductive polymers in water is low. question.

An object of the present invention is to provide a water-based active energy ray-curable resin composition that is excellent in storage stability and can form a cured film having excellent antistatic properties, solvent resistance, and adhesion to a plastic substrate. [Technical means]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned polyurethane (meth)acrylic acid is obtained from an active energy ray-curable resin composition containing a polyurethane (meth)acrylate, a conductive polymer, and water. Ester is a reaction product containing predetermined hydroxyl group-containing (meth)acrylates, polyisocyanates, and hydroxyl group-containing polyalkylene glycols as reaction components, and can solve the above-mentioned problems, thereby completing the present invention.

Specifically, the present inventors found that by using a conductive polymer in the water-based resin composition containing the above-mentioned polyurethane (meth)acrylate, the resin composition has excellent storage stability. Furthermore, it was found that such a resin composition can form a cured film excellent in antistatic property, solvent resistance, and plastic adhesiveness. That is, the present invention relates to one of the following active energy ray-curable resin compositions.

1. An active energy ray curable resin composition is characterized by containing: Polyurethane (meth)acrylate (A), which is a reactant containing the reaction components of hydroxyl-containing (meth)acrylate (a1), polyisocyanate (a2), and hydroxyl-containing polyalkylene glycols (a3) ; a conductive polymer (B); and water (C).

2. The active energy ray-curable resin composition according to the above item 1, wherein the component (a1) is a hydroxyl group-containing (meth)acrylate having at least three (meth)acryloyl groups in the molecule.

3. The active energy ray-curable resin composition according to the above item 1 or 2, wherein the component (a2) is a polyisocyanate having at least three isocyanate groups in the molecule.

4. The active energy ray-curable resin composition according to any one of the above items 1 to 3, wherein the component (a3) is a compound represented by the following general formula (1). (Chemical 1) H-(OCH ₂ CH ₂ )n-OR (1) (wherein R represents any one of an alkyl group, an allyl group, a (meth)acryloyl group, and an acyl group, and n represents 3 an integer of ~25.)

5. The active energy ray-curable resin composition according to any one of the above items 1 to 4, wherein the component (B) is a poly(thiophene).

6. The active energy ray-curable resin composition according to any one of the above items 1 to 5, further comprising (meth)acrylate (meth)acrylate (meth)acrylate having at least 3 (meth)acryloyl groups in the molecule. D).

7. The active energy ray-curable resin composition according to any one of the above items 1 to 6, which further contains a surface conditioner (E).

8. The active energy ray-curable resin composition according to any one of the above items 1 to 7, wherein, in terms of solid content, with respect to 100 parts by mass of the total amount of (A) component and (B) component, ( The content of the component B) is 0.1 to 20 parts by mass.

9. A cured film comprising the active energy ray-curable resin composition according to any one of the above items 1 to 8.

10. A film characterized by containing the cured film described in the above item 9. [Effect of invention]

The active energy ray-curable resin composition of the present invention has good dispersibility and excellent storage stability. In addition, the above-mentioned active energy ray-curable resin composition can form a cured film excellent in antistatic property, solvent resistance, and plastic adhesion even if the film is 1 μm or less, so it is used as an antistatic coating agent system for plastic films. useful. Moreover, since the said active energy ray-curable resin composition is a water-based composition, it is excellent in handleability and safety|security.

[Active energy ray-curable resin composition] The active energy ray-curable resin composition of the present invention contains a specific polyurethane (meth)acrylate (A) (hereinafter, referred to as (A) component) and a conductive polymer (B) (hereinafter, referred to as (B) component) and water (C) (hereinafter, referred to as (C) component).

In this specification, "(meth)acrylic acid" means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Similarly, "(meth)acrylate" means "at least one selected from the group consisting of acrylate and methacrylate", and "(meth)acryloyl" means "selected from acryl and methyl." at least one of the group consisting of acryloyl groups".

<Polyurethane (meth)acrylate (A)> (A) Component contains hydroxyl group-containing (meth)acrylate (a1) (hereinafter referred to as (a1) component), polyisocyanate (a2) (hereinafter referred to as (a2) component), and hydroxyl group-containing polyalkane A reactant of the reaction component of diols (a3) (hereinafter, referred to as (a3) component). (A) Component can be used individually by 1 type, or can be used in combination of 2 or more types.

(Hydroxy-containing (meth)acrylate (a1)) As the component (a1), as long as it is a compound having at least one hydroxyl group and at least one (meth)acryloyl group in the molecule, various conventional ones can be used without particular limitation. (a1) A component can be used individually by 1 type, or can be used in combination of 2 or more types.

From the viewpoint of excellent hardness and abrasion resistance of the cured film obtained, the larger the number of (meth)acryloyl groups in the molecule in the component (a1), the better. From the viewpoint of easy availability, the number of (meth)acryloyl groups in the molecule of the component (a1) is usually about 1 to 5.

(a1) Component, for example, hydroxyl-containing glycerol poly(meth)acrylate, hydroxyl-containing polyglycerol poly(meth)acrylate, hydroxyl-containing neotaerythritol poly(meth)acrylate, hydroxyl-containing Hydroxyl-containing polynepentaerythritol poly(meth)acrylate, hydroxyl-containing trimethylolpropane poly(meth)acrylate, hydroxyl-containing polytrimethylolpropane poly(meth)acrylate, hydroxyl-containing poly(trimethylolpropane) poly(meth)acrylate The mono (meth)acrylate and so on.

The above-mentioned hydroxyl-containing glycerol poly(meth)acrylates include, for example, glycerol di(meth)acrylate; and glycerol mono(meth)acrylate, glycerol di(meth)acrylate and triglycerol( A mixture of at least two of the group of meth)acrylates, etc.

The above-mentioned hydroxyl-containing polyglycerol poly(meth)acrylates include, for example, diglycerol di(meth)acrylate, diglycerol tri(meth)acrylate, triglycerol di(meth)acrylate, triglycerol Tri(meth)acrylate, triglycerol tetra(meth)acrylate, etc.

The above-mentioned hydroxyl-containing neotaerythritol poly(meth)acrylates include, for example: neotaerythritol di(meth)acrylate; neotaerythritol tri(meth)acrylate; At least one of the group consisting of alcohol mono(meth)acrylate, neotaerythritol di(meth)acrylate, neotaerythritol tri(meth)acrylate and neotaerythritol tetra(meth)acrylate A mixture of the two, etc.

The above-mentioned hydroxyl group-containing polypivalerythritol poly(meth)acrylates include, for example, dipeptaerythritol di(meth)acrylate, dipivalerythritol tri(meth)acrylate, Tetraol tetra(meth)acrylate, Dipiveaerythritol penta(meth)acrylate, Trinetaerythritol di(meth)acrylate, Tripivalerythritol tri(meth)acrylate, Tripivalerythritol Neopentaerythritol Tetra(meth)acrylate, Trinetaerythritol Penta(meth)acrylate, Trinetaerythritol Hexa(meth)acrylate, Trinetaerythritol Hepta(meth)acrylate And the mixture of at least two kinds selected from these (meth)acrylates; the mixture of dipivalerythritol penta(meth)acrylate and dipivalerythritol hexa(meth)acrylate, etc.

As said hydroxyl-containing trimethylolpropane poly(meth)acrylate, trimethylolpropane di(meth)acrylate etc. are mentioned, for example.

As said hydroxyl-containing polytrimethylolpropane poly(meth)acrylate, ditrimethylolpropane di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, etc. are mentioned, for example.

The above-mentioned hydroxyl-containing mono(meth)acrylates include, for example, hydroxyl-containing linear alkyl (meth)acrylates, hydroxyl-containing linear (meth)acrylate caprolactone adducts, Hydroxyl-containing branched alkyl (meth)acrylate, hydroxyl-containing branched alkyl (meth)acrylate caprolactone adduct, hydroxyl-containing cycloalkyl (meth)acrylate, hydroxyl-containing Cycloalkyl (meth)acrylate caprolactone adduct, polyalkylene glycol mono(meth)acrylate caprolactone adduct, glycerol mono(meth)acrylate, and the like.

Examples of the above-mentioned hydroxyl-containing linear alkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. esters, etc.

The above-mentioned hydroxyl-containing linear alkyl (meth)acrylate caprolactone adduct includes, for example, 3-hydroxypropyl (meth)acrylate caprolactone adduct, 2-hydroxy (meth)acrylate Ethyl caprolactone adduct, 4-hydroxybutyl (meth)acrylate caprolactone adduct, etc.

The above-mentioned hydroxyl group-containing branched alkyl (meth)acrylates include, for example, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate. esters, etc.

The above-mentioned hydroxyl-containing branched alkyl (meth)acrylate caprolactone adduct includes, for example, 2-hydroxypropyl (meth)acrylate caprolactone adduct, 2-hydroxy (meth)acrylate Butyl caprolactone adduct, (meth)acrylate 3-hydroxybutyl caprolactone adduct, etc.

As said hydroxyl-containing cycloalkyl (meth)acrylate, hydroxycyclohexyl (meth)acrylate etc. are mentioned, for example.

As the above-mentioned hydroxyl group-containing cycloalkyl (meth)acrylate caprolactone adduct, for example, (meth)acrylate hydroxycyclohexyl caprolactone adduct and the like are exemplified.

Examples of the above-mentioned polyalkylene glycol mono(meth)acrylate caprolactone adduct include polyethylene glycol mono(meth)acrylate caprolactone adduct, polypropylene glycol mono(meth)acrylate caprolactone Lactone adducts, etc.

From the viewpoint of being excellent in curability and solvent resistance of the cured film, the component (a1) is preferably a hydroxyl group-containing (meth)acrylate having at least three (meth)acryloyl groups in the molecule, more preferably A hydroxyl group-containing (meth)acrylate having one hydroxyl group and at least three (meth)acryloyl groups in the molecule. As the hydroxyl group-containing (meth)acrylate, the above-mentioned neotaerythritol tri(meth)acrylate, dipeoerythritol penta(meth)acrylate, and neotaerythritol tri(meth)acrylate are preferable. A mixture of esters and neotaerythritol tetra(meth)acrylate, a mixture of dipeotaerythritol penta(meth)acrylate and dipivalerythritol hexa(meth)acrylate.

Content of the (a1) component in the said reaction component is not specifically limited, From a viewpoint that the solvent resistance of a cured film is excellent, it is preferable to be about 20-80 mass % with respect to 100 mass % of the said reaction component in terms of solid content , more preferably about 30 to 70 mass %.

(polyisocyanate (a2)) As the component (a2), as long as it is a compound having at least two isocyanate groups in the molecule, various conventional ones can be used without particular limitation. The above-mentioned polyisocyanates may be used alone or in combination of two or more.

(a2) Component, for example, linear aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, biuret form and isocyanurate form of these diisocyanates , an allophanate body, an adduct; and a compound obtained by reacting two or more kinds selected from the group consisting of a biuret body, an isocyanurate body, an allophanate body and an adduct body etc.

Examples of the above-mentioned linear aliphatic diisocyanate include methylene diisocyanate, ethylidene diisocyanate, propylidene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, and hexamethylene diisocyanate. , Heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, tenamethylene diisocyanate, etc.

As said branched-chain aliphatic diisocyanate, diethylpentylene diisocyanate, trimethyl butylene diisocyanate, trimethyl pentylene diisocyanate, trimethyl hexamethylene diisocyanate, etc. are mentioned, for example.

The above-mentioned alicyclic diisocyanates include, for example, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate Isocyanate, cyclodecyl diisocyanate, tricyclodecyl diisocyanate, adamantane diisocyanate, norbornene diisocyanate, bicyclodecyl diisocyanate, etc.

The above-mentioned aromatic diisocyanates include, for example, dialkyldiphenylmethane diisocyanates such as 4,4'-diphenyldimethylmethane diisocyanate; 4,4'-diphenyltetramethylmethane diisocyanate, etc. Tetraalkyldiphenylmethane diisocyanate; 4,4'-diphenylmethane diisocyanate, 4,4'-bibenzyl diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, toluene diisocyanate Isocyanate, xylylene diisocyanate (xylylene diisocyanate), m-tetramethylxylylene diisocyanate (m-tetramethylxylylene diisocyanate), 1,5-naphthalene diisocyanate, and the like.

［式中，n^b 為1以上的整數；R^bA ～R^bE 各自獨立地為直鏈脂肪族二異氰酸酯殘基、支鏈脂肪族二異氰酸酯殘基、脂環式二異氰酸酯殘基及芳香族二異氰酸酯殘基中的任一個；R^bα ～R^bβ 各自獨立地為異氰酸酯基或 ［化2］

（n^b1 為0以上的整數；R^b1 ～R^b5 與R^bA ～R^bE 相同；R^b ’～R^b ’’各自獨立地為異氰酸酯基或R^bα ～R^bβ 自身的基團。就R^b4 ～R^b5 、R^b ’’而言，在各結構單元的每一個中，此等基團也可以不同。） 就R^bD ～R^bE 、R^bβ 而言，在各結構單元的每一個中，此等基團也可以不同。］As the said biuret body of the said diisocyanate, the compound etc. which are represented by the following structural formula are mentioned. [Change 1]

[In the formula, n ^b is an integer of 1 or more; R ^bA to R ^bE are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, and an aromatic diisocyanate residue. Any one of the isocyanate residues; R ^bα to R ^bβ are each independently an isocyanate group or [Chem 2]

(n ^b1 is an integer of 0 or more; R ^b1 to R ^b5 are the same as R ^bA to R ^bE ; R ^b ′ to R ^b ″ are each independently an isocyanate group or a group of R ^bα to R ^bβ itself. For R ^b4 For R ^b5 and R ^b ″, these groups may be different in each of the structural units.) For R ^bD to R ^bE and R ^bβ , in each of the structural units, These groups can also be different. ]

Specifically, the above-mentioned biuret body of the above-mentioned diisocyanate includes: DURANATE 24A-100, DURANATE 22A-75P, DURANATE 21S-75E (the above are manufactured by Asahi Kasei Co., Ltd.); Desmodur N3200A (hexamethylene diisocyanate Biuret) (the above are manufactured by Sumitomo Bayer Urethane Co., Ltd.) and the like.

［式中，nⁱ 為0以上的整數；R^iA ～R^iE 各自獨立地為直鏈脂肪族二異氰酸酯殘基、支鏈脂肪族二異氰酸酯殘基、脂環式二異氰酸酯殘基及芳香族二異氰酸酯殘基中的任一個；R^iα ～R^iβ 各自獨立地為異氰酸酯基或 ［化4］

（nⁱ¹ 為0以上的整數；Rⁱ¹ ～Rⁱ⁵ 與R^iA ～R^iE 相同；Rⁱ ’～Rⁱ ’’各自獨立地為異氰酸酯基或R^iα ～R^iβ 自身的基團。就Rⁱ⁴ ～Rⁱ⁵ 、Rⁱ ’’而言，在各結構單元的每一個中，此等基團也可以不同。） 就R^iD ～R^iE 、R^iβ 而言，在各結構單元的每一個中，此等基團也可以不同。］As the said isocyanurate body of the said diisocyanate, the compound etc. which are represented by the following structural formula are mentioned. [Change 3]

[In the formula, n ⁱ is an integer of 0 or more; R ^iA to R ^iE are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, and an aromatic diisocyanate residue. Any one of the isocyanate residues; R ^iα to R ^iβ are each independently an isocyanate group or [Chem 4]

(n ⁱ¹ is an integer of 0 or more; R ⁱ¹ to R ⁱ⁵ are the same as R ^iA to R ^iE ; R ⁱ ′ to R ⁱ ″ are each independently an isocyanate group or a group of R ^iα to R ^iβ itself. For R ⁱ⁴ For ~R ⁱ⁵ and R ⁱ ″, these groups may be different in each structural unit.) For R ^iD ~R ^iE and R ^iβ , in each of the structural units, These groups can also be different. ]

Specifically, the above-mentioned isocyanurate bodies of the above-mentioned diisocyanates include: DURANATE TPA-100, DURANATE TKA-100, DURANATE MFA-75B, DURANATE MHG-80B (the above are manufactured by Asahi Kasei Co., Ltd.); Coronate HXR, Coronate HX (the above is the isocyanurate of hexamethylene diisocyanate) (the above is manufactured by Tosoh Corporation); TAKENATE D-127N (the isocyanurate of hydrogenated xylylene diisocyanate) (The above is manufactured by Mitsui Chemicals Co., Ltd.); VESTANAT T1890/100 (isocyanurate of isophorone diisocyanate) (The above is manufactured by Evonik Japan Co., Ltd. )Wait.

［式中，n^a 為0以上的整數；R^aA 為烷基、芳基、聚醚基、聚酯基或聚碳酸酯基；R^aB ～R^aG 各自獨立地為直鏈脂肪族二異氰酸酯殘基、支鏈脂肪族二異氰酸酯殘基、脂環式二異氰酸酯殘基及芳香族二異氰酸酯殘基中的任一個；R^aα ～R^aγ 各自獨立地為異氰酸酯基或 ［化6］

（n^a1 為0以上的整數；R^a1 ～R^a6 與R^aB ～R^aG 相同；R^a ’～R^a ’’’各自獨立地為異氰酸酯基或R^aα ～R^aγ 自身的基團。就R^a1 ～R^a4 、R^a ’～R^a ’’而言，在各結構單元的每一個中，此等基團也可以不同。） 就R^aB ～R^aE 、R^aα ～R^aβ 而言，在各結構單元的每一個中，此等基團也可以不同。］As the said allophanate body of the said diisocyanate, the compound etc. which are represented by the following structural formula are mentioned. [Chemical 5]

[In the formula, n ^a is an integer of 0 or more; R ^aA is an alkyl group, an aryl group, a polyether group, a polyester group or a polycarbonate group; R ^aB to R ^aG are each independently a straight-chain aliphatic diisocyanate residue R ^aα to R ^aγ are each independently an isocyanate group or [Chem. 6]

(n ^a1 is an integer of 0 or more; R ^a1 to R ^a6 are the same as R ^aB to R ^aG ; R ^a ' to R ^a ''' are each independently an isocyanate group or a group of R ^aα to R ^aγ itself. For ^a1 to R ^a4 and R ^a ' to R ^a '', these groups may be different in each structural unit.) For R ^aB to R ^aE and R ^aα to R ^aβ , the These groups may also be different in each structural unit. ]

Specifically, as the said allophanate body of the said diisocyanate, Coronate 2793 (made by Tosoh Corporation), TAKENATE D-178N (made by Mitsui Chemicals Co., Ltd.), etc. are mentioned.

［式中，n^ad 為0以上的整數；R^adA ～R^adE 各自獨立地為直鏈脂肪族二異氰酸酯殘基、支鏈脂肪族二異氰酸酯殘基、脂環式二異氰酸酯殘基及芳香族二異氰酸酯殘基中的任一個；R^ad1 ～R^ad2 各自獨立地為 ［化8］

（式中，n^{ad ’} 為0以上的整數；R^ad’ ～R^ad’’ 與R^adA ～R^adE 相同；R^ad’’’ 為R^ad1 ～R^ad2 自身的基團；就R^ad’ ～R^ad’’’ 而言，在各結構單元的每一個中，此等基團也可以不同。） 就R^adD ～R^adE 、R^ad2 而言，在各結構單元的每一個中，此等基團也可以不同。］； 由以下結構式表示的甘油與二異氰酸酯的加成物： ［化9］

［式中，n^ad1 為0以上的整數；R^adα ～R^adε 各自獨立地為直鏈脂肪族二異氰酸酯殘基、支鏈脂肪族二異氰酸酯殘基、脂環式二異氰酸酯殘基及芳香族二異氰酸酯殘基中的任一個；R^adA ～R^adB 各自獨立地為 ［化10］

（式中，n^ad1’ 為0以上的整數；R^{adδ ’} ～R^{adε ’} 與R^adα ～R^adε 相同；R^{adB ’} 為R^adA ～R^adB 自身的基團；就R^{adδ ’} ～R^{adε ’} 、R^{adB ’} 而言，在各結構單元的每一個中，此等基團也可以不同。） 就R^adδ ～R^adε 、R^adB 而言，在各結構單元的每一個中，此等基團也可以不同。］等。The adduct of the above-mentioned diisocyanate may include an adduct of trimethylolpropane and diisocyanate represented by the following structural formula: [Chem. 7]

[In the formula, n ^ad is an integer of 0 or more; ^RadA to ^RadE are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, and an aromatic diisocyanate residue. Any of the isocyanate residues; ^Rad1 to ^Rad2 are each independently [Chemical 8]

(In the formula, n ^{ad '} is an integer greater than or equal to 0; Rad ^' to Rad'' are the same as ^RadA to ^RadE ; ^{Rad ''' is} a group of ^Rad1 to ^Rad2 itself; For Rad ^''' , these groups may be different in each structural unit.) For ^RadD to ^RadE and ^Rad2 , in each of the structural units, these groups Groups can also be different. ]; The adduct of glycerol and diisocyanate represented by the following structural formula: [Chem. 9]

[In the formula, n ^ad1 is an integer of 0 or more; ^Radα to ^Radε are each independently a linear aliphatic diisocyanate residue, a branched aliphatic diisocyanate residue, an alicyclic diisocyanate residue, and an aromatic diisocyanate residue. Any of the isocyanate residues; R ^adA to R ^adB are each independently [Chem. 10]

(In the formula, n ^ad1' is an integer greater than or equal to 0; ^{Radδ '} to ^{Radε '} are the same as ^Radα to ^Radε ; ^{RadB '} is a group of ^RadA to ^RadB itself; ^{Radδ '} to ^{Radε '} , ^{RadB '} , these groups may also be different in each of the structural units.) For ^Radδ to ^Radε and ^RadB , in each of the structural units, these groups can also be different. ]Wait.

Specifically, the above-mentioned adducts of the above-mentioned diisocyanates include: DURANATE P301-75E (the above are manufactured by Asahi Kasei Co., Ltd.); TAKENATE D-110N, TAKENATE D-160N (the above are manufactured by Mitsui Chemicals Co., Ltd.); Coronate L, Coronate HL (the above are manufactured by Tosoh Corporation), etc.

It should be noted that, in the above formulas, "straight-chain aliphatic diisocyanate residue, branched-chain aliphatic diisocyanate residue, alicyclic diisocyanate residue, and aromatic diisocyanate residue" means: The group remaining after removing the isocyanate group among the chain aliphatic diisocyanates, the branched aliphatic diisocyanates, the alicyclic diisocyanates, and the aromatic diisocyanates.

From the viewpoint of being excellent in the solvent resistance of the cured film, the component (a2) is preferably a polyisocyanate having at least three isocyanate groups in the molecule. As a polyisocyanate which has at least three isocyanate groups in a molecule|numerator, the said biuret body, the said isocyanurate body, the said allophanate body, and the said adduct are preferable.

The isocyanate group content (NCO%) of the component (a2) is not particularly limited, but is preferably about 10% to 30% from the viewpoint of excellent solvent resistance of the cured film.

The molar ratio (NCO/OH) of the isocyanate group contained in the component (a2) and the hydroxyl group contained in the component (a1) is not particularly limited, but is preferably about 1.2 to 6.0 from the viewpoint of excellent solvent resistance of the cured film. , more ideally about 1.5 to 3.0.

Although content of the (a2) component in the said reaction component is not specifically limited, From a viewpoint that the solvent resistance of a cured film is excellent, it is preferable to be about 15-75 mass % with respect to 100 mass % of said reaction components in terms of solid content , more preferably about 15 to 60 mass %.

(Hydroxy-containing polyalkylene glycols (a3)) As the component (a3), as long as it is a polyalkylene glycol having at least one hydroxyl group in the molecule, various known components can be used without particular limitation. (a3) A component may be used individually by 1 type, and may be used in combination of 2 or more types.

(a3) Component, for example, polyalkylene glycol, polyalkylene glycol monoalkyl ether, polyalkylene glycol mono(meth)acrylate, polyalkylene glycol monoallyl ether, polyalkylene glycol monoamide compounds, etc.

The above-mentioned polyalkylene glycols include, for example, polyethylene glycol, polypropylene glycol, polybutylene glycol, and polyethylene oxide/propylene oxide/butylene oxide having at least one structure of block or random copolymerization. ether glycol, polyoxytetramethylene glycol, polyethylene glycol polypropylene glycol polyethylene glycol (block copolymer), polypropylene glycol polyethylene glycol polypropylene glycol (block copolymer), polyethylene glycol Ethylene glycol polypropylene glycol (random copolymer), polytetramethylene ether glycol, polyethylene glycol polytetramethylene ether glycol (block copolymer), polyethylene glycol polytetramethylene ether glycol Polyethylene glycol (block copolymer), polyethylene glycol polytetramethylene ether glycol (random copolymer), polypropylene glycol polytetramethylene ether glycol polypropylene glycol (block copolymer), polytetramethylene glycol Methylene ether glycol polypropylene glycol polytetramethylene ether glycol (block copolymer), polypropylene glycol polytetramethylene ether glycol (random copolymer), etc.

The above-mentioned polyalkylene glycol monoalkyl ethers include, for example, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether, polyethylene glycol monoamyl ether, polyethylene glycol monohexyl ether, polyethylene glycol monoheptyl ether, polyethylene glycol monooctyl ether, polyethylene glycol lauryl ether, polyethylene glycol cetyl ether ether, polyethylene glycol stearyl ether, polyethylene glycol nonyl phenyl ether, polyethylene glycol tridecyl ether, polyethylene glycol oleyl ether, polyethylene glycol octyl phenyl ether, poly Polyoxyethylene oleyl cetyl ether (polyoxyethylene oleyl cetyl ether) and other polyethylene glycol derivatives; polypropylene glycol monomethyl ether and other polypropylene glycol derivatives, etc.

Examples of the polyalkylene glycol mono(meth)acrylate include polyethylene glycol derivatives such as polyethylene glycol mono(meth)acrylate, and polypropylene glycol derivatives such as polypropylene glycol mono(meth)acrylate. , Polyethylene glycol polypropylene glycol mono(meth)acrylate, poly(ethylene glycol tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol tetramethylene glycol) mono(methyl) Acrylate etc.

Examples of the above-mentioned polyalkylene glycol monoallyl ether include polyethylene glycol derivatives such as polyethylene glycol monoallyl ether, polypropylene glycol derivatives such as polypropylene glycol monoallyl ether, and polyethylene glycol Propylene glycol monoallyl ether, etc.

Examples of the polyalkylene glycol monoamide compound include polyethylene glycol derivatives such as polyethylene glycol monolaurate, polyethylene glycol monostearate, and polyethylene glycol monooleate.

From the viewpoint of being excellent in storage stability, the component (a3) is preferably a compound represented by the following general formula (1).

(Chemical 13) H-(OCH ₂ CH ₂ )n-OR (1) (wherein R represents any one of an alkyl group, an allyl group, a (meth)acryloyl group, and an acyl group, and n represents 3- an integer of 25.)

From the viewpoint of being excellent in storage stability, the component (a3) is particularly preferably polyethylene glycol monomethyl ether and polyethylene glycol mono(meth)acrylate.

(a3) Commercial products of the component include, for example: PEG#200T, PEG#200, PEG#300, PEG#400, PEG#600, PEG#1000, PEG#1500, PEG#1540, PEG#2000, PEG #4000, PEG#4000P, PEG#6000, PEG#6000P, PEG#11000, PEG#20000, UNIOX M-400, UNIOX M-550, UNIOX M-1000, UNIOX M-2000, UNIOX M-2500, UNIOX M -3000, UNIOX M-4000, BLEMMER PE-90, BLEMMER PE-200, BLEMMER PE-300, BLEMMER AE-90, BLEMMER AE-200, BLEMMER AE-400 (the above are manufactured by NOF Corporation), etc.

The physical properties of the component (a3) are not particularly limited. From the viewpoint of excellent storage stability, the hydroxyl value of the component (a3) (JIS K0070. Hereinafter, when referred to as the hydroxyl value, the same applies.) is preferably about 10 to 300 mgKOH/g, and more preferably from the same viewpoint It is about 30 to 140 mgKOH/g.

From the viewpoint of excellent storage stability and solvent resistance of the cured film, the number average molecular weight of the component (a3) is preferably about 200 to 3,000, and more preferably about 400 to 2,000. In addition, the number average molecular weight means the polystyrene conversion value in gel permeation chromatography, but the measurement method is not specifically limited, Various well-known means can be employ|adopted, and a commercially available measuring machine can also be used.

The amount of the component (a3) used in the above-mentioned reaction components is not particularly limited, but from the viewpoint of excellent storage stability, it is preferably about 5 to 50% by mass based on 100% by mass of the above-mentioned reaction components in terms of solid content, and more Ideally, it is about 10 to 30 mass %. When the usage-amount of (a3) component is 5 mass % or more, since the storage property of an active energy ray-curable resin composition is more excellent, and segregation with time of this composition can also be suppressed, it is preferable. Moreover, since the crosslinking density is high and curability is more sufficient that the usage-amount of a component (a3) is 50 mass % or less, and since the water resistance of the cured film obtained is high, it is preferable.

In the (A) component, the molar ratio of the hydroxyl group of the component (a1), the isocyanate group of the component (a2), and the hydroxyl group of the component (a3) is not particularly limited, but from the viewpoint of excellent storage stability and solvent resistance of the cured film More preferably, it is about 0.1 to 0.9:1:0.1 to 0.9, and more preferably about 0.4 to 0.8:1:0.1 to 0.6.

The reaction component in the (A) component may contain other components (hereinafter referred to as "other components") not belonging to any of the (a1) component, (a2) component, and (a3) component. The other components are not particularly limited as long as they are compounds having at least one functional group capable of reacting with an isocyanate group in the molecule. As a functional group which can react with an isocyanate group, a hydroxyl group, an amine group, etc. are mentioned, for example.

In addition, when (A) component has the structure of a salt, since the storage stability of an active energy ray-curable resin composition falls, it is not preferable. Examples of such component (A) include urethane (meth)acrylates obtained by mixing basic substances such as metal hydroxides, ammonia, and amines with a reaction component containing a carboxyl group-containing compound such as hydroxycarboxylic acid. The salt of urethane (meth)acrylate obtained by neutralization.

<Physical properties and manufacturing method of polyurethane (meth)acrylate (A)> The physical properties of the component (A) are not particularly limited. From the viewpoint of curability, the weight average molecular weight of the component (A) is more preferably about 1,000 to 10,000. In addition, the weight average molecular weight means the polystyrene conversion value in gel permeation chromatography, but the measurement method is not specifically limited, Various well-known means can be used, and a commercially available measuring machine can also be used.

From the viewpoint of being excellent in curability, the component (A) is preferably a compound having at least two (meth)acryloyl groups in the molecule.

The production method of the (A) component is not particularly limited as long as it is a method of reacting the (a1) component, the (a2) component, and the (a3) component, and various conventional production methods are exemplified. Specifically, for example, after the component (a2) and the component (a3) are reacted in the presence of a catalyst at an appropriate reaction temperature (for example, 60 to 90° C.), the component (a1) is added, and similarly, the component (a1) is added in the presence of a catalyst. Appropriate reaction temperature (for example, 60-90 degreeC etc.) reaction method etc.. Moreover, the order of making (a1) component, (a2) component, and (a3) component react is not specifically limited, The method of mixing each and making it react arbitrarily, the method of mixing all components together and making it react, etc. are mentioned.

The above-mentioned catalysts include, for example: organic tin catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; organic acid tin catalysts such as tin octoate; organic titanium catalysts such as ethyl acetate titanium; Zirconium catalysts; organic iron catalysts such as acetylacetone iron, etc. One of the above catalysts may be used alone, or two or more of them may be used in combination.

The content of the component (A) in the above-mentioned active energy ray-curable resin composition is not particularly limited, but from the viewpoint of excellent balance of hardness and wear resistance of the cured film, it is calculated as a solid content relative to active energy ray curing. 100 parts by mass of the resin composition is preferably about 20 to 90 parts by mass, and more preferably about 40 to 85 parts by mass.

<Conductive polymer (B)> The component (B) is a conductive polymer and imparts antistatic properties to the cured film.

The component (B) is not particularly limited as long as it is a conductive polymer. The component (B) is desirably various conventional heteroatom-containing π-conjugated conductive polymers. "Heteroatom" means atoms other than hydrogen and carbon (eg, nitrogen atom, sulfur atom, etc.), "heteroatom-containing π-conjugated system conductive polymer" means having the heteroatom in the molecule and the main chain of the molecule Organic polymer compounds that form π-conjugated structures. In addition, in this specification, (B) component is the state doped with various dopant. (B) component can be used individually by 1 type, or can be used in combination of 2 or more types.

Examples of the above-mentioned heteroatom-containing π-conjugated system conductive polymer include poly(thiophene)s, poly(thiophenevinylene)s, poly(thiophenevinylene)s, which are π-conjugated system conductive polymers having a heterocycle in which a heteroatom exists. (pyrrole) and so on. Moreover, poly(aniline)s etc. which are π-conjugated system conductive polymers which have an aromatic ring are mentioned.

An alkyl group, an alkoxy group, and an alkylene dioxy group may be bonded to the above-mentioned heterocyclic ring or aromatic ring in a branched or cyclic manner. As an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an octadecyl group, etc. are mentioned. As an alkoxy group, a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, a decyloxy group, an octadecyloxy group, etc. are mentioned. As an alkylene dioxy group, an ethylidene dioxy group, a propylidene dioxy group, a butylene dioxy group, etc. are mentioned.

The above-mentioned poly(thiophene)s are not particularly limited. Examples of the poly(thiophenes) include poly(thiophenes), poly(alkylthiophenes), poly(monoalkoxythiophenes), poly(dialkoxythiophenes), and poly(alkylene dioxythiophenes). thiophene), etc.

Examples of the above-mentioned poly(alkylthiophenes) include poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), and poly(3-butylthiophene). 3-hexylthiophene), poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene) alkylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene), and the like. Moreover, as said poly(monoalkoxythiophene)s, poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-butoxythiophene) are mentioned. -hexyloxythiophene), poly(3-heptyloxythiophene), poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-decyloxythiophene) (3-octadecyloxythiophene) and the like. Moreover, as said poly(dialkoxythiophene)s, poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dimethoxythiophene) are mentioned. propoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene), poly(3,4-diheptoxythiophene), poly(3,4 -dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-didodecyloxythiophene), and the like. Moreover, as said poly (alkylene dioxythiophene), poly (3, 4- ethylene dioxy thiophene), poly (3, 4- propylene dioxy thiophene), poly ( (3,4-butylene dioxythiophene) and the like.

Examples of the above-mentioned poly(thiophene vinylenes) include poly(thiophene vinylenes), poly(alkylthiophene vinylenes), poly(monoalkoxythiophene vinylenes), poly(dialkoxythiophene vinylenes), and poly(dialkoxythiophene vinylenes). ), poly(alkylene dioxythiophene vinylene), etc.

Examples of the above-mentioned poly(alkylthiophene vinylene)s include poly(3-methylthiophene vinylene), poly(3-ethylthiophene vinylene), poly(3-propylthiophene vinylene), poly(3-ethylthiophene vinylene), and poly(3-propylthiophene vinylene) -butylthiophene vinylene), poly(3-hexylthiophene vinylene), poly(3-heptylthiophene vinylene), poly(3-octylthiophene vinylene), poly(3-decylthiophene vinylene) , poly(3-dodecylthiophene vinylene), poly(3-octadecylthiophene vinylene), poly(3,4-dimethylthiophene vinylene), poly(3,4-dibutylene) Thiophene ethylene) and so on. In addition, examples of the above-mentioned poly(monoalkoxythiophene vinylene)s include poly(3-methoxythiophene vinylene), poly(3-ethoxythiophene vinylene), poly(3-butoxy vinylene) Thiophene vinylene), poly(3-hexyloxythiophene vinylene), poly(3-heptoxythiophene vinylene), poly(3-octyloxythiophene vinylene), poly(3-decyloxythiophene vinylene) ethylene), poly(3-dodecyloxythiophene vinylene), poly(3-octadecyloxythiophene vinylene) and the like. In addition, examples of the above-mentioned poly(dialkoxythiophene vinylene)s include poly(3,4-dimethoxythiophene vinylene), poly(3,4-diethoxythiophene vinylene), poly(3,4-diethoxythiophene vinylene), (3,4-dipropoxythiophene vinylene), poly(3,4-dibutoxythiophene vinylene), poly(3,4-dihexyloxythiophene vinylene), poly(3,4- Diheptyloxythiophene vinylene), poly(3,4-dioctyloxythiophene vinylene), poly(3,4-didecyloxythiophene vinylene), poly(3,4-didodecyloxy vinylene) thiophene ethylene) and so on. In addition, as said poly(alkylene dioxythiophene vinylene)s, poly(3,4-ethyldioxythiophene vinylene), poly(3,4-propyl dioxyethylene dioxy) can be mentioned. thiophene vinylene), poly(3,4-butylene dioxythiophene vinylene) and the like.

Examples of the above-mentioned poly(pyrroles) include poly(pyrroles), poly(alkylpyrroles), poly(monoalkoxypyrroles), poly(dialkoxypyrroles), and poly(alkylenes). dioxypyrroles), etc.

Examples of the above-mentioned poly(alkylpyrroles) include poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-propylpyrrole), poly(3-butylpyrrole), poly(3-butylpyrrole), and poly(3-propylpyrrole). 3-hexylpyrrole), poly(3-heptylpyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3-octadecylpyrrole) Alkylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), etc. In addition, examples of the above-mentioned poly(monoalkoxypyrrole)s include poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), and poly(3-methoxypyrrole). -hexyloxypyrrole), poly(3-heptyloxypyrrole), poly(3-octyloxypyrrole), poly(3-decyloxypyrrole), poly(3-dodecyloxypyrrole), poly(3-dodecyloxypyrrole) (3-octadecyloxypyrrole) and the like. In addition, as said poly(dialkoxypyrrole)s, poly(3,4-dimethoxypyrrole), poly(3,4-diethoxypyrrole), poly(3,4-dimethoxypyrrole) can be mentioned. propoxypyrrole), poly(3,4-dibutoxypyrrole), poly(3,4-dihexyloxypyrrole), poly(3,4-diheptoxypyrrole), poly(3,4 -dioctyloxypyrrole), poly(3,4-didecyloxypyrrole), poly(3,4-didodecyloxypyrrole) and the like. Moreover, as said poly (alkylene dioxypyrrole), poly (3, 4- ethylene dioxy pyrrole), poly (3, 4- propylene dioxy pyrrole), poly ( (3,4-butylene dioxypyrrole) and the like.

Examples of the above-mentioned poly(anilines) include poly(aniline), poly(2-methylaniline), poly(3-isobutylaniline), poly(2-aminobenzenesulfonic acid), and poly(3-amine). benzenesulfonic acid), etc.

Examples of the above-mentioned dopant include Lewis acids (PF ₅ , AsF ₅ , SbF ₅ , etc.), protonic acids (HF, HCl, H ₂ SO ₄ , p-toluenesulfonic acid, etc.), electrolyte anions (Cl ⁻ , Br ^- , sulfo anion, etc.), anionic polymers, etc.

Examples of the above-mentioned anionic polymer include polystyrene sulfonic acid (hereinafter referred to as PSS), polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacrylic acid ethyl sulfonic acid, polyacrylic acid butyl sulfonic acid, Poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polypropylene carboxylic acid Polyacrylcarboxylic acid, polymethacrylcarboxylic acid, poly-2-acrylamido-2-methylpropanecarboxylic acid, and polyisoprenecarboxylic acid, polyacrylic acid, and salts thereof At least one of the groups of species.

The (B) component is usually used in the form of an aqueous dispersion or an aqueous solution. Moreover, in this case, the solid content concentration of (B) component is about 0.1 to 10 weight% normally.

As the component (B), from the viewpoint of excellent antistatic properties of the cured film, poly(thiophene)s and/or poly(aniline)s are preferable, and poly(thiophene)s are particularly preferable. In addition, as the poly(thiophene)s, in consideration of availability and the like, there may be mentioned alkylenedioxypoly(thiophene) (especially 3,4-ethylendioxythiophene) doped with PSS. PEDOT)), and self-doped ethylenedioxypoly(thiophenes) obtained from thiophenes having sulfonic acid groups bonded to ethylenedioxy sites.

It should be noted that, for PEDOT doped with PSS, for example, 3,4-ethylenedioxythiophene (EDOT) as a monomer can be used as an oxidizing agent in an aqueous phase in the presence of PSS as a dopant. The polymerization is carried out, whereby it is obtained in the form of an aqueous dispersion of a complex of poly(3,4-ethylenedioxythiophene) and polystyrenesulfonic acid (PEDOT/PSS).

As the aqueous dispersion of PEDOT/PSS, commercially available products such as Baytron P (manufactured by Starck Corporation), Clevios P (manufactured by Heraeus Corporation), and Orgacon ICP1010 (manufactured by Agfa-Gevaert Co., Ltd., Japan) can also be used, for example.

In addition, self-doping ethylenedioxypoly(thiophene), for example, a monomer having a hydroxymethyl group bonded to the ethylidene moiety of 3,4-ethylenedioxythiophene can be combined with 2,4 -Butane sultone reaction and purification to obtain 3,4-ethylenedioxythiophene into which a sulfonic acid group has been introduced, which is then polymerized in an aqueous phase using an oxidizing agent to form a self-doping type Ethylenedioxypoly(thiophene) in the form of an aqueous solution.

An aqueous solution of self-doping ethylenedioxypoly(thiophene) obtained from a thiophene having a sulfonic acid group bonded to an ethylenedioxy moiety can also be obtained using, for example, SELFTRON (manufactured by Tosoh Corporation) or the like. Commercially available.

In addition, in the active energy ray-curable resin composition of the present invention, as long as the desired effect is not impaired, non-heteroatom-based conductive polymers such as poly(acetylene)s, poly(acetylenes) can also be used in combination phenylene), poly(phenylene vinylene), poly(acene), etc.

The content of the (B) component in the active energy ray-curable resin composition is not particularly limited, but from the viewpoint of excellent antistatic properties of the cured film, in terms of solid content, relative to the active energy ray-curable resin composition 100 parts by mass, ideally 0.1 to 20 parts by mass.

Content of (B) component in the said active energy ray-curable resin composition is not specifically limited, From the viewpoint of excellent antistatic property of a cured film, it is solid content conversion with respect to (A) component and (B) component The total amount is 100 parts by mass, desirably 0.05 to 25 parts by mass, more desirably 0.1 to 20 parts by weight, and particularly desirably 4 to 10 parts by weight.

＜Water (C)＞ As (C)component, if it is water, it will not specifically limit, For example, distilled water, ion-exchange water, ion-exchange distilled water, etc. are mentioned. Moreover, the water|moisture content contained in (B) component is also contained in (C)component.

The content of the component (C) in the active energy ray-curable resin composition is preferably 0.5 to 50 mass % of the solid content of the active energy ray-curable resin composition from the viewpoint of coatability. range to include.

((meth)acrylate (D)) The said active energy ray-curable resin composition may contain the (meth)acrylate (D) which has at least 3 (meth)acryloyl groups in a molecule|numerator.

From the viewpoint of being excellent in the solvent resistance of the cured film obtained, it is preferable that the number of (meth)acryloyl groups in the molecule in the component (D) is increased. The number of (meth)acryloyl groups in the molecule of the component (D) is usually about 3 to 5 from the viewpoint of easy acquisition.

(D) The poly(meth)acrylate which has at least 3 (meth)acryloyl groups in a molecule|numerator in (a1) component, trimethylolpropane tri(meth)acrylate, Ethylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate Trimethylolpropane tri(meth)acrylates such as trimethylolpropane tri(meth)acrylate and epichlorohydrin modified trimethylolpropane tri(meth)acrylate; glycerol tri(meth)acrylate, ethylene oxide Glycerol tri(meth)acrylates such as alkane-modified glycerol tri(meth)acrylate and propylene oxide-modified glycerol tri(meth)acrylate; neopentaerythritol tetra(meth)acrylate, epoxy Ethane-modified neotaerythritol tetra(meth)acrylate and propylene oxide-modified neotaerythritol tetra(meth)acrylate and other neotaerythritol tetrakis(meth)acrylates; dipivaltetrakis Alcohol hexa(meth)acrylate and caprolactone-modified dipivalerythritol hexa(meth)acrylate, etc.; Diglycerol tetra(meth)acrylate , Triglycerol penta(meth)acrylate and other (poly)glycerol poly(meth)acrylates; Trinepentaerythritol octa(meth)acrylate and tetranepentaerythritol ten(meth)acrylate, etc. (Poly) neotaerythritol poly (meth) acrylates; (poly) trimethylol propane poly (meth) acrylates such as ditrimethylol propane tetra (meth) acrylate; polyester ( Meth)acrylates, urethane (meth)acrylates, epoxy (meth)acrylates, polyether (meth)acrylates, polyol (meth)acrylates and polyacrylic acid (meth)acrylates ) acrylate, etc.

Examples of the above-mentioned urethane (meth)acrylate include reaction products of hydroxyl-containing (meth)acrylates and polyisocyanates, reaction products of hydroxyl-containing (meth)acrylates, polyols and polyisocyanates, and the like. . In addition, the said urethane (meth)acrylate is different from (A) component.

As said hydroxyl-containing (meth)acrylate, the thing similar to (a1) component is mentioned, for example. As a polyisocyanate, the thing similar to (a2) component is mentioned, for example.

Examples of the polyhydric alcohols include aliphatic dihydric alcohols such as alkylene glycol, alicyclic dihydric alcohols such as 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane, neotaerythritol, and diol. Trimethylolpropane, dipivoerythritol, polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, polyolefin polyol, etc.

The above-mentioned polyacrylic acid (meth)acrylate can be, for example, a reaction product of an acrylic copolymer and (meth)acrylic acid obtained by mixing epoxy group-containing mono(meth)acrylate and as needed Mono(meth)acrylate is obtained by polymerizing.

Examples of the epoxy group-containing mono(meth)acrylate include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, and 3,4-(meth)acrylate. Epoxycyclohexylmethyl ester, vinylcyclohexene monooxide (ie, 1,2-epoxy-4-vinylcyclohexane), and the like.

From the viewpoint of excellent storage stability as the component (D), neopentaerythritol poly(meth)acrylate having a hydroxyl group in the component (a1), dipiaerythritol poly(methyl) ) acrylate, glycerol poly(meth)acrylate.

As the above-mentioned neotaerythritol poly(meth)acrylate, for example, neotaerythritol di(meth)acrylate; neotaerythritol tri(meth)acrylate; and neotaerythritol mono(meth)acrylate At least two of the group consisting of neotaerythritol di(meth)acrylate, neotaerythritol tri(meth)acrylate and neotaerythritol tetra(meth)acrylate mixture, etc.

Examples of the above-mentioned dipipentaerythritol poly(meth)acrylate include, for example, dipivalerythritol tetra(meth)acrylate; dipivalerythritol penta(meth)acrylate; Group consisting of alcohol tri(meth)acrylate, dipivalerythritol tetra(meth)acrylate, dipivalerythritol penta(meth)acrylate, and dipivalerythritol hexa(meth)acrylate A mixture of at least two of them, etc.

Examples of the above-mentioned glycerin poly(meth)acrylate include: glycerol di(meth)acrylate; and glycerol mono(meth)acrylate, glycerol di(meth)acrylate, and glycerol tri(meth)acrylate. A mixture of at least two of the ester groups, etc.

Commercially available products of the above-mentioned neotaerythritol poly(meth)acrylate include, for example, ARONIX M-933, ARONIX M-934, ARONIX M-306, ARONIX M-305 (the above are manufactured by Toagosei Co., Ltd.), etc. . As a commercial item of the said dipeotaerythritol poly(meth)acrylate, ARONIX M-403, ARONIX M-402, ARONIX M-400 (the above are manufactured by Toagosei Co., Ltd.) etc. are mentioned, for example. As a commercial item of the said glycerol poly(meth)acrylate, ARONIX M920 (made by Toagosei Co., Ltd.) etc. are mentioned, for example.

(Physical properties of (meth)acrylate (D)) The physical properties of the component (D) are not particularly limited. From the viewpoint of being excellent in curability and solvent resistance of the cured film, the molecular weight of the component (D) is preferably about 300 to 10,000, and more preferably about 300 to 5,000.

In addition, in this specification, when only expressing as "molecular weight", it has the following meaning. That is, in the case of a structure such as neotaerythritol tetra(meth)acrylate that can uniquely express a compound by a specific chemical formula, the above-mentioned molecular weight refers to the formula weight. On the other hand, when the structure of a compound cannot be uniquely expressed by a specific chemical formula like a polymer poly(meth)acrylate, the said molecular weight means a weight average molecular weight.

From the viewpoint of excellent storage stability of the active energy ray-curable resin composition, the hydroxyl value of the component (D) is preferably about 80 to 300 mgKOH/g, more preferably about 200 to 300 mgKOH/g.

The content of the component (D) in the above-mentioned active energy ray-curable resin composition is not particularly limited. From the viewpoint of the balance of antistatic properties and hardness of the cured film, the content of the component is calculated as a solid content relative to the active energy ray-curable resin. 100 parts by mass of the composition is preferably about 0 to 50 parts by mass.

(Surface Conditioner (E)) The active energy ray-curable resin composition may contain a surface conditioner (E) (hereinafter, referred to as (E) component).

(E) A component may be used individually by 1 type, or may be used in combination of 2 or more types. (E) Component includes, for example, an acrylic type, a silicone type, a fluorine type, an acetylene glycol type, and the like.

Content of the (E) component in the said active energy ray curable resin composition is not specifically limited, From the viewpoint of the solvent resistance of the cured film, it is solid content conversion with respect to the said active energy ray curable resin composition 100 The part by mass is ideally about 0 to 10 parts by mass.

((meth)acrylate) The said active energy ray-curable resin composition may contain (meth)acrylate other than (D)component. (Meth)acrylate may be used individually by 1 type, or may be used in combination of 2 or more types.

Examples of the above (meth)acrylate include mono(meth)acrylate having one (meth)acryloyl group in the molecule, and di(meth)acrylate having two (meth)acryloyl groups in the molecule. base) acrylate, etc.

As said mono(meth)acrylate, the compound which has one (meth)acryloyl group in a molecule|numerator in (a1) component, the mono(meth)acrylate which does not contain a hydroxyl group etc. are mentioned, for example.

As said di(meth)acrylate, the compound which has two (meth)acryloyl groups in a molecule|numerator in (a1) component, the di(meth)acrylate which does not contain a hydroxyl group, etc. are mentioned, for example. Examples of the hydroxyl-free di(meth)acrylate include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate , Dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicyclopentadiene di (Meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, ethylene glycol diglycidyl ether di (Meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, hydroxypivalic acid-modified neopentyl Alcohol di(meth)acrylate, etc.

The content of the (meth)acrylate in the active energy ray-curable resin composition is not particularly limited, but is preferably 0 to 300 parts by mass based on 100 parts by mass of the active energy ray-curable resin composition in terms of solid content. about.

(Photopolymerization initiator) The active energy ray-curable resin composition may contain a photopolymerization initiator. A photopolymerization initiator may be used individually by 1 type, or may be used in combination of 2 or more types. Examples of photopolymerization initiators include 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-hydroxy-2-methyl ketone -1-Phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl yl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxyl Mixture of oxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester, 2,4,6-trimethylbenzyl- Diphenyl-phosphine oxide, 4-methylbenzophenone, etc.

From the viewpoint of curability and antistatic properties of the cured film, photopolymerization initiators are preferably used: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2- Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine Propane-1-one, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2- [2-Hydroxy-ethoxy]-ethyl ester mixture, more preferably: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane -1-keto, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2 - Mixtures of hydroxy-ethoxy]-ethyl esters.

Content of the photoinitiator in the said active energy ray curable resin composition is not specifically limited, From the viewpoint of the balance of the antistatic property, solvent resistance, etc. of the cured film, it is calculated as solid content with respect to the said active energy 100 parts by mass of the radiation-curable resin composition is preferably 0 to 20 parts by mass.

(solvent) A solvent can also be used for the said active energy ray-curable resin composition as long as the effect of this invention is not impaired. Examples of the solvent include methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary Butanol, diacetone alcohol, acetone, acetone acetone, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methyl cellulose, ethyl cellulose , 1,4-dioxane, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. One of the above-mentioned solvents may be used alone, or two or more of them may be used in combination. Desirable solvents are: ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tertiary butanol, diacetone alcohol, acetone, methyl cellulol, ethyl cellulol as a solvent mixed with water Su, 1,4-dioxane, propylene glycol monomethyl ether, etc.

In the above-mentioned active energy ray-curable resin composition, in order to improve the conductivity of the component (B), it is desirable to use a high-boiling-point high-polarity solvent in combination. Examples of high-boiling high-polarity solvents include ethylene glycol, dimethylsulfoxide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and tetrahydrothiophene-1,1 - Dioxide, Ethylene Carbonate, Propylene Carbonate, Triethylene Glycol Dimethyl Ether, Tetraethylene Glycol Dimethyl Ether, etc. In particular, from the viewpoint of the antistatic properties of the cured film, 1,3-dimethyl-2-imidazolidinone is preferably used in combination.

The content of the solvent in the active energy ray-curable resin composition is not particularly limited. The content of the solvent is desirably about 0 to 200 parts by mass relative to 100 parts by mass of the active energy ray-curable resin composition from the viewpoint of coatability. In addition, the content of the solvent is preferably contained within a range of about 0.5 to 50 mass % of the solid content concentration of the active energy ray-curable resin composition from the viewpoint of coatability.

(additive) The active energy ray-curable resin composition may contain, as additives, agents other than the above-mentioned (meth)acrylate, photopolymerization initiator, and solvent, as long as the effects of the present invention are not impaired. One of the additives may be used alone, or two or more of them may be used in combination. Examples of additives include binders, hardeners, antioxidants, active energy ray absorbers, light stabilizers, antifoaming agents, antifouling agents, preservatives, rust inhibitors, pH adjusters, lubricants, and antiblocking agents. , pigments, dyes, metal oxide particle dispersions, organic particle dispersions, etc.

Content of the said additive in the said active energy ray-curable resin composition is not specifically limited. The content of the additive is preferably about 0 to 50 parts by mass with respect to 100 parts by mass of the curable resin composition in terms of solid content.

[Physical properties and production method of active energy ray-curable resin composition]

The physical properties of the active energy ray-curable resin composition are not particularly limited. From the viewpoint of coatability, the solid content concentration of the active energy ray-curable resin composition is preferably about 0.5 to 50% by mass. In addition, from the viewpoint of coatability, the viscosity of the active energy ray-curable resin composition at a temperature of 25°C is desirably about 0.5 to 1000 mPa･s, more desirably about 0.5 to 100 mPa･s.

The said active energy ray-curable resin composition is obtained by mixing (A) component, (C) component, if necessary (D) component, the said (meth)acrylate, photoinitiator, additive. After mixing, it is emulsified (or dispersed), and then the (B) component, (E) component, and a solvent if necessary are mixed. It does not specifically limit as an emulsification method, Various well-known methods, such as an inverse emulsification method and a mechanical emulsification method, can be applied. Moreover, in the range which does not impair the effect of this invention, various conventional emulsifiers and dispersants can be used as needed. The emulsification conditions are also not particularly limited, but for example, the temperature is usually about 5 to 70°C, preferably about 10 to 50°C. In addition, the time is usually about 1 to 24 hours, preferably about 1 to 12 hours. In addition, the mixture of (A) component, (D) component, and a photoinitiator may be pre-emulsified before emulsification.

It does not specifically limit as an apparatus used for the said emulsification, For example, a propeller mixer, a turbo mixer, a homomixer, a disperser mixer, a super mixer, a colloid mill, a high pressure homogenizer, an ultrasonic wave etc. are mentioned. device, and a plurality of devices can be used in combination as appropriate.

The above-mentioned active energy ray-curable resin composition can be used as a coating agent for various plastic films, especially a scratch-resistant coating agent (hard coating agent). In addition, it can be used as various coating agents such as woodworking paints and printing inks.

[CURED FILM] The cured film of this invention is obtained from the said active energy ray-curable resin composition. Specifically, for example, it can be obtained by applying the coating agent to various plastic substrates so that the mass after drying is about 0.05 to 30 g/m ² , ideally about 0.1 to 20 g/m ² , so that After drying, it is hardened by irradiating active energy rays such as ultraviolet rays, electron beams, and radiation. The above-mentioned cured film is formed, for example, by coating and curing on a plastic substrate as an anti-scratch coating agent.

The above-mentioned plastic substrates include, for example: polycarbonate, polymethyl methacrylate, polystyrene, polyethylene terephthalate (PET), polyimide, polyolefin, nylon, epoxy resin, melamine Resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, etc. The form of the above-mentioned plastic base material includes, for example, a film form, a molded body, and the like.

The said cured film can be manufactured by various conventional methods. Specifically, for example, the above-mentioned active energy ray-curable resin composition is coated on the above-mentioned plastic base material, dried if necessary, and then irradiated with active energy rays such as ultraviolet rays, electron beams, and radiation to cure it. In addition, after coating the above-mentioned coating agent on the release film and irradiating it with active energy rays to harden it, an adhesive layer or the like is provided on it, and the above-mentioned plastic substrate is pasted thereon, and then the release film is peeled off, and the hardened film is transferred to The method of printing on the above-mentioned plastic substrate, etc.

Examples of active energy rays used in the curing reaction include ultraviolet rays and electron beams. As a light source of ultraviolet rays, an ultraviolet irradiation apparatus including a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED lamp can be used. It should be noted that the amount of light, the arrangement of the light source, the conveying speed, etc. can be adjusted as needed. For example, when a high-pressure mercury lamp is used, it is desirable to use the conveying speed for one lamp having a lamp output of about 80 to 160 W/cm. Hardening is carried out at about 5 to 50 m/min.

Examples of the coating method include bar coater coating, wire bar coating, mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. Printing, spray coating, etc.

The active energy ray-curable resin composition can be cured by active energy rays to form a cured film, and is therefore suitable for plastics that are easily deformed by heat.

[film] The film of this invention contains the said cured film. This film is an article which has the above-mentioned cured film and various base films as constituent elements.

As said base film, a plastic film etc. are mentioned, for example, Various conventional plastic films can be used. Examples of the plastic film include polycarbonate film, polyester film, polyolefin film, polystyrene film, epoxy resin film, melamine resin film, triacetate cellulose film, ABS resin film, AS resin film, acrylic film resin film and alicyclic polyolefin resin film, etc. From the viewpoint of transparency and adhesiveness with the cured film, the plastic film is preferably selected from a polycarbonate film, a triacetyl cellulose film, an acrylic resin film, and an alicyclic polyolefin resin film. A film in a group. In addition, the average thickness of the base film is not particularly limited, but is usually about 20 to 1000 μm, preferably 20 to 200 μm.

The above-mentioned thin film can be produced by various conventional methods. Specifically, for example, the above-mentioned active energy ray-curable resin composition is applied on the above-mentioned base film, dried if necessary, and then irradiated with the above-mentioned active energy ray and cured. Alternatively, a laminated film can also be produced by applying the active energy ray-curable resin composition of the present invention on the uncoated surface of the obtained base film, laminating another base film thereon, and then irradiating active energy rays.

As a coating method, the above-mentioned method etc. are mentioned, for example.

The coating amount is not particularly limited, but the mass after drying is desirably about 0.1 to 30 g/m ² , more desirably 1 to 20 g/m ² . Moreover, the average film thickness of the cured film formed on the base film is usually about 0.05 to 30 μm, preferably about 0.1 to 20 μm. [Example]

The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In each example, unless otherwise specified, parts and % are based on mass.

<Synthesis of urethane (meth)acrylate (A)> Manufacturing Example 1 Into a reaction vessel equipped with a stirring device and a cooling pipe, 47.9 parts of modified isocyanurate of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name "CORONATE HXR"), polyethylene glycol 84.0 parts of monomethyl ether (manufactured by NOF Corporation, trade name "UNIOX M-1000"), a mixture of dipipentaerythritol pentaacrylate and dipeptaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd. , trade name "ARONIX M-403") 117.6 parts, 0.06 parts of tin octoate, 0.15 parts of 4-methoxyphenol, and then the temperature in the system was raised to 70°C over about 15 minutes. Next, after keeping the inside of the reaction system at the same temperature for 1.5 hours, it was cooled to 60°C. Then, 50.4 parts of a mixture of dipivaloerythritol pentaacrylate and dipeotaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name "ARONIX M-403") and 0.12 part of tin octoate were added, followed by adding approx. The temperature in the system was raised to 75°C for 15 minutes. Next, after maintaining the reaction system at the same temperature for 1 hour, 0.15 part of 4-methoxyphenol was charged, and then cooled to obtain polyurethane (meth)acrylate 1 with a solid content of 100%.

Manufacturing example 2 Into a reaction vessel equipped with a stirring device and a cooling pipe, 42.9 parts of modified isocyanurate of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name "CORONATE HXR"), polyethylene glycol 50.7 parts of monomethyl ether (manufactured by NOF Corporation, trade name "UNIOX M-1000"), a mixture of neopentaerythritol triacrylate and neotaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd., trade name) name "ARONIX M-305") 66.3 parts, 0.12 parts of tin octoate, 0.15 parts of 4-methoxyphenol, and the temperature in the system was raised to 70°C over about 15 minutes. Next, after keeping the inside of the reaction system at the same temperature for 1.5 hours, it was cooled to 60°C. Next, 28.8 parts of a mixture of neotaerythritol triacrylate and neotaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd., trade name "ARONIX M-305") and 0.12 part of tin octoate were added, and the mixture was added for about 15 minutes. The temperature in the system was raised to 75°C. Next, after maintaining the reaction system at the same temperature for 1 hour, 0.15 part of 4-methoxyphenol was charged, and then cooled to obtain polyurethane (meth)acrylate 2 with a solid content of 100%.

Comparative Production Example 1 Into a reaction vessel equipped with a stirring device and a cooling pipe, 137.8 parts of modified isocyanurate of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name "CORONATE HXR"), rosin epoxy acrylic acid Esters (manufactured by Arakawa Chemical Industry Co., Ltd., trade name "BEAMSET101") 63.5 parts, 2-hydroxyethyl acrylate 37.8 parts, polyethylene glycol monomethyl ether (manufactured by NOF Corporation, trade name "UNIOX M- 1000") 9.5 parts and 0.15 parts of 4-methoxyphenol, then, 0.12 parts of tin octoate was charged under stirring, and the temperature of the system was then raised. After the temperature was kept at 70° C. for 1.5 hours, 11.8 parts of 2-hydroxyethyl acrylate was added, and the temperature was further incubated for 1 hour. Then, 39.6 parts of castor oil fatty acid (manufactured by Toyokuni Oil Co., Ltd., trade name "CO-FA") was added, and after maintaining the reaction system at the same temperature for 1 hour, 0.15 part of 4-methoxyphenol was added to obtain Polyurethane acrylate. The acid value of the urethane acrylate was 24.2 mgKOH/g. 200 parts of the polyurethane acrylates were kept at 60 to 70° C., 6.1 parts of triethylamine were added under stirring for neutralization, and the mixture was cooled to obtain a polyurethane (meth)acrylate salt with a solid content of 100%.

[Preparation of Active Energy Ray Curable Resin Composition] Example 1 76.9 parts of the above-mentioned polyurethane (meth)acrylate 1 and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane as a photopolymerization initiator -1-One (manufactured by IGM Resins B.V., trade name "OMNIRAD2959", solid content 100%) 9.0 parts, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetyloxy- A mixture of ethoxy]-ethyl ester and oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester (manufactured by IGM Resins B.V., trade name "OMNIRAD754", solid content 100% ) 4.5 parts were mixed and dissolved, and then 135.6 parts of water was slowly added with stirring to emulsify to obtain an emulsion having a solid content of 40%. Next, 400.0 parts of PEDOT/PSS aqueous dispersion (manufactured by Japan Agfa-Gevaert Co., Ltd., trade name "Orgacon ICP1010", solid content 1.2%) as a conductive polymer (4.8 parts solid content) was prepared in the emulsion. ), acetylene glycol-based surface conditioner (manufactured by Nissin Chemical Industry Co., Ltd., trade name "OLFINE EXP. 4200", solid content 75%) 6.4 parts (solid content 4.8 parts) and 367.6 parts of water to obtain solid content 10% active energy ray curable resin composition.

Example 2 and Comparative Examples 3 to 4 Except having changed the composition to the composition of Table 1, the active-energy-ray-curable resin composition with a solid content of 10% was produced by the same procedure as Example 1.

Example 3 45.3 parts of the above-mentioned urethane (meth)acrylate 1 and dipivalerythritol poly(meth)acrylate (manufactured by Toagosei Co., Ltd., trade name "ARONIX M-403", solid content 100%) 22.6 parts , Neotaerythritol poly(meth)acrylate (manufactured by Toagosei Co., Ltd., trade name "ARONIX M-306", solid content 100%) 9.0 parts, 1-[4-(2 -Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by IGM Resins B.V., trade name "OMNIRAD2959", solid content 100%) 9.0 parts, oxy -Phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester with oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy] -4.5 parts of a mixture of ethyl esters (manufactured by IGM Resins B.V., trade name "OMNIRAD754", solid content 100%) was mixed and dissolved, and then 135.6 parts of water was slowly added while stirring to emulsify to obtain solid content 40 % of the emulsion. Next, 400.0 parts of PEDOT/PSS aqueous dispersion (manufactured by Japan Agfa-Gevaert Co., Ltd., trade name "Orgacon ICP1010", solid content 1.2%) as a conductive polymer (4.8 parts solid content) was prepared in the emulsion. ), acetylene glycol-based surface conditioner (manufactured by Nissin Chemical Industry Co., Ltd., trade name "OLFINE EXP. 4200", solid content 75%) 6.4 parts (solid content 4.8 parts) and 367.6 parts of water to obtain solid content 10% active energy ray curable resin composition.

Examples 4 to 9 and 11 Except having changed the composition to the composition of Table 1, the same procedure as Example 3 was carried out, and the active energy ray-curable resin composition with a solid content of 10% was produced.

Example 10 44.0 parts of the above-mentioned polyurethane (meth)acrylate 2, neotaerythritol poly(meth)acrylate (manufactured by Toagosei Co., Ltd., trade name "ARONIX M-306", solid content 100%) 19.0 parts, 1-[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (manufactured by IGM Resins B.V., trade name " OMNIRAD2959", solid content 100%) 8.0 parts, oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester and oxy-phenyl - 4.0 parts of a mixture of 2-[2-hydroxy-ethoxy]-ethyl acetate (manufactured by IGM Resins B.V., trade name "OMNIRAD754", solid content 100%) was mixed and dissolved, and then slowly stirred while stirring 112.5 parts of water were added and emulsified to obtain an emulsion having a solid content of 40%. Next, 1666.7 parts of PEDOT/PSS aqueous dispersion (manufactured by Japan Agfa-Gevaert Co., Ltd., trade name "Orgacon ICP1010", solid content 1.2%) as a conductive polymer (20.0 parts solid content) was prepared in the emulsion. ), acetylene glycol-based surface conditioner (manufactured by Nissin Chemical Co., Ltd., trade name "OLFINE EXP. 4200", solid content 75%) 6.7 parts (solid content 5.0 parts) and 139.1 parts of water to obtain solid content 5% active energy ray curable resin composition.

Comparative Example 1 PEDOT/PSS aqueous dispersion (manufactured by Agfa-Gevaert Co., Ltd., Japan, trade name "Orgacon ICP1010", solid content 1.2%) 6250.0 parts (solid content 75.0 parts) as a conductive polymer, acetylene glycol-based surface Adjusting agent (manufactured by Nissin Chemical Industry Co., Ltd., trade name "OLFINE EXP. 4200", solid content 75%) 33.3 parts (solid content 25.0 parts) and 382.7 parts of water to obtain active energy ray hardening with a solid content of 1.5% Resin composition.

Comparative Example 2 The same procedure as in Example 3 was followed, except that the composition was changed to the composition of Table 1, and a mixed solvent of water and isopropyl alcohol (IPA) (water/IPA (mass ratio) = 54/46) was used instead of water An active energy ray-curable resin composition with a solid content of 10% is produced.

(Storage stability of active energy ray-curable resin composition) The active energy ray-curable resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 were put into a threaded pipe, and stored under normal temperature for one week in a light-shielding manner. The state of the active energy ray-curable resin composition was visually evaluated according to the following criteria. The results are shown in Table 1. 〇: The liquid state was maintained without any change in appearance even after being stored in a light-shielding manner for one week at room temperature. ×: Resin separation and/or conductive polymer aggregation after one week of light-shielded storage at room temperature.

[Preparation of Cured Film] 15 parts of the active energy ray-curable resin composition of Example 1 were diluted with 84 parts of water and 1 part of 1,3-dimethyl-2-imidazolidinone so as to be water with a solid content of 1.5% until the dispersion. The aqueous dispersion was coated on a polyethylene terephthalate film with a film thickness of 50 μm (manufactured by Toray Co., Ltd., trade name “Lumirror 50T60”) with a #3 bar coater to cure the film. The thickness was set to 0.1 μm, and it was dried at 80° C. for 2 minutes to prepare a thin film. Then, under the conditions of a high pressure mercury lamp 120 W/cm (1 lamp), an irradiation distance of 24 cm, and a belt speed of 22 m/min, a film with a cured film was obtained in one pass and a cumulative irradiation dose of 50 mJ/cm ² . Also from the active energy ray-curable resin compositions of Examples 3, 5 to 9, and 11 and Comparative Examples 3 to 4, it was performed in the same manner to obtain a cured film-attached film.

15 parts of active energy ray-curable resin compositions of Example 2 were diluted with 84 parts of isopropanol and 1 part of 1,3-dimethyl-2-imidazolidinone until it became an aqueous dispersion having a solid content of 1.5%. The aqueous dispersion was coated on a polyethylene terephthalate film with a film thickness of 50 μm (manufactured by Toray Co., Ltd., trade name “Lumirror 50T60”) with a #3 bar coater to cure the film. The thickness was set to 0.1 μm, and it was dried at 80° C. for 1 minute to prepare a thin film. Then, under the conditions of a high pressure mercury lamp 120 W/cm (1 lamp), an irradiation distance of 24 cm, and a belt speed of 22 m/min, a film with a cured film was obtained in one pass and a cumulative irradiation dose of 50 mJ/cm ² .

15 parts of the active energy ray-curable resin composition of Example 4 was diluted with water until it became an aqueous dispersion with a solid content of 1.5%. The aqueous dispersion was coated on a polyethylene terephthalate film with a film thickness of 50 μm (manufactured by Toray Co., Ltd., trade name “Lumirror 50T60”) with a #3 bar coater to cure the film. The thickness was set to 0.1 μm, and it was dried at 80° C. for 2 minutes to prepare a thin film. Then, under the conditions of a high pressure mercury lamp 120 W/cm (1 lamp), an irradiation distance of 24 cm, and a belt speed of 22 m/min, a film with a cured film was obtained in one pass and a cumulative irradiation dose of 50 mJ/cm ² .

30 parts of the active energy ray-curable resin composition of Example 10 was diluted with 70 parts of water until it became an aqueous dispersion with a solid content of 1.5%. The aqueous dispersion was coated on a polyethylene terephthalate film with a film thickness of 50 μm (manufactured by Toray Co., Ltd., trade name “Lumirror 50T60”) with a #3 bar coater to cure the film. The thickness was set to 0.1 μm, and it was dried at 80° C. for 2 minutes to prepare a thin film. Then, under the conditions of a high pressure mercury lamp 120 W/cm (1 lamp), an irradiation distance of 24 cm, and a belt speed of 22 m/min, a film with a cured film was obtained in one pass and a cumulative irradiation dose of 50 mJ/cm ² .

For the resin composition of Comparative Example 1, the aqueous dispersion with a solid content of 1.5% was directly coated on a polyethylene terephthalate film with a film thickness of 50 μm (manufactured by Toray Co., Ltd., (trade name "Lumirror 50T60") so that the film thickness of the film after curing was 0.1 μm, and it was dried at 80° C. for 2 minutes to prepare a film with a film.

15 parts of active energy ray-curable resin compositions of Comparative Example 2 were diluted with 84 parts of water and 1 part of 1,3-dimethyl-2-imidazolidinone until it became an aqueous dispersion having a solid content of 1.5%. However, since the obtained aqueous dispersion was separated, it could not be applied to a polyethylene terephthalate film, and the following evaluation could not be performed.

(Antistatic) The surface resistivity of the cured film of the above-mentioned cured film-attached film of Example 1 was measured with a surface resistivity meter (manufactured by Mitsubishi Chemical Co., Ltd., trade name "Hiresta MCP-HT-450"), and a voltage was applied according to JIS K 6911. 10 ~ 500V to measure. The results are shown in Table 1. It evaluated similarly about the said thin film with a cured film of Examples 2-11 and Comparative Examples 1 and 3-4.

(solvent resistance) The cured film of the said film with a cured film of Example 1 was reciprocated 10 times with a width of 5 cm with a cotton swab soaked in methyl ethyl ketone, the presence or absence of dissolution of the cured film was observed, and the solvent resistance was evaluated according to the following criteria. The results are shown in Table 1. It evaluated similarly about the said thin film with a cured film of Examples 2-11 and Comparative Examples 1 and 3-4. ○: There was no dissolution of the cured film at all. △: The back-and-forth trace of the cotton swab remains on the cured film. ×: The cured film was dissolved.

(adhesion) On the cured film of the above-mentioned cured film-attached film of Example 1, 11 scratches were formed at intervals of 1 mm reaching the film substrate using a tool guide and a tool, and 100 checkerboards were produced in the same manner as the scratches were orthogonally formed. grid. The cellophane tape was firmly crimped to the checkered portion, peeled off at a stretch, and the checkered state was visually observed and evaluated. The results are shown in Table 1. It evaluated similarly about the said thin film with a cured film of Examples 2-11 and Comparative Examples 1 and 3-4. ○: There was no peeling of the cured film at all. ×: There is peeling of the cured film.

[Table 1]

The compounding quantity of Table 1 is the value of the mass part converted into solid content. Notes and abbreviations in Table 1 are as follows. * Since the aqueous dispersion of the active energy ray-curable resin composition cannot be applied, it cannot be evaluated. (Abbreviation and detailed description of compound) ICP1010: PEDOT/PSS aqueous dispersion (trade name "Orgacon ICP1010", solid content 1.2%), manufactured by Japan Agfa-Gevaert Co., Ltd. SELFTRON: Self-doping type ethylidenedioxypoly(thiophene) aqueous solution (trade name "SELFTRON H", solid content 1.2%), manufactured by Tosoh Corporation. AQUAPASS: Aqueous solution of polyaniline sulfonic acid (trade name "aquaPASS 01-x", solid content 5%), manufactured by Mitsubishi Chemical Corporation. M403: Dipionaerythritol poly(meth)acrylate with a hydroxyl value of 90 mgKOH/g (trade name "ARONIX M-403", solid content 100%), manufactured by Toagosei Co., Ltd. M306: Neotaerythritol poly(meth)acrylate with a hydroxyl value of 160 mgKOH/g (trade name "ARONIX M-306", solid content 100%), manufactured by Toagosei Co., Ltd. M3150: Trimethylolpropane EO-modified acrylate (trade name "MIRAMER M-3150", solid content 100%), manufactured by MIWON Corporation. EXP4200: Acetylene glycol-based surface conditioner (trade name "OLFINE EXP. 4200", solid content 75%), manufactured by Nissin Chemical Industry Co., Ltd. OMNI2959: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name "OMNIRAD2959", solid content 100%), IGM Manufactured by Resins B.V. OMNI1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name "OMNIRAD1173", solid content 100%), manufactured by IGM Resins B.V. OMNI754: Oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester with oxy-phenyl-acetic acid 2-[2-hydroxy- Ethoxy]-ethyl ester mixture (trade name "OMNIRAD754", solid content 100%), manufactured by IGM Resins B.V.

Claims (10)

An active energy ray curable resin composition is characterized by containing: Polyurethane (meth)acrylate (A), which is a reactant containing the reaction components of hydroxyl-containing (meth)acrylate (a1), polyisocyanate (a2), and hydroxyl-containing polyalkylene glycols (a3) ; a conductive polymer (B); and water (C). The active energy ray-curable resin composition according to claim 1, wherein the component (a1) is a hydroxyl group-containing (meth)acrylate having at least three (meth)acryloyl groups in the molecule. The active energy ray-curable resin composition according to claim 1 or 2, wherein the component (a2) is a polyisocyanate having at least three isocyanate groups in the molecule. The active energy ray-curable resin composition according to any one of claims 1 to 3, wherein the component (a3) is a compound represented by the following general formula (1), (Chemical 1) H-(OCH ₂ CH ₂ )n-OR (1) (in the formula, R represents any one of an alkyl group, an allyl group, a (meth)acryloyl group, and an acyl group, and n represents an integer of 3 to 25). The active energy ray-curable resin composition according to any one of claims 1 to 4, wherein the component (B) is a poly(thiophene). The active energy ray-curable resin composition according to any one of claims 1 to 5, further comprising a (meth)acrylate (D) having at least three (meth)acryloyl groups in the molecule. . The active energy ray-curable resin composition according to any one of claims 1 to 6, further comprising a surface conditioner (E). The active energy ray-curable resin composition according to any one of claims 1 to 7, wherein, in terms of solid content, (B) Content of a component is 0.1-20 mass parts. A cured film comprising the active energy ray-curable resin composition according to any one of claims 1 to 8. A film characterized by containing the cured film described in claim 9.