KR20220044113A - Active energy ray-curable resin composition and laminate - Google Patents

Abstract

(assignment)
The present invention provides an active energy ray-curable resin composition and a laminate.
(Solution)
As an active energy ray-curable resin composition constituting a resin layer in a laminate including a substrate and a resin layer,
(meth)acrylate (A) and
Compound (B) having a fluorine atom
including,
An active energy ray-curable resin composition satisfying the following conditions 1 and 2.
Condition 1: The indentation hardness (N/mm 2 ) of the resin layer is 450 or more and 600 or less.
Condition 2: The elongation at break of the resin layer is 3.7% or more and 10.0% or less.

Description

ACTIVE ENERGY RAY-CURABLE RESIN COMPOSITION AND LAMINATE

The present disclosure relates to an active energy ray-curable resin composition and a laminate.

Conventionally, various plastics have been used in various fields, such as the main body of home appliances such as refrigerators, televisions, and air conditioners, and frames and displays of information terminals such as remote controls, mobile phones, smartphones, tablets and PCs, automobile parts, and automobile interior materials. there is being used. Although plastics and the like have advantages such as workability, transparency, lightness, and low cost, they have a disadvantage in that they are relatively easily damaged.

In order to improve such a defect, a resin layer excellent in abrasion resistance is formed on the surface of plastics etc., and the abrasion resistance of the surface is improved without impairing the advantage with which plastics etc. are equipped.

Japanese Patent Laid-Open No. 2004-1350

Nowadays, flexible type displays and smartphones are attracting attention, and scratch resistance and flexibility are required for these devices. Patent Document 1 discloses a resin layer having excellent scratch resistance, but there is no description about the flexibility required for a flexible type display or smartphone.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the said subject was solved by a predetermined|prescribed active energy ray-curable resin composition and laminated body, as a result of earnestly examining. Moreover, this invention is for solving at least a part of the said subject, Comprising: It can implement|achieve as the following aspects or application examples.

The present disclosure provides the following items.

(Item 1)

As an active energy ray-curable resin composition constituting a resin layer in a laminate including a substrate and a resin layer,

(meth)acrylate (A) and

Compound (B) having a fluorine atom

including,

An active energy ray-curable resin composition satisfying the following conditions 1 and 2.

Condition 1: The indentation hardness (N/mm 2 ) of the resin layer is 450 or more and 600 or less.

Condition 2: Elongation at break of the resin layer is 3.7% or more and 10.0% or less.

(Item 2)

(A) The active energy ray-curable resin composition as described in item 1 in which component contains urethane (meth)acrylate (a1) and/or hydroxyl-containing (meth)acrylate (a2).

(Item 3)

(a1) component is a reaction product of polyisocyanate (a1-1) and hydroxyl group-containing (meth)acrylate (a1-2), mass ratio of (a1-1) component and (a1-2) component ((a1-1) The active energy ray-curable resin composition according to item 2, wherein /(a1-2)) is 15/85 to 50/50.

(Item 4)

(B) The active energy ray-curable resin composition according to any one of items 1 to 3, wherein the component is a compound having a fluorine atom and a polymerizable unsaturated group.

(Item 5)

The active energy ray-curable resin composition according to any one of items 1 to 4, comprising an antistatic agent (C).

(Item 6)

(C) The active energy ray-curable resin composition in any one of items 1-5 whose component is a polymer provided with a quaternary ammonium base group.

(Item 7)

A laminate comprising a substrate and a resin layer, wherein the resin layer is a cured product of the active energy ray-curable resin composition according to any one of items 1 to 6.

A laminate including a resin layer composed of an active energy ray-curable resin composition provided in the present disclosure has good scratch resistance and flexibility.

Throughout the present disclosure, numerical ranges such as respective physical properties and content can be appropriately set (eg, by selecting from the values of the upper and lower limits described in each item below). Specifically, for the numerical value α, when the lower limit of the numerical value α is exemplified by A1, A2, A3, etc., and the upper limit of the numerical value α is exemplified by B1, B2, B3, etc., the range of the numerical value α is A1 or more, A2 or more, A3 or more, B1 or less, B2 or less, B3 or less, A1 to B1, A1 to B2, A1 to B3, A2 to B1, A2 to B2, A2 to B3, A3 to B1, A3 to B2, A3 to B3, etc. This is exemplified. In addition, in this indication, "to" is used in the meaning which includes the numerical value described before and after that as a lower limit and an upper limit. Hereinafter, each component constituting the active energy ray-curable resin composition provided in the present disclosure, a resin layer, a laminate, and the like will be described in detail.

<(meth)acrylate (A)>

As (meth)acrylate (A) (in this indication, it is also called "(A) component"), (meth)acrylate containing a chain hydrocarbon group, (meth)acryl containing an alicyclic hydrocarbon group The (meth)acrylate containing a rate, an aromatic hydrocarbon group, the (meth)acrylate containing a heterocyclic ring, etc. are illustrated. (A) You may obtain a component, for example by making monomers react. Further, in the present disclosure, the chain structure refers to a structure not having a cyclic structure, and may include a linear structure and/or a branched structure.

As (meth)acrylate containing a chain hydrocarbon group, mono(meth)acrylate containing a chain hydrocarbon group, di(meth)acrylate containing a chain hydrocarbon group, tri(meth)acrylate containing a chain hydrocarbon group, chain hydrocarbon tetra(meth)acrylate containing a group, penta(meth)acrylate containing a chain hydrocarbon group, hexa(meth)acrylate containing a chain hydrocarbon group, etc. are illustrated.

Mono (meth) acrylate containing a chain hydrocarbon group, mono (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, Butanediol mono(meth)acrylate, pentanediol mono(meth)acrylate, hexanediol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, neopentyl glycol mono ( meth) acrylate, ethoxylated neopentyl glycol mono (meth) acrylate, hydroxypivalate neopentyl glycol mono (meth) acrylate, trimethylol propane mono (meth) acrylate, ethoxylated trimethylol propane mono (meth) Acrylate, propoxylated trimethylolpropane mono(meth)acrylate, tris(2-hydroxyethyl)isocyanurate mono(meth)acrylate, glycerol mono(meth)acrylate, etc. are illustrated.

As di (meth) acrylate containing a chain hydrocarbon group, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, polyethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, bis(methacryloyloxy)propanol, decanediol di(meth)acrylate, hexanediol di(meth)acrylate, nonanedi Old di(meth)acrylate, polytetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl Glycol di(meth)acrylate etc. are illustrated.

As tri(meth)acrylate containing a chain hydrocarbon group, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, glycerin tri(meth)acrylate, sorbitol tri(meth)acrylate, tris2 -Hydroxyethyl isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO (ethylene oxide) modified trimethylolpropane tri(meth)acrylate, PO (propylene oxide) modified trimethylolpropane tri(meth)acrylate, EO modified phosphoric acid tri(meth)acrylate, trimethylolethane tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, etc. are illustrated.

As tetra (meth) acrylate containing a chain hydrocarbon group, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate etc. are exemplified.

Examples of the penta (meth) acrylate containing a chain hydrocarbon group include dipentaerythritol penta (meth) acrylate, sorbitol penta (meth) acrylate, and ditrimethylolpropane penta (meth) acrylate.

As hexa(meth)acrylate containing a chain hydrocarbon group, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and aliphatic urethane (meth)acrylate (product name "Miramer PU-610", manufactured by Miwon Specialty chemical) and the like.

As other (meth)acrylates containing a chain hydrocarbon group, 16-20 functional acrylates containing a dendrimer structure (product names "Sirius-501", "SUBARU-501", Osaka Organic Chemical Industry Co., Ltd.) (OSAKA ORGANIC CHEMICAL INDUSTRY LTD.)) and the like are exemplified.

Examples of the (meth)acrylate containing an alicyclic hydrocarbon group include tricyclodecanedimethanoldi(meth)acrylate and dimethyloltricyclodecanedi(meth)acrylate.

As (meth)acrylate containing an aromatic hydrocarbon group, bisphenol A di(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, bis(meth) ) Acrylic acid [3,3'-[isopropylidenebis(p-phenyleneoxy)]bis(2-hydroxypropane)]-1,1'-diyl, bisphenol A diglycidyl ether (meth)acrylic acid addition water and the like are exemplified. Moreover, (meth)acrylic acid is methacrylic acid and/or acrylic acid.

Examples of the (meth)acrylate containing a heterocycle include ethoxylated isocyanuric acid tri(meth)acrylate, caprolactone-modified tris((meth)acrylooxyethyl)isocyanurate, and the like.

As another (meth)acrylate, urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, etc. are illustrated.

Various well-known methods are illustrated as a synthesis method of urethane (meth)acrylate. As various known synthesis methods of urethane (meth)acrylate,

(1) A method of further urethanating a hydroxyl group-containing (meth)acrylate with a prepolymer having an isocyanate group obtained by urethanizing a polyol and a polyisocyanate;

(2) A method of further reacting an isocyanate group-containing (meth)acrylate with a prepolymer having a hydroxyl group obtained by urethanizing a polyol and a polyisocyanate;

(3) a method of reacting polyisocyanate with hydroxyl group-containing (meth)acrylate;

(4) A method of reacting a polyol with an isocyanate group-containing (meth)acrylate

etc. are exemplified.

In the synthesis method of urethane (meth)acrylate, various well-known catalysts (dibutyltin dilaurate, etc.) can also be used suitably as needed.

In the synthesis method of urethane (meth)acrylate, it is possible to obtain by making each component react under the temperature and pressure at the time of urethanation reaction.

As the polyol, polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, polyolefin polyol, neopentyl glycol, 3-methyl-1,5-pentanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1, 6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecanedimethylol, bis-[hydroxymethyl]-cyclohexane, etc. are illustrated. Substances exemplified as polyols and those known as polyols can be used alone or in combination of two or more.

As polyether polyol, polyalkylene glycol (polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.) etc. are illustrated. As the polyether polyol, a commercially available product may be used. As said product, the product name "adeca polyether P series", "adeca polyether G series", "adeca polyether EDP series" (made by ADEKA Corporation), etc. are illustrated.

Polyester polyols obtained by reaction of polyols with polycarboxylic acids (succinic acid, phthalic acid, malonic acid, maleic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, etc.), cyclic esters (propiolactone, β- a ring-opening polymer of methyl-δ-valerolactone, ε-caprolactone, etc.), and a trivalent reaction product of a polyol, a polycarboxylic acid, and a cyclic ester, and the like. As the polyester polyol, a commercially available product may be used. As the said product, product name "Kurare Polyol P series", "Kuraray Polyol F series" (product of Kuraray Co., Ltd.), product name "PLACCEL 205" (Co.) Daicel (made by Daicel Corporation), a product name "Polylite OD-X-2155" (made by DIC Corporation), etc. are illustrated.

Examples of the polycarbonate polyol include a reaction product of a polyol and phosgene, and a ring-opened polymer of a cyclic carbonate (such as an alkylene carbonate). Examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate. As the polycarbonate polyol, a commercially available product may be used. As said product, the product name "Kurare Polyol C series" (Kuraray Co., Ltd. product) etc. are mentioned.

Examples of the acrylic polyol include homopolymers or copolymers of acrylic monomers containing at least one hydroxyl group in one molecule, or those obtained by copolymerizing other monomers with those copolymers. As the acrylic polyol, a commercially available product may be used. As the said product, the product name "ARUFON UH-2000 series" (product of Dong-A Synthesis Co., Ltd. TOAGOSEI CO., LTD.) etc. are illustrated.

Examples of the polyolefin polyol include polybutadiene containing two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, chlorinated compounds thereof, and the like. As the polyolefin polyol, a commercially available product may be used. As the said product, the product name "NISSO-PB GI series" (Nippon Soda Co., Ltd. product) etc. are illustrated.

As polyisocyanate, the polyisocyanate containing a chain hydrocarbon group, the polyisocyanate containing an alicyclic hydrocarbon group, the polyisocyanate containing an aromatic hydrocarbon group, etc. are illustrated. As polyisocyanate containing a chain|strand hydrocarbon group, hexamethylene diisocyanate etc. are illustrated. As polyisocyanate containing an alicyclic hydrocarbon group, isophorone diisocyanate, dicyclohexylmethane diisocyanate, etc. are illustrated. Examples of the polyisocyanate containing an aromatic hydrocarbon group include tolylene diisocyanate, xylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, and the like. As another polyisocyanate, 1, 5- naphthalene diisocyanate, the adduct of the polyisocyanate exemplified above, and various well-known polyisocyanates, the multimer of these isocyanate, etc. are illustrated. As such polyisocyanate, biuret, nurate, adduct, allophanate and the like are exemplified. As a burette of polyisocyanate, the product names "DURANATE 24A-100", "buret 22A-75P", "buret 21S-75E" (all products of Asahi Kasei Corp.) etc. are illustrated. . As a nurate of polyisocyanate, product name "CORONATE HK", "Coronate HXR" (all are Tosoh Corporation products), etc. are illustrated. As an adduct of polyisocyanate, the product name "Coronate HL" (made by Tosoh Corporation), etc. are illustrated. As an allophanate of polyisocyanate, a product name "Coronate 2770" (made by Tosoh Corporation), etc. are illustrated. Moreover, the polyisocyanate of this indication is also the thing of about 3 or more and 10 or less of average isocyanate groups. In addition, the average number of isocyanate groups is computable by the following formula. Average number of isocyanate groups = (number average molecular weight (Mn) x isocyanate group concentration (%)) / (42.02 x 100). The isocyanate group concentration (%) in the formula is a value measured according to the method described in JIS K 1603-1:2007. Substances exemplified as polyisocyanates and those known as polyisocyanates can be used alone or in combination of two or more.

As the hydroxyl group-containing (meth)acrylate, a hydroxyl group-containing (meth)acrylate containing a chain hydrocarbon group, a hydroxyl group-containing (meth)acrylate containing an alicyclic hydrocarbon group, a hydroxyl group-containing (meth)acrylate containing an aromatic hydrocarbon group, etc. is exemplified As a hydroxyl group-containing (meth)acrylate containing a chain hydrocarbon group, 1-hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxy Examples include oxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. do. Examples of the hydroxyl group-containing (meth)acrylate containing an alicyclic hydrocarbon group include 4-(hydroxymethyl)cyclohexylmethyl (meth)acrylate. Hydroxyphenyl (meth)acrylate etc. are illustrated as hydroxyl-containing (meth)acrylate containing an aromatic hydrocarbon group. Substances exemplified as the hydroxyl group-containing (meth)acrylate and those known as the hydroxyl group-containing (meth)acrylate can be used alone or in combination of two or more.

As isocyanate group-containing (meth)acrylate, 2-isocyanate ethyl (meth)acrylate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 1,1-(bis(meth)acryloyl oxymethyl) ethyl isocyanate etc. are illustrated. A substance exemplified as an isocyanate group-containing (meth)acrylate and a known substance as an isocyanate group-containing (meth)acrylate can be used alone or in combination of two or more.

Various well-known methods are illustrated as a synthesis method of polyester (meth)acrylate. As various known synthesis methods of polyester (meth)acrylate,

(1) A method of reacting a carboxyl group-containing (meth)acrylate (carboxyethyl (meth)acrylate, carboxypolycaprolactone mono (meth)acrylate, etc.) with a hydroxyl-terminated polyester obtained by reacting a polycarboxylic acid with a polyol;

(2) Method of reacting hydroxyl group-containing (meth)acrylate with carboxyl-terminated polyester obtained by reacting polycarboxylic acid and polyol

etc. are exemplified.

In these methods, it is considered that various well-known catalysts are used suitably as needed.

As the epoxy (meth)acrylate, a carboxyl group-containing (meth)acrylate is added to an epoxy resin containing at least two epoxy groups in one molecule (bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, etc.) What is obtained by subjecting it to addition reaction is exemplified.

In these methods, it is considered that various well-known catalysts are used suitably as needed.

(A) The component may use a commercially available product. As the product, pentaerythritol triacrylate ((product names "A-TMM-3", "A-TMM-3L", manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), ( Product name “Miramer M301”, manufactured by MIWON), (product name “ARONIX M-309”, manufactured by Dong-A Synthesis Co., Ltd.), ditrimethylolpropane tetraacrylate (product name “ARONIX M-408”, Dong-A Synthesis Co., Ltd.), ethoxylated pentaerythritol tetra(meth)acrylate (product name “SR494”, manufactured by Sartomer), dipentaerythritol penta(meth)acrylate (product name “SR399”, manufactured by Sartomer), di Pentaerythritol poly(meth)acrylate (a mixture of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate) ((product name "KAYARAD DPHA", Nippon Kayaku Co., Ltd.) , Ltd.), (Product name 「A-9550」, Shin-Nakamura Chemical Co., Ltd. product), (Product name 「Aronix M-403」, 「Aronix M-400」, 「Aronix M-402」 , "Aronix M-404", "Aronix M-405", "Aronix M-406", manufactured by Dong-A Synthesis Co., Ltd.), tripentaerythritol poly(meth)acrylate (product name "Viscoat #802") ， TriPEA", Osaka Organic Chemical Co., Ltd. product), polyfunctional acrylate containing dendrimer structure (product names "Sirius-501", "SUBARU-501", Osaka Organic Chemical Industry Co., Ltd. product), urethane (meta) ) Acrylates (product names “UV1700B”, “UV7620EA”, “UV7610B”, “UV7600B”, “UV7650B”, manufactured by Mitsubishi Chemical Corporation), (product names “DPHA40H”, “UX5003”, Kaya Japan Co., Ltd. product), (product name 「BEAMSET 577」, product of ARAKAWA CHEMICAL INDUSTRIES, LTD.), (product name 「8UX-015A」, Daise (product name of Taisei Fine Chemical Co., Ltd.), (product name 「U15HA」, product of Shin-Nakamura Chemical Industry Co., Ltd.), (product name 「Miramer PU610」, product of Miwon Specialty Chemical), ( Product name "Etercure 6196-100", product of Eternal Materials), bisphenol A type epoxy acrylate (product name "Aronix OT-2501", manufactured by Dong-A Synthesis Co., Ltd.), etc. are illustrated.

(A) A well-known thing can be used individually or in combination of 2 or more types as the substance illustrated as component and (A) component. (A) component, Preferably they are urethane (meth)acrylate (a1) and/or hydroxyl-containing (meth)acrylate (a2). (a1) Balance of a softness|flexibility and abrasion resistance becomes favorable by using a component. Moreover, (a2) component has high reactivity, and since the hardened|cured material of the active-energy-ray-curable resin composition of this indication becomes high hardness, it is preferable. (a1) component, More preferably, polyisocyanate (a1-1) (in this indication, it is also called "(a1-1) component") and hydroxyl-containing (meth)acrylate (a1-2) (this indication) In the present invention, it is a reaction product with "(a1-2) component"), and more preferably a polyisocyanate containing a chain hydrocarbon group, a polyisocyanate containing an alicyclic hydrocarbon group, a burette of a polyisocyanate containing a chain hydrocarbon group, Biuret of polyisocyanate containing alicyclic hydrocarbon group, nurate of polyisocyanate containing chain hydrocarbon group, nurate of polyisocyanate containing alicyclic hydrocarbon group, adduct of polyisocyanate containing chain hydrocarbon group, alicyclic hydrocarbon group At least one selected from the adduct of polyisocyanate, allophanate of polyisocyanate containing a chain hydrocarbon group, and allophanate of polyisocyanate containing an alicyclic hydrocarbon group, and hydroxyl group-containing (meth)acrylic containing a chain hydrocarbon group It is a reactant with the rate. (a2) component, More preferably, it is a hydroxyl-containing (meth)acrylate containing a chain|strand-shaped hydrocarbon group. (A) Since it becomes excellent in abrasion resistance by providing 2 or more (meth)acryloyl group number, component is preferable.

Content ratio (mass ratio, solid content conversion, [(a1-1) component/() a1-2) The upper limit of component])) is 50/50, 45/55, 40/60, 35/65, 30/70, 29/71, 28/72, 27/73, 26/74, 25/75 , 20/80, and the like, and the lower limit is 45/55, 40/60, 35/65, 30/70, 29/71, 28/72, 27/73, 26/74, 25/75, 20/80 , 15/85, and the like are exemplified. In one embodiment, content ratio (mass ratio, solid content conversion, [(a1-1) component/(a1-2) component]) of (a1-1) component and (a1-2) component is 15/ About 85-50/50 is preferable.

(a1-1) 10, 9, 8, 7, 6, 5, 4, 3 etc. are illustrated as for the upper limit of the number of the isocyanate groups provided in one molecule of component, The lower limit is 9, 8, 7, 6, 5, 4, 3, 2, etc. are exemplified. In one embodiment, as for the number of the isocyanate groups provided in 1 molecule of (a1-1) component, about 2-10 are preferable.

(A) When using in combination of 2 or more types of component, it is considered to contain each type as (A) component in about 80% or less, respectively. For example, when (A) component is used in combination of two types, and the 1st type is called (a1) component and the 2nd type is (a2) component, the content ratio (mass ratio, solid content conversion, [(a1) The upper limit of component / (a2) component]) is 80/20, 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35/ 65, 30/70, 25/75, etc. are exemplified, and the lower limit is 75/25, 70/30, 65/35, 60/40, 55/45, 50/50, 45/55, 40/60, 35 /65, 30/70, 25/75, 20/80 and the like are exemplified. In one embodiment, as for content ratio (mass ratio, solid content conversion, [(a1) component/(a2) component]) of (a1) component and (a2) component, about 20/80-80/20 is preferable Do.

As for the upper limit of the number of (meth)acryloyl groups of the hydroxyl-containing (meth)acrylate used as (a1) component and/or (a2) component, 9, 8, 7, 6, 5, 4, 3, 2 etc. exemplified, and the lower limit is exemplified by 8, 7, 6, 5, 4, 3, 2, 1, and the like. In one embodiment, as for the number of (meth)acryloyl groups of the hydroxyl-containing (meth)acrylate used as (a1) component and/or (a2) component, about 1-9, More preferably, It is about 2-4. By setting it as below the said upper limit, it becomes more excellent in flexibility in a resin layer.

(A) The upper limit of the molecular weight of the component is exemplified by 50,000, 40,000, 30,000, 20,000, 10,000, 5,000, 1,000, 500, 250, 100, and the like, and the lower limit is 40,000, 30,000, 20,000, 10,000, 5,000, 1,000, 500, 250, 100, 50 and the like are exemplified. In one embodiment, as for the molecular weight of (A) component, about 50-50,000 are preferable.

The upper limit of content (solid content conversion) of (A) component which occupies in 100 mass % of all structural units of solid content conversion of (A) component of this indication and (B) component is 99.9, 99.5, 99, 98, 97 , 96, 95, 94, 93, 92, 91, 90, 85, 80, 75% by mass and the like, and the lower limit is 99.5, 99, 98, 97, 96, 95, 94, 93, 92, 91, 90, 85, 80, 75, 70 mass % etc. are illustrated. In one embodiment, content of (A) component (solid content conversion) which occupies in 100 mass % of precursor units of solid content conversion of (A) component of this indication and (B) component (solid content conversion) has the effect of this indication favorably From what is shown, about 70-99.9 mass % is preferable, More preferably, it is 80-99.9 mass %, More preferably, it is 85-99.9 mass %, Especially preferably, it is 90-99.9 mass %.

<Compound (B) having a fluorine atom>

The active-energy-ray-curable resin composition of this indication contains the compound (B) (in this indication, it is also called "(B) component") provided with a fluorine atom. (B) Component may be equipped with a polymerizable unsaturated group other than a fluorine atom. That is, as component (B), the compound etc. which are provided with a fluorine atom and are not provided with a polymerizable unsaturated group, a fluorine atom, and a polymerizable unsaturated group are illustrated. As the polymerizable unsaturated group, a carbon-carbon double bond, a carbon-carbon triple bond, and the like are exemplified. As a polymerizable unsaturated group, a vinyl group, a (meth)acryloyl group, etc. are specifically illustrated. Component (B) is an agent that can be used as an antifouling agent.

(B) You may use a commercially available product as component. As this product, product names "OPTOOL DAC-HP", "OPTOOL DSX-E", "OPTOOL UD120" (DAIKIN INDUSTRIES, LTD.), product names "Megaface" (MEGAFACE)RS75", "Megaface RS76-E", "Megaface RS76-NS", "Megaface RS851", "Megaface RS852", "Megaface RS853", "Megaface RS854" (DIC Corporation) (DIC Corporation), product name "X71-1203M" (Shin-Etsu Chemical Co., Ltd.), product name "SUA1900L10", "SUA1900L6" (Shin-Nakamura Chemical Co., Ltd.) product), product names "FTERGENT 710FL", "FutaGent 710FM", "FutaGent 710FS", "FutaGent 730LM", "FutaGent 610FM", "FutaGent 683", "FutaGent 601AD", " Futagent 601ADH2", "futagent 602A", "futagent 650AC", "futagent 681" (product of NEOS COMPANY LIMITED), etc. are illustrated.

(B) What is known as the substance illustrated as component and (B) component can be used individually or in combination of 2 or more types. (B) A component is a compound provided with a fluorine atom and a polymerizable unsaturated group because abrasion resistance and abrasion resistance are favorable. (B) Since sliding of the hardened|cured material of the active-energy-ray-curable resin composition of this indication will become favorable when component (B) contains silicon further, it is preferable.

(A) The upper limit of content ratio (mass ratio, solid content conversion, [(A) component/(B) component]) of (A) component and (B) component is 99.9/0.1, 99.8/0.2, 99.7/0.3, 99.6/0.4 , 99.5/0.5, 99.4/0.6, 99.3/0.7, 99.2/0.8, 99.1/0.9, 99/1, 98/2, 97/3, 96/4, 95/5, 90/10, etc. are exemplified, and the lower limit Silver, 99.8/0.2, 99.7/0.3, 99.6/0.4, 99.5/0.5, 99.4/0.6, 99.3/0.7, 99.2/0.8, 99.1/0.9, 99/1, 98/2, 97/3, 96/4, 95/5, 90/10, 85/15 and the like are exemplified. In one embodiment, since content ratio (mass ratio, solid content conversion, [(A) component/(B) component]) of (A) component and (B) component shows the effect of this indication favorably, , about 85/15 to 99.9/0.1 is preferable.

The upper limit of content (solid content conversion) of (B) component which occupies in 100 mass % of precursor units of solid content conversion of (A) component of this indication and (B) component is 15, 10, 9, 7, 5, 3, 1, 0.9, 0.7, 0.5, 0.3, 0.1 mass % etc. are illustrated, and a lower limit is 10, 9, 7, 5, 3, 1, 0.9, 0.7, 0.5, 0.3, 0.1, 0.05 mass % etc. are illustrated . In one embodiment, as for content (conversion of solid content) of (B) component which occupies in 100 mass % of precursor units of solid content conversion of (A) component and (B) component of this indication, about 0.05-15 mass % It is preferable, More preferably, it is 0.05-10 mass %, More preferably, it is 0.05-5 mass %, Especially preferably, it is 0.05-3 mass %, Especially preferably, it is 0.05-1 mass %. By setting it as more than the said minimum, the effect as an antifouling agent can fully be exhibited. By carrying out below the said upper limit, compatibility with another component becomes favorable and transparency of a resin layer becomes excellent.

<Antistatic agent (C)>

The active energy ray-curable resin composition of the present disclosure contains an antistatic agent (C) (also referred to as “(C) component” in the present disclosure). Examples of the antistatic agent include an anionic antistatic agent, a cationic antistatic agent, a nonionic antistatic agent, and an antistatic agent using an alkali metal salt.

As anionic antistatic agent, a sulfonic acid type, a sulfuric ester type, phosphorus containing type, etc. are illustrated. Examples of the sulfonic acid type include an alkylsulfonate, an alkylbenzenesulfonate, an alkylnaphthalenesulfonate, and an alkyldiphenylsulfonate. As a sulfuric acid ester type, an alkyl sulfate ester salt, an alkylethoxy sulfate ester salt, etc. are illustrated. Examples of the phosphorus-containing type include alkyl phosphate esters, alkyl phosphites, alkyl phosphonic acids, and alkyl phosphonic acid esters.

Examples of the cationic antistatic agent include aliphatic amine salts, quaternary ammonium salts, and alkylpyridinium salts.

Examples of the quaternary ammonium salt include hydrocarbon group-containing quaternary ammonium salts, nitrogen ring-containing quaternary ammonium salts, and polymers having a quaternary ammonium salt group.

Hydrocarbon group-containing quaternary ammonium salts refer to quaternary ammonium salts which may contain any one of an alkyl group, a benzene ring, and an alicyclic ring. As hydrocarbon group-containing quaternary ammonium salts, trioctylmethylammonium chloride, trioctylethylammonium chloride, tridecylmethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryldimethylbenzyl Ammonium chloride, stearyl dimethyl ammonium chloride, tricapryl methyl ammonium chloride, tetrabutyl ammonium chloride, benzyl trimethyl ammonium chloride, benzyl triethyl ammonium chloride, etc. are illustrated. These bromide, iodide, sulfite, sulfate or hydrogen sulfate may be used.

Examples of the nitrogen ring-containing quaternary ammonium salts include quaternary ammonium salts in which the nitrogen ring comprises a pyridine ring, a picoline ring, a quinoline ring, an imidazoline ring, a morpholine ring, and the like. The nitrogen ring-containing quaternary ammonium salts may have a linear or branched alkyl group. When the nitrogen ring-containing quaternary ammonium salts have a linear or branched alkyl group, the upper limit of the number of carbon atoms in the alkyl group is exemplified by 30, 25, 20, 15, 10, 8, 6, etc., and the lower limit is 25 , 20, 15, 10, 8, 6, 4 and the like are exemplified. In one embodiment, when the nitrogen ring-containing quaternary ammonium salts have a linear or branched alkyl group, the alkyl group preferably has about 4 to 30 carbon atoms. Further, the nitrogen ring-containing quaternary ammonium salts may be bromides, iodides, sulfites, sulfates or hydrogen sulfates thereof.

As a polymer having a quaternary ammonium base, Japanese Unexamined Patent Application, First Publication No. Hei 9-194528, Japanese Unexamined Patent Application Laid-Open No. Hei 11-60614, Japanese Unexamined Patent Application, First Publication No. 2014-167104, Japanese Unexamined Patent Application, First Publication No. 2016-003283 What is shown in is exemplified.

The polymer having a quaternary ammonium salt group includes, for example, a vinyl monomer (c1) having a quaternary ammonium salt structure (in the present disclosure, also referred to as “component (c1)”), hydroxyl group-containing vinyl monomers and lactones. A vinyl monomer (c2) made by cyclic addition and having a weight average molecular weight of 4,000 to 10,000 (also referred to as "component (c2)" in the present disclosure), a branched alkyl ester group having 3 to 5 carbon atoms, and an alicyclic structure A vinyl monomer (c3) that does not contain (in the present disclosure, also referred to as “(c3) component”), and, if necessary, other vinyl monomers (c4) (in the present disclosure, also referred to as “(c4) component”) ) is a copolymer formed by polymerization of a predetermined mass ratio.

(c1) component can be used without a restriction|limiting in particular, if it is a vinyl monomer provided with a quaternary ammonium salt structure in a molecule|numerator. (c1) component, Preferably, Formula (1):CH2 ₌ C( ^R1 )-CO ^- ABN ⁺ ( ^R2 )(R3)( ^R4 )*X ^- (in formula, R< ¹ > is H or CH ₃ , R ² to R ⁴ is an alkyl group having about 1 to 3 carbon atoms, A is O or NH, B is an alkylene group having about 1 to 3 carbon atoms, and X is a counter anionic species) It is a (meth)acrylate compound. As X ⁻ , Cl ⁻ , SO ₄ ² - , SO ₃ ⁻ , C ₂ H ₅ SO ₄ ⁻ , Br ⁻ and the like are exemplified. As for X ^- , Cl ^- is the most preferable from the point of the antistatic ability of (C)component. (c1) As a commercial item of component, product name "LIGHT ESTER DQ-100" Kyoeisha Chemical Co., Ltd. product, product name "DMAEA-Q" KJ Chemicals Co., Ltd. ( Kohjin co., Ltd.) products and the like are exemplified.

The component (c2) is a ring-opening polyaddition reaction of hydroxyl group-containing vinyl monomers and lactones, and can be used without any particular limitation. Moreover, when another long-chain monomer (for example, a vinyl monomer having an alkylene oxide structure at the end of an alkyl group in the molecule, etc.) is used instead of the component (c2), the antistatic ability of the component (C) tends to be insufficient. As said hydroxyl-containing vinyl monomer, hydroxyl-containing (meth)acrylate, a hydroxyl-containing vinyl monomer, etc. are illustrated. Examples of the hydroxyl group-containing (meth)acrylate include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxyethyl (meth)acryloylamide. . Examples of the hydroxyl group-containing vinyl monomer include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, and hydroxydiethylene glycol vinyl ether. The hydroxyl group-containing vinyl monomers are particularly preferably hydroxyl group-containing (meth)acrylates from the viewpoint of radical copolymerizability. Examples of the lactones include β-propiolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone and ε-caprolactone. As for the lactones, ?-caprolactone and/or ?-valerolactone are particularly preferable from the point of reactivity in ring-opening polymerization.

(c2) Various well-known methods are illustrated as a synthesis|combining method of a component. (c2) Specific examples of the method for synthesizing the component include a method in which the lactones are subjected to a ring-opening polyaddition reaction using the hydroxyl group-containing vinyl monomers as an initiator. By appropriately selecting the input ratio of hydroxyl group-containing vinyl monomers and lactones, reaction temperature, and catalyst species and amount, the polyester structure is repeated and the above weight average molecular weight is achieved. In the case of the ring-opening polyaddition reaction, inorganic acids, alkali metals, lithium compounds, tin compounds, metal alkoxides and the like are exemplified as catalysts. As the inorganic acid, sulfuric acid, phosphoric acid, and the like are exemplified. As an alkali metal, lithium, sodium, potassium, etc. are illustrated. Examples of the lithium compound include n-butyllithium and t-butyllithium. Examples of the tin compound include dibutyltin dilaurylate, dibutyltin dioctoate, dibutyltin mercaptide, and tin acrylate. As the metal alkoxide, titanium tetrabutoxide and the like are exemplified. The amount of the catalyst used in the ring-opening polyaddition reaction is usually about 0.01 to 10% by mass based on 100% by mass in total of the hydroxyl group-containing vinyl monomers and lactones. (c2) The upper limit of the weight average molecular weight of the component is 10,000, 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, etc. are exemplified, and the lower limit is 9,500, 9,000, 8,500, 8,000, 7,500, 7,000, 6,500, 6,000, 5,500, 5,000, 4,500, 4,000, and the like are exemplified. In one embodiment, as for the molecular weight of (c2) component, about 4,000-10,000 are preferable. When the weight average molecular weight of the component (c2) is less than 4000, the compatibility between the component (A) and the component (C) becomes insufficient, and the active energy ray-curable resin composition tends to be cloudy or the transparency of the cured product tends to be impaired. (c2) The thing with the weight average molecular weight of a component exceeding 10000 is difficult to synthesize|combine. In the present disclosure, the weight average molecular weight refers to a polystyrene conversion value by gel permeation chromatography.

(c3) Component can be used without a restriction|limiting in particular, as long as it is a vinyl monomer which is equipped with a C3-C5 branched alkylester group and is not equipped with an alicyclic structure. (c3) As a component, isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, isopentyl (meth)acrylate, 2- Methylbutyl (meth)acrylate etc. are illustrated.

(c4) A component is an arbitrary component. (c4) As a component, mono (meth)acrylates and aromatic ring structure vinyl monomers provided with a hydrocarbon group of less than C3 or 6 or more are illustrated. Examples of mono (meth) acrylates having a hydrocarbon group having less than 3 or 6 or more carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, hexyl (meth) acrylate, and ethylhexyl (meth) acrylate. do. As aromatic ring structure vinyl monomers, styrene, (alpha)-methylstyrene, 4-methylstyrene, benzyl (meth)acrylate, phenyl (meth)acrylate, etc. are illustrated.

(C)component is obtained by making radical copolymerization of (c1)component, (c2)component, and (c3)component, and (c4)component by various well-known methods as needed. (C) Reaction temperature at the time of synthesizing component is usually about 40-160 degreeC, and reaction time is about 2-12 hours. Examples of the radical polymerization initiator in the copolymerization reaction include inorganic peroxides, organic peroxides, and azo compounds. As the inorganic peroxide, hydrogen peroxide, ammonium persulfate, potassium persulfate and the like are exemplified. As the organic peroxide, benzoyl peroxide, dicumyl peroxide, lauryl peroxide and the like are exemplified. As the azo compound, 2,2-azobis(isobutyronitrile), 2,2'-azobis(methylbutyronitrile), and the like are exemplified. The usage-amount of the radical polymerization initiator at the time of a copolymerization reaction is about 0.01-10 mass % with respect to the total mass of normally (c1) component - (c4) component. A chain transfer agent may be used during the copolymerization reaction. As the chain transfer agent, lauryl mercaptan, dodecyl mercaptan, 2-mercaptobenzothiazole, bromine trichloromethane and the like are exemplified. The usage-amount of a chain transfer agent is about 0.01-10 mass % with respect to the gross mass of normally (c1) component - (c4) component. When the copolymerization reaction is carried out by solution polymerization, an organic solvent may be used. Examples of the organic solvent include glycol ether solvents, alcohol solvents, ketone solvents, aromatic solvents, ester solvents, haloalkane solvents, and amide solvents. Examples of the glycol ether solvent include ethylene glycol monoethyl ether and propylene glycol monomethyl ether. As an alcohol solvent, methanol, ethanol, n-propanol, etc. are illustrated. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. As an aromatic solvent, benzene, toluene, xylene, etc. are illustrated. As an ester solvent, ethyl acetate, butyl acetate, etc. are illustrated. As a haloalkane solvent, chloroform etc. are illustrated. As an amide solvent, dimethylformamide etc. are illustrated. As an organic solvent, a glycol ether solvent is preferable from the point of the dissolving power of (c1) component - (c4) component.

Although the copolymerization ratio (mass ratio) of (c1) component, (c2) component and (c3) component is not specifically limited, Considering compatibility, antistatic property of a cured film, anti-glare property, etc., it is preferable is 20 to 70:20 to 40:5 to 50, more preferably 40 to 55:20 to 40:10 to 30, still more preferably 45 to 55:25 to 35:10 to 25. Moreover, when adding (c4) component, the copolymerization ratio (mass ratio) of (c1) component, (c2) component, (c3) component, and (c4) component becomes like this. Preferably it is 20-70:20-40:5-50: It is 1-20, More preferably, it is 40-55:20-40:10-30:1-10, More preferably, it is 45-55:25-35:10-25:1-10.

(C) The physical property of component is 0.05 dl/g or more, specifically 0.1 the intrinsic viscosity in 25 degreeC of the propylene glycol monomethyl ether dilution solution (about 1-2 mass %) of (C)component, for example, It is about 1 dl/g. By setting the intrinsic viscosity to 0.05 dl/g or more, component (C) is less likely to bleed out on the surface of the cured product of the active energy ray-curable resin composition, and the antistatic property of the cured product is improved.

Examples of the nonionic antistatic agent include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenol ethers, polyoxyethylene alkylamine amides, and sorbitans.

As an alkali metal of the antistatic agent using an alkali metal salt, lithium, sodium, potassium, etc. are illustrated.

(C) What is known as the substance illustrated as component and (C)component can be used individually or in combination of 2 or more types. (C) component, since transparency of the hardened|cured material of the active-energy-ray-curable resin composition of this indication is favorable and inexpensive, Preferably it is a cationic antistatic agent, More preferably, it is a quaternary ammonium salt, More preferably It is a polymer provided with a quaternary ammonium base.

The upper limit of content ratio (mass ratio, solid content conversion, [(A)component/(C)component]) of (A)component and (C)component is 99/1, 98/2, 97/3, 96/4 , 95/5, 94/6, 93/7, 92/8, 91/9, 90/10, 85/15, and the like, and the lower limit is 98/2, 97/3, 96/4, 95/ 5, 94/6, 93/7, 92/8, 91/9, 90/10, 85/15, 80/20 and the like are exemplified. In one embodiment, since content ratio (mass ratio, solid content conversion, [(A) component/(C)component]) of (A) component and (C)component shows the effect of this indication favorably, , about 80/20 to 99/1 is preferable.

The upper limit of content ratio (mass ratio, solid content conversion, [(B)component/(C)component]) of (B)component and (C)component is 20/80, 15/85, 10/90, 9/91 , 8/92, 7/93, 6/94, 5/95, 4/96, 3/97, 2/98, etc. are exemplified, and the lower limit is 15/85, 10/90, 9/91, 8/ 92, 7/93, 6/94, 5/95, 4/96, 3/97, 2/98, 1/99 and the like are exemplified. In one embodiment, since content ratio (mass ratio, solid content conversion, [(B)component/(C)component]) of (B)component and (C)component shows the effect of this indication favorably, , about 1/99 to 20/80 is preferable.

The upper limit of content (solid content conversion) of (C)component which occupies in 100 mass % of precursor units of solid content conversion of (A)component of this indication, (B)component, and (C)component (solid content conversion) is 30, 25, 20, 15 , 10, 5, 4, 3 mass %, etc. are illustrated, and 25, 20, 15, 10, 5, 4, 3, 2 mass % etc. are illustrated as for a lower limit. In one embodiment, content (solid content conversion) of (C)component which occupies in 100 mass % of precursor units of solid content conversion of (A) component of this indication, (B) component, and (C)component (solid content conversion) is 2- About 30 mass % is preferable, More preferably, it is 2-20 mass %, More preferably, it is 2-15 mass %, Especially preferably, it is 2-10 mass %. By setting it as more than the said minimum, the effect as an antistatic agent can fully be exhibited. By setting it as below the said upper limit, compatibility with another component becomes favorable and it is excellent in transparency of a resin layer.

<Photoinitiator (D)>

It is also considered that the active energy ray-curable resin composition of this indication contains a photoinitiator (D) (in this indication, it is also called "(D)component"). As a photoinitiator, a radical type photoinitiator, a cationic photoinitiator, an anionic photoinitiator, etc. are illustrated.

Examples of the radical type photopolymerization initiator include an alkylphenone type photopolymerization initiator, an acylphosphine oxide type photopolymerization initiator, a hydrogen extraction type photopolymerization initiator, and an oxime ester type photopolymerization initiator.

As the alkylphenone type photoinitiator, benzyl dimethyl ketal such as 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl α-hydroxyalkylphenone such as -propan-1-one, α-aminoalkylphenone such as 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, etc. are illustrated. .

Examples of the acylphosphine oxide type photoinitiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and the like.

As a hydrogen extraction type photoinitiator, phenylglyoxylic acid methyl ester etc. are illustrated.

As an oxime ester type photoinitiator, 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-) methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) and the like are exemplified.

As a cationic photopolymerization initiator, a mixture of iodonium, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate (1-) and propylene carbonate, triarylsulfonium hexafluorophosphate, triarylsulfoniumtetrakis-(pentafluorophenyl)borate and the like are exemplified.

Examples of the anionic photopolymerization initiator include a cobaltamine-based complex, o-nitrobenzyl alcohol carbamic acid ester, and oxime ester.

As the photopolymerization initiator, a commercially available product may be used. As the product, 2,2-dimethoxy-1,2-diphenylethan-1-one (product name “Omnirad (hereinafter also referred to as “Omnirad”) 651”, manufactured by IGM Resins), 1-[4- (2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (product name “Omnirad 2959”, manufactured by IGM Resins), 2-hydroxy-1-{ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (product name "Omnirad 127", manufactured by IGM Resins), 2-methyl -1-(4-methylthiophenyl)-2-morpholinopropan-1-one (product name “Omnirad 907”, manufactured by IGM Resins), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Product name 「Omnirad TPO H」, manufactured by IGM Resins), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (product name 「Omnirad 819, manufactured by IGM Resins), methyl phenylglyoxylate Ester (product name 「Omnirad MBF」, manufactured by IGM Resins), 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)] (product name 「IRGACURE OXE 01」, BASF Japan Co., Ltd. product), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) (product name "IRGACURE") OXE 02", manufactured by BASF Japan Co., Ltd.), iodonium, (4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate (1-) and a mixture of propylene carbonate (product name "Omnicat") (hereinafter also referred to as “Omnicat”) 250”, manufactured by IGM Resins), triarylsulfonium hexafluorophosphate (product name “Omnicat 270”, manufactured by IGM Resins), triarylsulfonium tetrakis-(penta Fluorophenyl) borate (product name "IRGACURE 290", BASF Japan Ltd. product) etc. are illustrated.

Substances exemplified as the photopolymerization initiator and those known as the photopolymerization initiator may be used alone or in combination of two or more. The photopolymerization initiator is preferably a radical photopolymerization initiator, more preferably an alkylphenone type photoinitiator, and still more preferably α-aminoalkylphenone and/or α-hydroxyalkylphenone because of its excellent curing rate. , particularly preferably 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2) -Methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-one at least one selected from propan-1-one.

The upper limit of content (solid content conversion) of component (D) which occupies in 100 mass % of precursor units of solid content conversion of the active energy ray-curable resin composition of this indication (solid content conversion) is 20, 15, 10, 8, 6, 4, 2, 1 , 0.5 mass %, etc. are illustrated, and 15, 10, 8, 6, 4, 2, 1, 0.5, 0.1 mass %, etc. are illustrated as for a lower limit. In one embodiment, as for content (in conversion of solid content) of component (D) which occupies in 100 mass % of precursor units of solid content conversion of the active energy ray-curable resin composition of this indication (solid content conversion), about 0.1-20 mass % is preferable.

<Other compounds that can be combined>

In the active energy ray-curable resin composition of the present disclosure, if necessary, binder resins, non-slip agents, slip agents, preservatives, inorganic particles, rust inhibitors, pH adjusters, pigments, dyes, lubricants other than those exemplified above, Various additives, such as a leveling agent, a catalyst, an antifoamer, and a photosensitizer (amines, quinones, etc.) can also be mix|blended.

In the active energy ray-curable resin composition of the present disclosure, if necessary, a solvent (E) (in the present disclosure, also referred to as “(E) component”) may be blended, and the viscosity may be adjusted and used. As a solvent, water, an organic solvent, etc. are illustrated. Various well-known things may be sufficient as an organic solvent. Examples of the organic solvent include ketone solvents, aromatic solvents, alcohol solvents, glycol solvents, glycol ether solvents, ester solvents, petroleum solvents, haloalkane solvents, and amide solvents.

Examples of the ketone solvent include methyl ethyl ketone, acetyl acetone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone.

As an aromatic solvent, toluene, xylene, etc. are illustrated.

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, butanol and the like.

Examples of the glycol solvent include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol and the like.

As the glycol ether solvent, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol di Ethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoiso Butyl ether, ethylene glycol mono-t-butyl ether, etc. are illustrated.

Examples of the ester solvent include ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

As the petroleum solvent, Solvesso #100 (product of EXXON Corporation), Solvesso #150 (product of Exxon Corporation), and the like are exemplified.

As a haloalkane solvent, chloroform etc. are illustrated.

As an amide solvent, dimethylformamide etc. are illustrated.

Substances exemplified as solvents and known solvents can be used alone or in combination of two or more.

The upper limit of the content ratio of the solvent to the solid content of the active energy ray-curable resin composition of the present disclosure (mass ratio, [active energy ray-curable resin composition/solvent of the present disclosure]) is 99/1, 95/5, 90/10, 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90, 5/95, etc. are exemplified, and the lower limit is 95/5, 90/10 , 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, 20/80, 10/90, 5/95, 1/99, and the like are exemplified. In one embodiment, the content ratio of the solvent to the solid content of the active energy ray-curable resin composition of the present disclosure (mass ratio, [active energy ray-curable resin composition/solvent of the present disclosure]) is about 1/99 to 99/1 desirable. By reducing the amount of the solvent, the thickness of the resin layer of the present disclosure can be increased.

<Method for producing active energy ray-curable resin composition>

The active energy ray-curable resin composition of the present disclosure may be obtained by mixing component (A), component (B), and component (C), component (D) and component (E) as needed at room temperature and normal pressure.

<Laminate>

The present disclosure provides a laminate including a substrate and a resin layer. In addition, in the present disclosure, the present disclosure also provides a method for manufacturing a laminate including a step of curing the active energy ray-curable resin composition of the present disclosure applied to at least one side of the substrate with active energy rays. The cured product thus obtained is also referred to as a resin layer in the present disclosure.

As the substrate to which the active energy ray-curable resin composition of the present disclosure is applied, a glass substrate, a metal substrate, a plastic substrate, and the like are exemplified. As the plastic substrate, a thermoplastic plastic substrate, a thermosetting plastic substrate, and the like are exemplified. As the thermoplastic plastic substrate, a general-purpose plastic substrate, an engineering plastic substrate, and the like are exemplified. As the general-purpose plastic substrate, olefin-based, polyester-based, acrylic-based, vinyl-based, polystyrene-based and the like are exemplified. As an olefin type, polyethylene, polypropylene, norbornene, etc. are illustrated. As a polyester type, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc. are illustrated. As an acrylic type, polymethyl methacrylate (PMMA) etc. are illustrated. As a vinyl type, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, etc. are illustrated. Examples of the polystyrene-based resin include polystyrene (PS) resin, styrene/acrylonitrile (AS) resin, and styrene/butadiene/acrylonitrile (ABS) resin. As the engineering plastic substrate, general-purpose infrastructure, super-enfrastructure, and the like are exemplified. As general-purpose equipment, polycarbonate, polyamide (nylon), etc. are exemplified. Polyether ether ketone (PEEK) etc. are illustrated as super enpra. Examples of the thermosetting plastic substrate include polyimide, epoxy resin, and melamine resin. As another plastic base material, triacetyl cellulose resin etc. are illustrated. The plastic substrate may be a copolymer of a plurality of plastics described above. The substrate of the present disclosure may be a multilayer including a plurality of the above-described substrates. In addition, the base material may be surface-treated (corona discharge, etc.). In addition, on one side or both sides of the substrate, between the layer on which the active energy ray-curable resin composition of the present disclosure is formed, other layers (for example, an easily adhesive layer, an anchor layer, etc.) formed may be sufficient. Since the base material is excellent in transparency, dimensional stability, mechanical properties, chemical resistance, etc., Preferably it is a polyester type, More preferably, it is a polyethylene terephthalate film. Since the base material is excellent in heat resistance, dimensional stability, mechanical properties, and the like, it is preferably polyimide. The upper limit of the thickness of the substrate is exemplified by 300, 275, 250, 225, 200, 175, 150, 125, 100, 75, 50, 25, 10 μm, and the lower limit is 275, 250, 225, 200, 175, 150, 125, 100, 75, 50, 25, 10, 1 μm and the like are exemplified. In one embodiment, the thickness of the substrate is preferably 1 to 300 μm, more preferably 25 to 250 μm, still more preferably 50 to 200 μm, particularly preferably 50 to 150 μm, particularly more Preferably it is 75-125 micrometers.

As a method of applying the active energy ray-curable resin composition of the present disclosure on a substrate, roll coater application, reverse roll coater application, bar coater application, Mayer bar application, air knife application, gravure application, reverse gravure application, offset printing, Flexo printing, screen printing, and the like are exemplified. Moreover, although the application amount is not specifically limited, Usually, it is the range from which the mass after drying becomes 0.01-20 g/m< ² >, Preferably it is 0.025-10 g/m< ² >, More preferably, it is 0.05-5 g/m< ² >. As for the upper limit of the thickness of the resin layer, 50, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05 micrometer etc. are illustrated, and a lower limit is, 45, 40, 35, 30, 25, 20, 15, 10, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01 μm and the like are exemplified. The thickness of the resin layer is preferably 0.01 to 50 µm, more preferably 0.05 to 25 µm, still more preferably 0.1 to 10 µm, particularly preferably 0.5 to 10 µm, even more preferably 1 to 5 µm. am.

As a method of curing by irradiation with active energy rays, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp or an LED that emits light in a wavelength range of 150 nm to 450 nm The method of irradiating about ¹⁰ mK/cm2 or ^more and 10,000 mK/cm2 or less using a etc. is illustrated. Before irradiation with an active energy ray, you may heat and dry it as needed. After irradiation with an active energy ray, if necessary, it may be heated and completely hardened. As the heating conditions, about 30 seconds to 30 minutes are exemplified at about 60 to 150°C, and preferably about 50 seconds to 10 minutes at 70 to 130°C is considered.

It is considered that the active energy ray-curable resin composition of the present disclosure is used as in the following (1) to (12). Although it is preferable to use the active energy ray-curable resin composition of the present disclosure, that is, as a hard coating layer, it is also contemplated for use in various applications that can exhibit the effects achieved by the active energy ray-curable resin composition of the present disclosure.

(1) Cured product of the active energy ray-curable resin composition of the present disclosure, substrate

(2) Cured product of the active energy ray-curable resin composition of the present disclosure, a primer layer, and a substrate

(3) the cured product of the active energy ray-curable resin composition of the present disclosure, the substrate, and the pressure-sensitive adhesive layer

(4) Cured product of the active energy ray-curable resin composition of the present disclosure, a primer layer, a base material, and an adhesive layer

(5) Antifouling layer, cured product of active energy ray-curable resin composition of the present disclosure, substrate

(6) Antifouling layer, cured product of the active energy ray-curable resin composition of the present disclosure, primer layer, and substrate

(7) antifouling layer, cured product of the active energy ray-curable resin composition of the present disclosure, substrate, and pressure-sensitive adhesive layer

(8) antifouling layer, cured product of the active energy ray-curable resin composition of the present disclosure, primer layer, substrate, and pressure-sensitive adhesive layer

(9) a low-refractive-index layer, a high-refractive-index layer, a cured product of the active energy ray-curable resin composition of the present disclosure, a substrate;

(10) a low refractive index layer, a high refractive index layer, a cured product of the active energy ray-curable resin composition of the present disclosure, a substrate, and an adhesive layer

(11) a low refractive index layer, a high refractive index layer, a cured product of the active energy ray-curable resin composition of the present disclosure, a primer layer, and a substrate

(12) a low refractive index layer, a high refractive index layer, a cured product of the active energy ray-curable resin composition of the present disclosure, a primer layer, a base material, and an adhesive layer

The resin layer of the laminate of the present disclosure satisfies Conditions 1 and 2.

Condition 1 is that the indentation hardness (N/mm<2>) of the resin layer of a laminated body is 450 or more and 600 or less. The press-fitting hardness (N/mm 2 ) of the resin layer of the laminate is a numerical value corresponding to the strain of the resin layer of the laminate. The upper limit of the indentation hardness (N/mm2) of the resin layer of the laminate is exemplified by 600, 575, 550, 525, 500, 475, and the like, and the lower limit is exemplified by 575, 550, 525, 500, 475, 450, etc. do. In one embodiment, the indentation hardness (N/mm<2>) of the resin layer of a laminated body becomes like this. Preferably it is 450-600. Since the rigidity of a laminated body can be maintained appropriately by using below the said upper limit, it becomes possible to obtain a flexible laminated body. By setting it as more than the said minimum, a laminated body can be equipped with hard-coat property. That is, it is important to be within the above range in order to make a constant flexible performance and a constant hard coating performance compatible.

Condition 2 is that the breaking elongation of the resin layer of the laminate is 3.7% or more and 10.0% or less. The breaking elongation of the resin layer of the laminate is a numerical value corresponding to the strain of the resin layer. The upper limit of the elongation at break (%) of the resin layer of the laminate is exemplified by 10.0, 9.0, 8.0, 7.0, 6.0, 5.0, 4.0, 3.9, 3.8, and the like, and the lower limit is 9.0, 8.0, 7.0, 6.0, 5.0 , 4.0, 3.9, 3.8, 3.7 and the like are exemplified. In one embodiment, the breaking elongation (%) of the resin layer of a laminated body becomes like this. Preferably it is 3.7-10.0. By using below the said upper limit, it becomes possible to suppress that the resin layer of a laminated body becomes soft too much, and to maintain hard-coat property. By setting it as more than the said minimum, the resin layer of a laminated body can be equipped with flexibility. That is, it is important to be within the above range in order to make a constant flexible performance and a constant hard coating performance compatible. The elongation at break of condition 2 refers to the ratio of the length (cm) elongated from the length (cm) of the laminate at 0% when the state before stretching the laminate is 0%. Specifically, using a commercially available tensile tester such as Tensilon universal tester (product name "RTG-1250", manufactured by A&D Company, Limited), the sample was tested at a speed of 10 mm/min at room temperature. It is stretched in the longitudinal direction and calculated from the following formula using the length when cracks are seen in the sample and the length of the sample before tensioning.

Elongation at break (%) = 100 × (L-Lo)/Lo

Lo: the length of the sample before tensioning

L: the length of the sample when cracks begin to appear

[Example]

Specific examples of the present disclosure will be described below with reference to Examples, but the present disclosure is not limited to these examples. In addition, in the Examples, all parts and % are based on solid content unless otherwise specified.

(c2) The weight average molecular weight of the component is an actual value measured under the following conditions using a commercially available molecular weight measuring instrument below.

Molecular weight measuring instrument: Product name 「HLC-8220GPC」, manufactured by Tosoh Corporation

Column: Product name 「TSKGel G6000PWXL-CP」, 「TSKGel G3000PWXL-CP」, all manufactured by Tosoh Corporation

Developing solvent: 0.1M NaNO ₃ and 0.1M acetic acid solution

Flow rate: 0.5mL/min

Sample concentration: 0.5g/L

<Synthesis Example 1-1: Synthesis of (meth)acrylate (A-1)>

310 parts of isophorone diisocyanate (also referred to as "IPDI" in this disclosure), pentaerythritol tri/tetraacrylate (product name "Aronix") in a 300 mL 4-neck flask equipped with a stirrer, thermometer, cooler and dry gas inlet tube M305", manufactured by Dong-A Synthesis Co., Ltd.) (in the present disclosure, also referred to as "PETA") and 690 parts of tin octylate were added, and then the temperature in the system was raised to about 80°C over about 1 hour. Then, at the same temperature, after maintaining the reaction system for 2 hours, it cooled and obtained the urethane acrylate (A-1).

<Synthesis Examples 1-2 to 1-5 and Comparative Synthesis Examples 1-1 to 1-3: Poly(meth)acrylates (A-2) to (A-5) and poly(meth)acrylates (A-C1) ) to (A-C3) synthesis>

Synthesis Examples 1-2 to 1-5 and Comparative Synthesis Examples 1-1 to 1-3 were made in the same manner as in Synthesis Example 1-1, except that the composition described in Table 1 was changed (meta ) acrylates (A-2) to (A-5) and (meth)acrylates (A-C1) to (A-C3) were obtained.

The meanings of terms in Table 1 are as follows.

IPDI: isophorone diisocyanate (product of Tokyo Chemical Industry Co., Ltd.)

HDInu: Nurate of hexamethylene diisocyanate (product name "Coronate HXR", manufactured by Tosoh Corporation)

HDIad: Adduct of hexamethylene diisocyanate (product name "Coronate HL", manufactured by Tosoh Corporation)

HDIbi: burette of hexamethylene diisocyanate (product name "Desmodule N3200", manufactured by Covestro AG)

HDI: Hexamethylene diisocyanate (product name "Coronate HDI", manufactured by Tosoh Corporation)

PETA: pentaerythritol tri/tetraacrylate (product name 「Aronix M305」, manufactured by Dong-A Synthesis)

HEA: hydroxyethyl acrylate (product of Osaka Organic Chemical Co., Ltd.)

DPPA: dipentaerythritol penta/hexaacrylate (product name 「Aronix M400」, manufactured by Dong-A Synthesis)

<Synthesis Example 2-1: Synthesis of antistatic agent (C-1)>

130 parts of hydroxyethyl methacrylate, 1140 parts of ε-caprolactone, and 1.3 parts of tin octylate were added to a reactor equipped with a stirring device and a cooling tube, heated to 150° C., kept warm for 6 hours, and then cooled , a monofunctional vinyl monomer containing a polyester structure having a weight average molecular weight of 5500 (hereinafter also referred to as “component (c2-1)”) was obtained. 100 parts of methacryloyloxyethyl trimethylammonium chloride (DMC) (hereinafter also referred to as "(c1-1)" component) and 60 parts of (c2-1) component to a reactor equipped with a stirring device and a cooling tube 40 parts and 800 parts of propylene glycol monomethyl ether (PGME) were added to part, isopropyl methacrylate (henceforth "(c3-1) component"), and it heated up to 90 degreeC. Then, 8 parts of 2,2'-azobis(methylbutyronitrile) (AMBN) and 32 parts of PGME were added to initiate a polymerization reaction, kept at 100° C. for 6 hours, and then cooled, and a polymer containing a quaternary ammonium salt structure ( A solution of C-1) (non-volatile content 20%) was obtained.

<Example 1: Preparation of active energy ray-curable resin composition (1)>

50 parts of urethane acrylate (A-1), 50 parts of PETA, and 1-[4-(2-hydroxyl) as a photopolymerization initiator in a 300 mL 4-neck flask equipped with a stirrer, thermometer, cooler and dry gas inlet tube. Ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (product name "Omnirad 2959", manufactured by IGM Resins) as a compound having 5 parts, a fluorine atom and a polymerizable unsaturated group (B) component (product name "Megaface RS-90") was mix|blended in 0.5 part solid content ratio, it diluted with PGME, and the active energy ray hardening type resin composition (1) of 30% of non-volatile matter was prepared.

<Examples 2-5: Preparation of active energy ray-curable resin compositions (2) to (5)>

Examples 2 to 5 were carried out in the same manner as in Example 1, except that the composition shown in Table 2 was changed to obtain active energy ray-curable resin compositions (2) to (5).

<Example 6: Preparation of active energy ray-curable resin composition (6)>

50 parts of urethane acrylate (A-1), 50 parts of PETA, and 1-[4-(2-hydroxyl) as a photopolymerization initiator in a 300 mL 4-neck flask equipped with a stirrer, thermometer, cooler and dry gas inlet tube. 5 parts of ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (product name "Omnirad 2959", manufactured by IGM Resins), as an antistatic agent, a polymer containing a quaternary ammonium salt structure (C -1) is a compound having 5 parts, a fluorine atom and a polymerizable unsaturated group, and (B) component (product name "MEGAFACE RS-90") is blended in a solid content ratio of 0.5 parts, diluted with PGME, and nonvolatile matter A 30% active energy ray-curable resin composition (6) was prepared.

<Examples 7 to 10 and Comparative Examples 1 to 10: Preparation of active energy ray-curable resin compositions (7) to (10) and (C1) to (C10)>

Examples 7 to 10 and Comparative Examples 1 to 10 were carried out in the same manner as in Example 6, except that the composition shown in Tables 2 and 3 was changed, and active energy ray-curable resin compositions (7) to (10) and (C1) to (C10) were obtained.

<Evaluation Example 1: Preparation of the laminate 1>

On a PET film with a film thickness of 100 µm (COSMOSHINE A4100 manufactured by TOYOBO CO., LTD.), the active energy ray-curable resin composition (1) was applied, and the cured film had a film thickness of 3 µm. It was coated with a bar coater #10 so as to become Next, the obtained film was cured using an ultraviolet curing device (product name: UBT-080-7A/BM, Multiply CO., LTD product, high pressure mercury lamp 300 mJ/cm ² ), and the laminate (1) was got it

<Evaluation Examples 2 to 10 and Comparative Evaluation Examples 1 to 10: Preparation of laminates (2) to (10) and (C1) to (C10)>

In Evaluation Examples 2 to 10 and Comparative Evaluation Examples 1 to 10, the active energy ray-curable resin composition (1) was changed to the active energy ray-curable resin composition (2) to (10) or (C1) to (C10), respectively. Except for that, the same method as in Evaluation Example 1 was carried out to obtain laminates (2) to (10) and (C1) to (C10).

<Performance evaluation (1): Indentation hardness (N/㎟)>

An indenter was pressed against the surface of the resin layer of the laminate, and the indentation hardness was calculated from the obtained load displacement curve. As the indenter tip correction method, the Tanaka method was applied. As for the load removal fitting method, a tangent line was obtained by approximating a straight line from 65% to 100% of the upper part.

Measuring device: ENT-2100, ultra-micro indentation hardness tester manufactured by ELIONIX INC.

Indenter: Triangular pyramid indenter Berkovich

Maximum load: 1.0mN

Load increase rate: 1.0 mN/10 sec

Holding time under maximum load: 5 seconds

Load removal speed: 1.0 mN/10 sec

Temperature of measurement environment: 30℃

Humidity of measurement environment: 50%

<Performance evaluation (2): Elongation at break>

The elongation at break was evaluated for the sample in which the laminate was cut out into a rectangular shape of 1 cm in length and 10 cm in width.

Measuring device: Tensilon universal testing machine (product name 「RTG-1250」, manufactured by A&D Co., Ltd.)

Tensile speed: 10mm/min

Load cell: 100N

Number of tests: 5

Distance between chucks: 50mm

Temperature of measurement environment: 23℃

Humidity of measurement environment: 50%

<Performance evaluation (3): Steel wool test>

About the resin layer surface of a laminated body, based on JISK7136:2000, the haze value was measured using the color haze meter. After that, for the surface of the resin layer of the laminate, #0000 steel wool (product name "BONSTAR B-204", Nippon Steel Wool Co., Ltd.) ) using a 500 g/cm ² load, a speed of 100 mm/sec, and a moving distance of 30 mm, after reciprocating and rubbing 500 times, again in accordance with JIS K7136:2000, the haze value was measured using a color haze meter. The difference in haze value before and after rubbing with steel wool was evaluated according to the following criteria.

AAA: less than 0.15

AA: More than 0.15 and less than 0.20

A: More than 0.20 and less than 0.30

B: more than 0.30

<Performance evaluation (4): mandrel test>

Conforms to the mandrel test described in JIS-K5600-5-1 (test that winds a sample on a stainless steel cylinder with diameters 2, 3, 4, 5, 6, 8, 10, 12, 16, 20, 25, 32 mm) Thus, when the laminate was wound around a stainless steel column so that the resin layer was on the outside, the minimum diameter of the column in which cracks (cracks) did not occur in the resin layer was measured and evaluated according to the following criteria.

AA: Minimum diameter 4mm or less

A: The minimum diameter is 5mm

B: Minimum diameter 6mm or more

<Performance evaluation (5): abrasion resistance test>

Using an eraser (product name 「military rubber stick」, manufactured by Minoan) as the head of the friction tester, press it vertically from above with a load of 1000 g on the surface of the resin layer of the laminate. After reciprocating and rubbing, after removing the attached eraser, the water contact angle was measured and evaluated according to the following reference|standard. In addition, the method of measuring the water contact angle is as follows. 2.0 μL of water droplets were dropped on the part rubbed with an eraser in the resin layer of the laminate, and a contact angle measuring device (product name “Drop Master DM-300”, Kyowa Interface Science Co., Ltd) product) was used, and the water contact angle at a temperature of 23°C and a relative humidity of 50% was measured by a droplet method measuring 1000 ms after droplet dropping by the θ/2 method.

AAA: Water contact angle greater than 106°

AA: Water contact angle greater than 104° and less than or equal to 106°

A: The contact angle of water is greater than 103° and less than or equal to 104°

B: The contact angle of water is 103° or less

The meanings of terms in Tables 2 and 3 are as follows.

ATM-4E:EO-modified pentaerythritol tetra(meth)acrylate (product name "NK Ester ATM-4E", manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

DPCA-30: caprolactone-modified dipentaerythritol hexa (meth) acrylate (product name "KAYARAD DPCA-30", manufactured by Nippon Kayaku Co., Ltd.)

DPH-12E: ethoxylated dipentaerythritol hexaacrylate (product name "A-DPH-12E", manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

Photoinitiator: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (product name "Omnirad 2959", manufactured by IGM Resins)

Claims (7)

As an active energy ray-curable resin composition constituting a resin layer in a laminate including a base material and a resin layer,
(meth)acrylate (A) and
Compound (B) having a fluorine atom
including,
An active energy ray-curable resin composition satisfying the following conditions 1 and 2.
Condition 1: The indentation hardness (N/mm 2 ) of the resin layer is 450 or more and 600 or less.
Condition 2: Elongation at break of the resin layer is 3.7% or more and 10.0% or less.
According to claim 1,
(A) Active energy ray-curable resin composition in which component contains urethane (meth)acrylate (a1) and/or hydroxyl-containing (meth)acrylate (a2).
3. The method of claim 2,
(a1) component is a reaction product of polyisocyanate (a1-1) and hydroxyl-containing (meth)acrylate (a1-2), mass ratio of (a1-1) component and (a1-2) component ((a1-1) An active energy ray-curable resin composition in which /(a1-2)) is 15/85 to 50/50.
4. The method according to any one of claims 1 to 3,
(B) The active energy ray-curable resin composition whose component is a compound provided with a fluorine atom and a polymerizable unsaturated group.
5. The method according to any one of claims 1 to 4,
An active energy ray-curable resin composition comprising an antistatic agent (C).
6. The method according to any one of claims 1 to 5,
(C) The active energy ray hardening-type resin composition whose component is a polymer provided with a quaternary ammonium base group.
A laminate comprising a substrate and a resin layer, wherein the resin layer is a cured product of the active energy ray-curable resin composition according to any one of claims 1 to 6.