JP2017155143A - Active energy ray-curable composition and cured article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of being readily cured by active energy ray such as UV ray, and a cured article having excellent moistureproofness, substrate adhesiveness and flexibility.SOLUTION: An active energy ray-curable composition includes 5 to 40% by mass of the following (A) component, 50 to 85% by mass of the following (B) component, 0.1 to 10% by mass of the following (C) component, and 3 to 30% by mass of the following (D) component. The (A) component: a compound that has at least one structural unit of a structural unit derived from hydrogenated polybutadiene polyol and a structural unit derived from hydrogenated isoprene polyol and at least one group of an acryloyl group and a methacryloyl group, (B) component: a compound that has at least one group of the acryloyl group and the methacryloyl group and has neither a structural unit derived from the hydrogenated polybutadiene polyol nor a structural unit derived from hydrogenated isoprene polyol, (C) component: a photopolymerization initiator, and (D) component: a layered material.SELECTED DRAWING: None

Description

  The present invention relates to an active energy ray-curable composition and a cured product thereof.

  Various package structures are known for electronic devices and their circuits. These structures are generally composed of a base material, a cover, an organic part such as a light emitting diode disposed between the base material and the cover, and a sealing material for bonding the base material and the cover together. One or both of the substrate and the cover can be made of a transparent material, such as glass or plastic, and can transmit light. One of the substrate and the cover may be made of steel or aluminum. The organic component is easily deteriorated by oxygen or water vapor. For example, an organic electroluminescent device consists of an anode, a light emitting layer, and a cathode, and a low work function metal layer is used as the cathode to ensure efficient electron injection and low operating voltage, but this metal layer contains oxygen. When the metal layer chemically reacts with oxygen or the like, the lifetime of the device is shortened. Therefore, the organic component is covered with a coating film composed of an inorganic barrier film or a laminated barrier film in which an inorganic layer and an organic layer are laminated to protect the surface and the periphery of the organic component. In recent years, with increasing flexibility, it is important that these coating films not only prevent permeation of oxygen and water vapor, but also have excellent flexibility and adhesion.

  From the viewpoint of moisture-proof insulation, Patent Document 1 includes (A) acryloxy polybutadiene or acryloxy hydrogenated polybutadiene, (B) bisphenol A-based (meth) acrylate, and (C) long-chain aliphatic acrylate such as lauryl acrylate. The composition is shown. Since this composition contains a component having an aromatic ring, there is a concern of coloring. Patent Document 1 mentions adhesion to glass but does not mention flexibility.

  As measures for improving both moisture resistance and flexibility, Patent Document 2 discloses (A) a polybutadiene polymer having a (meth) acryloyl group at the terminal, (B) a (meth) acrylate monomer, (C) a photopolymerization initiator, D) A resin composition for encapsulating an electronic device comprising a hydrocarbon having a number average molecular weight of less than 50,000 is shown. Component (D) has the effect of imparting flexibility as a plastic component in addition to imparting water vapor barrier properties, but is a non-crosslinked component that is not incorporated into the curing system, and therefore bleeds during long-term use. There is concern. For this reason, when this resin composition is used for a flexible image display apparatus, there is a question about long-term reliability, and it is considered that the balance of blending is difficult.

  A technique based on the detour theory is widely known as one technique for imparting high barrier properties to the coating film. The bypass theory is a theory that by dispersing filler in the matrix component, moisture and gas pass through the filler gap, that is, bypass and pass through the filler, so that the permeation amount per unit time becomes small. .

  Methods for imparting high barrier properties using fillers are described in Patent Document 3 and Patent Document 4. Patent Document 3 discloses a resin composition containing 0.1 to 20 parts by mass of a layered silicate modified with a surfactant with respect to 100 parts by mass of a binder component. However, since the binder component is thermoplastic, a heating furnace or a special coating apparatus is required to use this resin composition. Patent Document 4 discloses a composition serving as a barrier material against moisture and oxygen in which 20 to 100 parts by mass of a plate silicate is dispersed in a stacking manner with respect to 100 parts by mass of a binder component. However, Patent Document 4 does not have a technical description for arranging plate-like silicates in a stacking manner, and the resin composition has a large amount of plate-like silicate, so that adhesion to the base material is increased. It is difficult to apply to flexible substrates.

Japanese Patent No. 5012235 Japanese Patent No. 5778304 JP 2003-105200 A JP2013-028722A

  Therefore, the present invention solves the above-mentioned problems of the prior art, a composition that can be easily cured with active energy rays such as ultraviolet rays, and excellent moisture resistance, substrate adhesion and flexibility. It is an object of the present invention to provide a cured product having the following.

As a result of intensive studies to solve the problems of the above-described conventional technology,
(A) a compound having at least one structural unit of a structural unit derived from a hydrogenated polybutadiene polyol and a structural unit derived from a hydrogenated isoprene polyol, and having at least one of an acryloyl group and a methacryloyl group; B) Compound having at least one of acryloyl group and methacryloyl group and having no structural unit derived from hydrogenated polybutadiene polyol and no structural unit derived from hydrogenated isoprene polyol, (C) photopolymerization initiation The present inventors have found that the above problems can be solved by using an agent and (D) a layered substance, and have completed the present invention.

The aspect of this invention for solving the said subject is the following [1]-[9].
[1] 5-40 mass% of following (A) component, 50-85 mass% of (B) component, 0.1-10 mass% of (C) component, and 3-30 mass% of (D) component are included. An active energy ray-curable composition.
Component (A): a compound having at least one structural unit of a structural unit derived from a hydrogenated polybutadiene polyol and a structural unit derived from a hydrogenated isoprene polyol, and having at least one of an acryloyl group and a methacryloyl group Component (B): Compound (C) which has at least one of acryloyl group and methacryloyl group and does not have a structural unit derived from hydrogenated polybutadiene polyol and a structural unit derived from hydrogenated isoprene polyol : Photopolymerization initiator (D) component: Layered material

[2] The active energy ray-curable composition according to [1], wherein the component (A) contains at least one selected from the following (a-1) and (a-2).
(A-1) Reaction product of hydrogenated polybutadiene polyol or hydrogenated isoprene polyol and an acryloyl group-containing isocyanate compound and / or methacryloyl group-containing isocyanate compound (a-2) Hydrogenated polybutadiene polyol or hydrogenated isoprene polyol; Reaction product obtained by transesterification with lower alkyl ester of acrylic acid and / or lower alkyl ester of methacrylic acid

[3] The component (B) contains at least one of an acryloyl group-containing compound having a cycloaliphatic group and a methacryloyl group-containing compound having a cycloaliphatic group, [1] or [2] Active energy ray-curable composition.
[4] The active energy ray-curable composition according to any one of [1] to [3], wherein the component (D) is a clay mineral having a crystal structure.
[5] The active energy ray-curable composition according to [4], wherein the clay mineral having a crystal structure is a swellable silicate.
[6] The active energy ray-curable composition according to [5], wherein the swellable silicate is smectite clay and / or swellable mica.
[7] The active energy ray according to any one of [1] to [3], wherein the component (D) is an ion exchange reaction product of a swellable silicate and an organic quaternary amine compound. A curable composition.
[8] The active energy ray curing according to [7], wherein the organic quaternary amine compound is N, N-dimethyl-N-benzyl-N- [2- (acryloyloxy) ethyl] ammonium chloride. Mold composition.
[9] A cured product obtained by curing the active energy ray-curable composition according to any one of [1] to [8].

  The active energy ray-curable composition of the present invention can be easily mounted only by irradiating active energy rays, and the cured product has high moisture resistance, flexibility and adhesion.

  Below, (A)-(D) component which concerns on one Embodiment of this invention is demonstrated in detail. The “(meth) acryloyl group” in the present invention is a general term for an acryloyl group and a methacryloyl group, and means one or both of an acryloyl group and a methacryloyl group. The “(meth) acryloyl group-containing compound” is a general term for an acryloyl group-containing compound and a methacryloyl group-containing compound, and means one or both of an acryloyl group and a methacryloyl group. The “(meth) acrylate compound” is a general term for an acrylate compound and a methacrylate compound, and means one or both of an acryloyl group and a methacryloyl group. The same applies to compounds having “(meth)” in the compound name. Examples of active energy rays include ultraviolet rays, visible rays, infrared rays, electron beams, α rays, γ rays, and X rays.

1. Component (A) The component (A) has at least one of a structural unit derived from a hydrogenated polybutadiene polyol and a structural unit derived from a hydrogenated isoprene polyol, and at least one of an acryloyl group and a methacryloyl group. It is a compound which has these groups. The “hydrogenated polybutadiene polyol” of the present invention is a polyol obtained by hydrogenating a polybutadiene polyol. The “hydrogenated polyisoprene polyol” of the present invention is a polyol obtained by hydrogenating and reducing polyisoprene polyol.

  The component (A) is usually produced using hydrogenated polybutadiene polyol or hydrogenated polyisoprene polyol as a raw material. These hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol preferably have 2 or more hydroxyl groups and 2 to 4 hydroxyl groups in one molecule. The hydroxyl value of these hydrogenated polybutadiene polyol and hydrogenated polyisoprene polyol is preferably 10 to 80 mgKOH / g, more preferably 17 to 70 mgKOH / g, and particularly preferably 23 to 65 mgKOH / g. When the component (A) is produced using a hydrogenated polybutadiene polyol or a hydrogenated polyisoprene polyol having a hydroxyl value in the range of 10 to 80 mgKOH / g, the volume shrinkage during polymerization of the component (A) does not become too large. The cohesive force of the polymer of component (A) does not become too high, and the composition has good viscosity, so that it can maintain good handling properties and can be handled easily.

  Examples of commercially available hydrogenated polybutadiene polyol or hydrogenated polyisoprene diol include NISSO-PB GI-1000, GI-2000, GI-3000 (manufactured by Nippon Soda Co., Ltd.), KRASOL HLBH-P 2000, KRASOL HLBH-P 3000. (Clay Valley (USA), LLC), Epaul (made by Idemitsu Kosan Co., Ltd.) and the like.

  Examples of component (A) include hydrogenated polybutadiene polyol or hydrogenated isoprene polyol, a reaction product of a polyisocyanate compound and a (meth) acryloyl group-containing compound having an alcoholic hydroxyl group, hydrogenated polybutadiene polyol or hydrogenated isoprene. Reaction product by addition reaction of polyol, (meth) acryloyl group-containing compound having isocyanato group, and polyisocyanate compound used as necessary, hydrogenated polybutadiene polyol or hydrogenated isoprene polyol, and lower alkyl acrylate The reaction product etc. which are obtained by transesterification with ester and / or the lower alkyl ester of methacrylic acid can be mentioned. Here, lower alkyl means alkyl having 1 to 5 carbon atoms.

The polyisocyanate compound is a compound having two or more isocyanato groups in one molecule.
Specific examples of the polyisocyanate compound include, for example, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl). ) Biuret of cyclohexane, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, isophorone diisocyanate, Hexamethylene diisocyanate biuret, isophorone diisocyanate isocyanurate, hexamethylene diisocyanate isocyanurate, lysine triisocyanate, Examples include lysine diisocyanate, hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate, and norbornane diisocyanate. These polyisocyanate compounds may be used alone or in combination of two or more.

  In order to maintain high moisture resistance of the cured product obtained from this composition, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanate) are used as the polyisocyanate compound. Natomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, diphenylmethane-4,4′-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 2,4,4-trimethylhexa Methylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate and norbornane diisocyanate are preferred, and methylene bis (4-cyclohexylisocyanate) and norbornane diisocyanate are further preferred. Preferred.

  The (meth) acryloyl group-containing compound having an alcoholic hydroxyl group is not particularly limited as long as it is a compound having an alcoholic hydroxyl group and a (meth) acryloyl group in one molecule, and specifically, 2-hydroxyethyl. Examples include acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and 2-hydroxyethyl acrylamide. In consideration of the reactivity with the isocyanato group, the polymerizability of the product and the moisture resistance of the product, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate and 2-hydroxyethyl acrylamide are preferable, and 2-hydroxyethyl acrylate, 4- More preferred is hydroxybutyl acrylate.

The (meth) acryloyl group-containing compound having an isocyanato group is not particularly limited as long as it is a compound having a (meth) acryloyl group and an isocyanato group in the same molecule. Specifically, 1,1- (bisacryloyl Examples include oxymethyl) ethyl isocyanate, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 2- [2- (methacryloyloxy) ethoxy] ethyl isocyanate, and the like. Among these, considering the reactivity with the alcoholic hydroxyl group and the polymerizability of the reaction product, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate are 2-isocyanatoethyl methacrylate and 2-isocyanatoethyl acrylate are more preferable.
The lower alkyl means alkyl having 1 to 5 carbon atoms, preferably alkyl having 1 to 3 carbon atoms.

  A preferred example of the component (A) is a reaction product of a hydrogenated polybutadiene polyol or hydrogenated isoprene polyol and an acryloyl group-containing isocyanate compound and / or a methacryloyl group-containing isocyanate compound (hereinafter referred to as “component (a-1)”). And a reaction product obtained by a transesterification reaction between a hydrogenated polybutadiene polyol or hydrogenated isoprene polyol and a lower alkyl ester of acrylic acid and / or a lower alkyl ester of methacrylic acid (hereinafter referred to as “component (a-2)”). ”.). Since reaction products such as the component (a-1) and the component (a-2) generally generate substances having a wide variety of structures, it is difficult to express them with characteristics and structures. .

  As a typical example of component (a-1), the structural formula of the reaction product of hydrogenated polybutadiene diol and 2-((meth) acryloyloxy) ethyl isocyanate is represented by formula (1), hydrogenated polyisoprene diol and The structural formula of the reaction product with 2-((meth) acryloyloxy) ethyl isocyanate is shown in Formula (2).

（式（１）中、２つのＲ⁵は、それぞれ独立にＨ又はＣＨ₃を表し、ｘ、ｙ、ｚは１以上の整数を表す。）

(In formula (1), two R ^{5 s} each independently represent H or CH ₃ , and x, y, and z each represent an integer of 1 or more.)

（式（２）中、２つのＲ⁶は、それぞれ独立にＨ又はＣＨ₃を表し、ｄ、ｅ、ｆは１以上の整数を表す。）

(In formula (2), two R ^{6 s} each independently represent H or CH ₃ , and d, e, and f each represent an integer of 1 or more.)

  A method for producing a reaction product using a hydrogenated polybutadiene polyol and an acryloyl group-containing isocyanate compound and / or a methacryloyl group-containing isocyanate compound as essential raw material components is used in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate. An example is a method of synthesizing by reacting a hydrogenated polybutadiene polyol with an acryloyl group-containing isocyanate compound and / or a methacryloyl group-containing isocyanate compound in the presence.

  Although there is no particular restriction on the order in which the raw materials are charged in this reaction, usually, the hydrogenated polybutadiene polyol is charged first, and then, if necessary, a polymerization inhibitor is added to the range of 30 to 120 ° C. Then, the acryloyl group-containing isocyanate compound and / or the methacryloyl group-containing isocyanate compound are added dropwise or in portions, and reacted.

  The feed molar ratio of the raw material is adjusted according to the molecular weight of the target compound, but the total number of isocyanate groups in the acryloyl group-containing isocyanate compound and / or methacryloyl group-containing isocyanate compound relative to the number of hydroxyl groups in the hydrogenated polybutadiene polyol. The ratio is preferably in the range of the number of isocyanate groups / number of hydroxyl groups = 0.9 to 1.1.

  As a typical example of the component (a-2), a structural formula of a (meth) acrylate compound produced by a transesterification reaction between a hydrogenated polybutadiene diol and a lower alkyl ester of acrylic acid and / or a lower alkyl ester of methacrylic acid is represented by the formula ( 3) shows the structural formula of the (meth) acrylate compound produced by the transesterification reaction between the hydrogenated polyisoprene diol and the lower alkyl ester of acrylic acid and / or the lower alkyl ester of methacrylic acid.

（式（３）中、２つのＲ⁷は、それぞれ独立にＨ又はＣＨ₃を表し、ｌ、ｍ、ｎは１以上の整数を表す。）

(In formula (3), two R ^{7 s} each independently represent H or CH ₃ , and l, m, and n each represent an integer of 1 or more.)

（式（４）中、２つのＲ⁸は、それぞれ独立にＨ又はＣＨ₃を表し、ａ、ｂ、ｃは１以上の整数を表す。）

(In formula (4), two R ^{8 s} each independently represent H or CH ₃ , and a, b, and c each represent an integer of 1 or more.)

  When the (meth) acrylate compound of the component (A) is produced by transesterification of a hydrogenated polyolefin polyol and a lower alkyl ester of acrylic acid and / or a lower alkyl ester of methacrylic acid, generally, A method of conducting a transesterification reaction by heating an acrylic acid lower alkyl ester and / or a methacrylic acid lower alkyl ester in the presence of a transesterification catalyst, and distilling off the generated lower alkyl alcohol, For example, it can be produced by the method described in JP2011-192853A or JP2006-45284A.

  The content of the component (A) in the active energy ray-curable composition of the present invention is preferably 5 to 40% by mass and more preferably 10 to 30% by mass with respect to the total amount of the composition.

  When the content of the component (A) in the present invention is 5 to 40% by mass relative to the total amount of the composition, the coating strength of the cured product obtained by curing the active energy ray-curable composition of the present invention. The cured product can be imparted with flexibility, and the curability of the composition is not impaired, so that the cured product is not sticky and moisture resistance can be imparted.

2. Component (B) Component (B) has at least one of an acryloyl group and a methacryloyl group, and does not have a structural unit derived from a hydrogenated polybutadiene polyol and a structural unit derived from a hydrogenated isoprene polyol. A compound.

  Component (B) is a compound having only one (meth) acryloyl group (that is, a monofunctional (meth) acryloyl group-containing compound) or a compound having a plurality (that is, polyfunctional (meth) acryloyl group-containing). Compound).

  A compound having only one (meth) acryloyl group (that is, a monofunctional (meth) acryloyl group-containing compound) means a compound having only one acryloyl group or methacryloyl group. A compound having a plurality of (meth) acryloyl groups (that is, a polyfunctional (meth) acryloyl group-containing compound) means a compound having a total of two or more acryloyl groups and methacryloyl groups.

  Specific examples of the component (B) having only one (meth) acryloyl group include (meth) acryloyl-containing compounds having a cyclic ether group such as glycidyl acrylate, tetrahydrofurfuryl acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, and the like. , Cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, norbornyl acrylate, N-acryloyloxyethyl hexahydrophthalimide, cyclohexyl methacrylate , Isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate A monofunctional (meth) acryloyl group-containing compound having a cyclic aliphatic group such as dicyclopentanyl methacrylate, dicyclopentanyl ethyl methacrylate, norbornyl methacrylate, N-methacryloyloxyethyl hexahydrophthalimide, 4-tert-butyl Cyclohexyl acrylate, lauryl acrylate, cetyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate, isoamyl acrylate, 4-tert-butylcyclohexyl methacrylate, lauryl methacrylate, cetyl methacrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate Tert-butyl methacrylate, isooctyl methacrylate, Monofunctional (meth) acryloyl group-containing compound having a chain aliphatic group such as amyl methacrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxy-3 And monofunctional (meth) acryloyl group-containing compounds having an aromatic ring such as -phenoxypropyl methacrylate, N-acryloyloxyethylphthalimide, and N-methacryloyloxyethylphthalimide.

  Among these monofunctional (meth) acryloyl group-containing compounds, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyloxyethyl acrylate, Norbornyl acrylate, N-acryloyloxyethylhexahydrophthalimide, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyl ethyl methacrylate, norbornyl Has a cyclic aliphatic group such as methacrylate and N-methacryloyloxyethylhexahydrophthalimide A functional (meth) acryloyl group-containing compounds, more preferred, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl oxyethyl acrylate.

  Examples of the polyfunctional (meth) acryloyl group-containing compound as component (B) are polyfunctional (meth) having a cyclic aliphatic group such as tricyclodecane dimethanol diacrylate and tricyclodecane dimethanol dimethacrylate. Acryloyl group-containing compound, 2,2-bis [4- (acryloyloxyethoxy) phenyl] propane, 2,2-bis [[4- (acryloyloxypoly (ethoxy)] phenyl] propane, 2,2-bis [4 -(Acryloyloxyethoxy) phenyl] methane, 2,2-bis [[4- (acryloyloxypoly (ethoxy)] phenyl] methane, 2,2-bis [4- (methacryloyloxyethoxy) phenyl] propane, 2, 2-bis [[4- (methacryloyloxypoly (ethoxy)] phenyl] propane, 2,2-bis [4- (methacryloyl) Oxyethoxy) phenyl] methane, 2,2-bis [[4- (methacryloyloxypoly (ethoxy)] phenyl] methane and other polyfunctional (meth) acryloyl group-containing compounds such as 1,9-nonamethylenedi Acrylate, 1,10-decamethylene diacrylate, 2-methyl-1.8-octylene diacrylate, 1,6-hexamethylene diacrylate, 3-methyl-1,5-pentylene diacrylate, 2,4-diethyl- Examples thereof include polymonofunctional (meth) acryloyl group-containing compounds having a chain aliphatic group such as 1,5-pentylene diacrylate.

  Among these polymonofunctional (meth) acryloyl group-containing compounds, polyfunctional (meth) acryloyl groups having a cyclic aliphatic group such as tricyclodecane dimethanol diacrylate and tricyclodecane dimethanol dimethacrylate are preferred. Containing compounds, and 2,2-bis [4- (acryloyloxyethoxy) phenyl] propane, 2,2-bis [[4- (acryloyloxypoly (ethoxy)] phenyl] propane, 2,2-bis [4- (Acryloyloxyethoxy) phenyl] methane, 2,2-bis [[4- (acryloyloxypoly (ethoxy)] phenyl] methane, 2,2-bis [4- (methacryloyloxyethoxy) phenyl] propane, 2,2 -Bis [[4- (methacryloyloxypoly (ethoxy)] phenyl] propane, 2,2-bis [4- (methacryloyl Ruoxyethoxy) phenyl] methane, 2,2-bis [[4- (methacryloyloxypoly (ethoxy)] phenyl] methane and other polyfunctional (meth) acryloyl group-containing compounds, and more preferred , Tricyclodecane dimethanol diacrylate, 2,2-bis [4- (acryloyloxyethoxy) phenyl] propane, 2,2-bis [[4- (acryloyloxypoly (ethoxy)] phenyl] propane, 2, 2-bis [4- (acryloyloxyethoxy) phenyl] methane and 2,2-bis [[4- (acryloyloxypoly (ethoxy)] phenyl] methane.

  The component (B) contained in the active energy ray-curable composition of the present invention preferably contains at least one of an acryloyl group-containing compound having a cycloaliphatic group and a methacryloyl group-containing compound having a cycloaliphatic group. Furthermore, the total amount of the acryloyl group-containing compound having a cycloaliphatic group and the methacryloyl group-containing compound having a cycloaliphatic group is preferably 50% by mass or more, and 70% by mass or more based on the total amount of the component (B). It is particularly preferred. (B) Compatibility of (B) component and (A) component improves by including at least one of the acryloyl group containing compound which has a cycloaliphatic group, and the methacryloyl group containing compound which has a cycloaliphatic group. Tend.

  Moreover, it is preferable that content of (B) component of the active energy ray hardening-type composition of this invention is the range of 50-85 mass% with respect to the total amount of a composition, More preferably, it is 50-80 mass. %, Particularly preferably 50 to 75% by mass. When the component (B) is included in the range of 50 to 85% by mass with respect to the total amount of the active energy ray-curable composition of the present invention, the viscosity of the active energy ray-curable composition does not become too high, and A good balance can be achieved between the curability of the composition and the substrate adhesion of the cured product of the present invention described later, which is preferable.

3. Component (C) The photopolymerization initiator as component (C) can include compounds that generate radicals upon irradiation with active energy rays. Examples include acetophenone photopolymerization initiators and acylphosphine oxides. Photopolymerization initiator, oxime photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, thioxanthone photopolymerization initiator, sulfide photopolymerization initiator, azo photopolymerization initiator or peroxide And a photopolymerization initiator.

  As the acetophenone photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 2-hydroxy-1- (4-isopropenylphenyl) -2-methylpropan-1-one oligomer, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone 2-methyl-1- [4- (methylthio) phenyl]- - morpholino propane -1, and the like.

Examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Examples of oxime photopolymerization initiators include 1,2-octadione, 1- [4- (phenylthio)-, 2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Methylbenzoyl) -9-carbazol-3-yl]-, 1- (o-acetyloxime) and the like.

  Examples of the benzoin photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

  Benzophenone photopolymerization initiators include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 2,4,6-trimethylbenzophenone, 3, 3'-dimethyl-4-methoxybenzophenone.

  Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and the like.

Examples of the sulfide photopolymerization initiator include diphenyl disulfide, dibenzyl disulfide, and tetramethylammonium monosulfide.
Examples of the azo photopolymerization initiator include azobisisobutyronitrile, 2,2′-azobispropane, hydrazine, and the like.
Examples of the peroxide photopolymerization initiator include benzoyl peroxide and di-t-butyl peroxide.

  The photopolymerization initiator (C) is preferably an acetophenone photopolymerization initiator or an acylphosphine oxide photopolymerization initiator from the viewpoint of solubility in the obtained active energy ray-curable composition. Among them, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, 2, 4,6-trimethylbenzoyl-diphenylphosphine oxide is particularly preferred. Moreover, ESACURE KTO46 which is a photoinitiator composition in which 2,4,6-trimethylbenzoyldiphenylphosphine oxide is blended can also be suitably used. These (C) photoinitiators are used individually or in combination of 2 or more types.

  (C) Content of a photoinitiator is 0.1-10 with respect to the total amount of an active energy ray curable composition from the point of the balance of the intensity | strength of an active energy ray curable composition, a softness | flexibility, and adhesiveness. It is preferable that it is mass%, and it is more preferable that it is 0.2-7 mass%. (C) If content of a photoinitiator is 0.1 mass% or more, the sclerosis | hardenability of a composition is enough, and if it is 10 mass% or less, high moisture-proof property of hardened | cured material can be maintained.

4). (D) Layered material The active energy ray-curable composition of the present invention contains a layered material in order to further improve moisture resistance. Here, a layered substance is a substance formed by laminating multiple layers with van der Waals forces, and surfaces with densely arranged atoms, such as graphite and mica, have a slightly weaker bonding force. It is a substance having a crystal structure such that they are bonded together and arranged in parallel. One aspect of the layered substance has a layered crystal structure, and by ion exchange or the like, guests such as atoms, molecules and ions that are not originally included in the structure of the crystal can enter a specific part in the crystal, Thereby, the crystal structure does not change. The position where the guest in the layered material enters, that is, the host position, is between the planar layers. Typical examples of such layered materials include clay minerals having a layered crystal structure, layered carbon such as graphite, and chalcogenides of transition metals. Each of these substances develops unique properties by incorporating metal atoms, inorganic molecules, organic molecules, and the like as guests into the crystal. The layered material of the above embodiment is characterized in that the distance between the layers can be flexibly supported by the size of the guest and the interaction between the guest and the host layer. A compound obtained by including a guest in a layered substance as a host is called an intercalation compound, and there are a wide variety of intercalation compounds depending on the combination of a host and a guest. Interlayer compounds are also an embodiment of layered materials. Unlike the guest adsorbed on the surface, the guests between the layers are in a unique environment constrained from two directions by the host layer. Therefore, it is considered that the characteristics of the intercalation compound not only depend on the structures and properties of the host and guest, but also reflect the host-guest interaction.

  Examples of the clay mineral having a layered crystal structure include smectite group clay, which is a swellable silicate, and swellable mica. Specific examples of the smectite group clay include, for example, montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, soconite, stevensite, bentonite, and the like, and substitutions and derivatives thereof, and mixtures thereof. Examples of the swellable mica include lithium-type teniolite, sodium-type teniolite, lithium-type tetrasilicon mica, and sodium-type tetrasilicon mica, and substitutions and derivatives thereof, and mixtures thereof. Some of the above-mentioned swellable mica have a structure similar to percurites, and such percurites and the like can also be used.

  When the layered substance is spherical or scaly, the average particle diameter of the primary particles of the layered substance is preferably 0.01 μm or more and 30 μm or less. When the average particle size of the primary particles is less than 0.01 μm, the cohesive force is strong, so that not only is the dispersion difficult, but also the particle size is too small to prevent water permeation. When the average particle diameter of the primary particles exceeds 30 μm, the cured product obtained by curing the active energy ray-curable composition is brittle and its mechanical strength may be insufficient. The primary particles mean the smallest unit particles constituting the powder. A primary particle is a term used in contrast to a secondary particle or the like in which primary particles are aggregated. The average particle size is obtained by weighing 50 mg of sample, adding it to 50 mL of distilled water, and adding 0.2 ml of 2% Triton (trade name of a surfactant manufactured by GE Healthcare Biosciences), and an output of 150 W. After being dispersed for 3 minutes by an ultrasonic homogenizer, a cumulative mass of 50% by mass obtained by measurement with a user diffraction particle size distribution meter, for example, a laser diffraction light scattering particle size distribution meter (trademark: Microtrac MT3300, manufactured by Nikkiso) Is the diameter.

  Usually, the host layer of the layered material has exchangeable cations. The exchangeable cation is an ion such as sodium or calcium on the surface of the layered crystal. Since these ions have ion exchange properties with a cationic substance, various substances having a cationic property can be inserted as a guest between layers of a layered crystal to form an interlayer compound which is a layered substance. When a cationic substance is intercalated between the layers of the host layer and the layers are sufficiently nonpolarized, the bonding force between the layers of the layered crystal becomes small, so that it can be more finely dispersed.

  Examples of the cationic substance include quaternary ammonium salts and quaternary phosphonium salts. Among them, an organic quaternary ammonium salt having a carbon chain is preferably used because it can sufficiently depolarize the layers of the layered crystal. Examples of the quaternary ammonium salt include lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, and dipolyoxyethylene alkyl. Examples include methylammonium salt, polyoxypropylene methyldiethylammonium salt, dimethylaminopropylpropylacrylamide methyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt and the like. Examples of the quaternary phosphonium salt include dodecyltriphenylphosphonium salt, methyltriphenylphosphonium salt, lauryltrimethylphosphonium salt, stearyltrimethylphosphonium salt, trioctylphosphonium salt, distearyldimethylphosphonium salt, distearylbenzylphosphonium salt, and the like. . Among these, N, N-dimethyl-N-benzyl-N- [2- (acryloyloxy) ethyl] ammonium chloride not only has a large effect of depolarizing the layers of the layered crystal, but also has an acryloyl group. The components (A), (B), and (D) can be chemically bonded by photocuring, and the mechanical strength of the cured product of the active energy ray-curable composition can be maintained at a high level. Representative examples of commercially available intercalation compounds that are ion exchange reaction products of layered materials and quaternary ammonium salts include organic bentonite “Esven E”, “Esven NX”, “Esven NZ”, and “Esven NX80” manufactured by Hojun Co., Ltd. “Esben N270” “Organite” “Organite D” “Organite T” “Lucentite SPN” can be mentioned.

  The component (D) is preferably an ion exchange reaction product of a swellable silicate and an organic quaternary amine compound, but an ion exchange reaction product of a swellable silicate and an organic quaternary amine compound is Because it includes a wide variety of structures, it is difficult to define the structure and characteristics of the structure itself.

  Even the composition obtained by removing the (D) layered substance from the active energy ray-curable composition of the present invention exhibits moisture resistance, but in order to further improve the moisture resistance, (D) an interlayer substance is included. The active energy ray-curable composition is required from the viewpoint of maintaining the balance of strength, flexibility and adhesion of the cured product of the active energy ray-curable composition and maintaining high moisture resistance and flexibility. It is preferable that it is 3-30 mass% with respect to the total amount of, and it is more preferable that it is 4-20 mass%.

5. Other Components In order to give the cured product of the present invention higher adhesion to various substrates, the composition of the present invention may contain a phosphate ester-containing acrylate compound. When the phosphate ester-containing acrylate is contained, the content thereof is preferably 0.2 to 10% by mass, and 0.5 to 5% by mass with respect to the total amount of the active energy ray-curable composition. Is more preferable. If the phosphate ester-containing acrylate compound is 0.2 to 10% by mass, the cured product of the present invention can easily be provided with adhesiveness as expected for various substrates, and the curability of the composition can be maintained. The possibility that the cured product is sticky is low.

Various additives may be added to the active energy ray-curable composition of the present invention in order to impart viscosity, operability, cured product characteristics, and the like according to the application.
For example, in order to increase the sensitivity of reactivity of the active energy ray-curable composition, an allyl ester compound and a polyfunctional thiol compound are added, and these thiol reactions are used to impart curability in the presence of oxygen. Can do.

  A compound having a gas trapping function may be added to promote a barrier effect against water vapor or gas. Examples of such additives include inorganic compounds such as silica gels, calcium silicate, zeolite, calcium carbonate, activated carbon and the like.

  A volatile solvent may be added for the purpose of improving the operability during application of the active energy ray-curable composition, the adhesion of various substrates, and the like. Examples of the volatile solvent include alcohols, ketones, esters and the like. Specific examples of volatile solvents include methanol, ethanol, toluene, cyclohexane, isophorone, cellosolve acetate, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, xylene, ethylbenzene, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, isoamyl acetate , Ethyl lactate, methyl ethyl ketone, acetone, cyclohexanone and the like. These solvents may be used alone or in combination of two or more. However, from the viewpoint of environmental load, the curable composition is preferably solvent-free, and the active energy ray-curable composition of the present invention can be solvent-free.

  Furthermore, the active energy ray-curable composition of the present invention includes a polymerization inhibitor, a modifier, an antifoaming agent, a fluorescent brightening agent, a surfactant, a plasticizer, a flame retardant, and an antioxidant depending on the purpose. UV absorbers, foaming agents, fungicides, antistatic agents, magnetic materials, conductive materials, antibacterial / sterilizing materials, porous adsorbents, fragrances, coloring agents, and the like may be added.

  Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol, and the like. The content of the polymerization inhibitor can usually be 0.01 to 5 parts by mass with respect to 100 parts by mass of the active energy ray-curable composition. If content of a polymerization inhibitor is the range of 0.01-5 mass parts, it will be easy to balance the storage stability and polymerizability of an active energy ray hardening-type composition.

  Examples of the modifier include a leveling agent for improving leveling properties. As the leveling agent, for example, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, etc. can be used. . These may be used alone or in combination of two or more. Content of a leveling agent can be 0.01-10 mass parts normally with respect to 100 mass parts of active energy ray hardening-type compositions. If the content of the leveling agent is 0.01 to 10 parts by mass, it is preferable because the effect of adding the leveling agent can be exhibited and the surface tack and mechanical strength are not deteriorated.

  The antifoaming agent is not particularly limited as long as it has an action of eliminating or suppressing bubbles generated or remaining when the active energy ray-curable composition of the present invention is applied. Examples of the antifoaming agent include known antifoaming agents such as silicone oil, fluorine-containing compounds, polycarboxylic acid compounds, polybutadiene compounds, and acetylenic diol compounds. Specific examples thereof include, for example, BYK-077 (manufactured by Big Chemie Japan), SN deformer 470 (manufactured by San Nopco), TSA750S (manufactured by Momentive Performance Materials LLC), silicone oil SH-203 (Toray Dow). Corning Corp.) and other silicone antifoam agents, Dappo SN-348 (San Nopco), Dappo SN-354 (San Nopco), Dappo SN-368 (San Nopco), Disparon 230HF (Enomoto Kasei) Acrylic polymer antifoaming agent such as Surfynol DF-110D (manufactured by Nisshin Chemical Industry Co., Ltd.), acetylenic diol type antifoaming agent such as Surfynol DF-37 (Nisshin Chemical Industry Co., Ltd.), FA-630, etc. Fluorine-containing silicone-based antifoaming agents can be mentioned. These may be used alone or in combination of two or more. The content of the antifoaming agent can be usually 0.001 to 5 parts by mass with respect to 100 parts by mass of the active energy ray-curable composition. If the content of the antifoaming agent is 0.01 to 5 parts by mass, the effect of adding the antifoaming agent can be exhibited and the surface tack and mechanical properties are not deteriorated, which is preferable.

  Examples of the colorant include known inorganic pigments, organic pigments, organic dyes, and the like, and each is blended according to a desired color tone. These may be used alone or in combination of two or more. Usually, content of these coloring agents is 0.01-50 mass parts with respect to 100 mass parts of active energy ray hardening-type compositions.

6). Method for preparing active energy ray curable composition The method for preparing the active energy ray curable composition of the present invention comprises (A) component, (B) component, (C) component and (D) component, and if necessary. The method is not particularly limited as long as it can mix and disperse other components used. Examples of the method of mixing and dispersing include the following methods.
(A) Each component is charged into a glass beaker, can, plastic cup, aluminum cup or the like and kneaded with a stirring rod, a spatula or the like.
(B) Each component is kneaded with a double helical ribbon blade, a gate blade, or the like.
(C) Kneading each component with a planetary mixer.
(D) Each component is kneaded by a bead mill.
(E) Each component is kneaded with three rolls.
(F) Each component is kneaded by an extruder-type kneading extruder.
(G) Each component is kneaded by a rotating or revolving mixer.

7). Processing method of curable composition The application | coating or coating method in the case of apply | coating the active energy ray hardening-type composition of this invention on a base material, for example, and forming a coating film is not specifically limited. For example, in addition to spray method and dip method, natural coater, curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater, curtain coater, kiss roll, squeeze roll, reverse roll, air blade, knife belt coater, floating knife , A method using a knife over roll, a knife on blanket or the like.

  A cured product can be obtained by curing the active energy ray-curable composition of the present invention. For example, a sheet material made of a cured product can be obtained by processing the active energy ray-curable composition of the present invention into a sheet and curing it. This sheet | seat material may contain other components other than the composition of this invention as needed.

  Examples of the active energy rays used for curing include ultraviolet rays, visible rays, infrared rays, electron beams, α rays, γ rays, X rays, and the like, and ultraviolet rays are preferable because an apparatus serving as a light source is inexpensive.

  The light source for curing the active energy ray-curable composition is not particularly limited, and specific examples include black light, UV-LED lamp, high pressure mercury lamp, pressurized mercury lamp, metal halide lamp, xenon lamp, electrodeless discharge. A lamp. Of these light sources, black light and LED lamps (UV-LED lamps) are preferable because they are safe and economical.

  Here, the black light means that a near-ultraviolet phosphor is applied to a special outer tube glass cut from radiation of visible light and ultraviolet light having a wavelength of 300 nm or less, and a wavelength of 300 nm to 430 nm (wavelength peak is around 350 nm). It is a lamp that only emits near ultraviolet rays. The UV-LED lamp is a lamp using a light emitting diode that emits ultraviolet rays.

The irradiation amount of the active energy ray may be an amount sufficient to cure the active energy ray curable composition, depending on the composition, amount, thickness, shape of the cured product to be formed, etc. To select. For example, if the ultraviolet rays are irradiated to cure the thin film of the active energy ray-curable composition formed by a coating method may be a 200 mJ / cm ² or more 5000 mJ / cm ² or less of the exposure amount, more preferably from 1000 mJ / cm ² or more 3000 mJ / cm ² or less of the exposure amount.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited at all by these examples.
<Evaluation of moisture resistance>
Each of the active energy ray-curable compositions according to Examples and Comparative Examples was applied onto a glass plate subjected to a release treatment with a Baker type applicator so as to have a thickness of 80 μm. The obtained coating film was exposed at a cumulative exposure of ² J / cm ² using a high-pressure mercury lamp with an illuminance of 100 mW / cm ² to cure the coating film, and a test sheet was produced. The moisture permeability of the obtained test sheet was measured using a cup method moisture measuring device. The measurement method was in accordance with JIS Z 0208, and the measurement conditions were 40 ° C. and 90% RH. The moisture resistance was judged to be better as the moisture permeability was lower.

<Evaluation of curability>
Each of the active energy ray-curable compositions according to Examples and Comparative Examples was subjected to an easy-adhesion-treated PET film (manufactured by Panac Co., Ltd., trade name: Cosmo Shine 4100 film thickness 120 μm) with a baker-type applicator so as to have a thickness of 80 μm. It apply | coated to the surface which carried out the easy adhesion process. The obtained coating film was exposed at a cumulative exposure of ² J / cm ² using a high-pressure mercury lamp with an illuminance of 100 mW / cm ² to cure the coating film, and a test sheet was prepared. The obtained test sheet was subjected to a finger tack test, and the curability was evaluated in three stages according to the following evaluation criteria.
A (Excellent): Tackiness was not felt.
B (Average): Tackiness was slightly felt.
C (Poor): An uncured component adhered to the finger.

<Evaluation of flexibility>
Test sheets for active energy ray-curable compositions according to Examples and Comparative Examples were obtained in the same manner as in the evaluation of curability. The obtained test sheet was subjected to a bending resistance test according to JIS K 5600 using a 7 mm diameter mandrel. Flexibility was evaluated in three stages according to the following evaluation criteria.
A (Excellent): The test sheet could be bent, no peeling or cracking from the PET was observed, and no discoloration such as whitening was observed.
B (Average): The test sheet could be bent, and peeling and cracking from the PET were not observed, but discoloration such as whitening was observed.
C (Poor): The sample was not bent or peeled or cracked.

<Evaluation of adhesion>
Each of the active energy ray-curable compositions according to Examples and Comparative Examples was subjected to an easy-adhesion-treated PET film (manufactured by Panac Co., Ltd., trade name: Cosmo Shine 4100 film thickness 120 μm) with a baker type applicator so as to have a thickness of 80 μm. It apply | coated to the surface which carried out the easy adhesion process. To the obtained coating film, another easy-adhesion-treated PET film was bonded so that the surface subjected to the easy-adhesion treatment was in contact with the coating film, and the coating film was integrated using a high-pressure mercury lamp with an illuminance of 100 mW / cm ^2. The coating was cured by exposure at ² J / cm ² to prepare a test sheet. Adhesiveness was evaluated in three stages according to the following evaluation criteria, with the force required to peel the two easy-adhesion-treated PET films of the obtained test sheet from each other as adhesiveness.
A (Excellent): The adhesion was strong, the PET films were not peeled off, and the PET film was damaged.
B (Average): Although resistance was felt when the PET films were peeled apart, they could be peeled off.
C (Poor): When the PET films were peeled apart, no resistance was felt and the PET films could be peeled off.

(Synthesis Example 1)
A 300 mL separable flask equipped with a condenser, a dropping funnel, a thermometer and a stirrer was charged with 180 g of hydroxyl-terminated hydrogenated polybutadiene (hydroxyl value 47.1 mg KOH / g, manufactured by Nippon Soda Co., Ltd., trade name: NISSO = PB GI-2000) and Dioctyltin dilaurate (20 mg) was added, and the internal temperature was raised to 50 ° C. using an oil bath. Thereafter, 22.86 g of 2-isocyanate ethyl acrylate (manufactured by Showa Denko KK, trade name: Karenz AOI (registered trademark)) was dropped over 15 minutes from the dropping funnel. During the dropwise addition, the internal temperature was not allowed to exceed 70 ° C. After completion of the dropwise addition, the internal temperature was maintained at 70 ± 2 ° C. and stirring was continued. When no absorption of C═O stretching vibration of the isocyanato group was observed in the infrared absorption spectrum, stirring was stopped and the reaction was terminated. A hydrogenated polybutadiene urethane acrylate having a number average molecular weight of 2610 (hereinafter referred to as hydrogenated butadiene skeleton acrylate) was obtained.

(Synthesis Example 2)
In a 300 mL separable flask equipped with a condenser, dropping funnel, thermometer and stirrer, hydroxyl-terminated hydrogenated polyisoprene (hydroxyl value 45 mg KOH / g, Idemitsu Kosan Co., Ltd., trade name: Epol)) 222 g, methyl acrylate 59.4 g , 61.0 g of n-hexane, 0.0703 g of hydroquinone monomethyl ether and 0.0410 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine-n-oxyl were charged. While passing the obtained mixture through a calcium chloride tube, air was blown into the mixture, and reflux dehydration was performed at 75 to 80 ° C. After confirming that the water content contained in this mixture was 200 ppm by mass or less with a Karl Fischer moisture meter, 4.4 g of tetra-n-butyl titanate was added as a transesterification catalyst and produced. Methanol was allowed to react at a reaction temperature of 80 to 85 ° C. for 10 hours with stirring while distilling out of the reaction system under reflux of n-hexane as the azeotropic solvent. After completion of the reaction, it was confirmed by high performance liquid chromatography that the conversion rate of hydroxyl-terminated hydrogenated polyisoprene in the reaction mixture was 99% or more, and then transferred to an eggplant flask and methyl acrylate using a rotary evaporator. And it concentrated at the pressure reduction degree 70-2 kPa until 95% or more of n-hexane distilled off, and the hydrogenated polyisoprene acrylate (henceforth hydrogenated isoprene frame | skeleton acrylate) whose number average molecular weight is 2640 was obtained.

The conversion rate was determined by the following operation. After diluting 0.1 g of the reaction mixture with 20 mL of n-hexane, 0.3 g of p-nitrobenzoyl chloride and 0.5 g of pyridine were added to the resulting diluted solution, and reacted at 50 ° C. for 10 minutes in a sealed state. 10 g of water was added and stirred. After standing, the supernatant is analyzed by liquid chromatography (hereinafter referred to as LC),
formula:
[Conversion rate] (%) = [1− (alcohol LC area at the end of reaction ÷ alcohol LC area at the start of reaction) × (sample mass at the start of reaction ÷ sample mass at the end of reaction)] × 100
Based on the above, the conversion rate was obtained.

(Production Example 1)
20 g of swellable synthetic mica (product name: Somashifu ME-100, manufactured by Katakura Corp. Aguri Co., Ltd.) was dispersed in 900 g of ion-exchanged water and sufficiently swollen for 2 days. Next, 120 g of a 10% aqueous solution of N, N-dimethyl-N-benzyl-N- [2- (acryloyloxy) ethyl] ammonium chloride was added to this dispersion while stirring, and the mixture was stirred at 80 ° C. for 1 hour. Thereafter, the heating was stopped and the mixture was further stirred for 12 hours. This solution is transferred to a centrifuge tube and centrifuged (10,000 rotations, 20 minutes). After removing the supernatant, 10 times the amount of ion-exchanged water is added to the volume of the precipitate and stirred. The operation of centrifuging again and removing the supernatant was repeated 4 times to remove excess N, N-dimethyl-N-benzyl-N- [2- (acryloyloxy) ethyl] ammonium chloride. Thereafter, the precipitate was dried using a freeze dryer until the water content was less than 2%, whereby a layered material 1 was obtained. Thus, the average particle diameter of the primary particles of the layered substance 1 produced by ion exchange of the swellable synthetic mica was 6 μm.

Example 1
As component (A), 20 g of hydrogenated butadiene skeleton acrylate obtained in Synthesis Example 1, and as component (B), tricyclodecane dimethylol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., (trade name) Light Acrylate DCP-A) 68 g, ( The active energy ray curing is carried out by finely dispersing 5 g of 5 minutes for 5 minutes at 10,000,000 revolutions by using a homogenizer with 2 g of ESACURE KTO46 as component C) and 10 g of layered material 1 obtained in Production Example 1 as component (D). Mold composition A-1 was obtained. The active energy ray-curable composition A-1 was evaluated for the moisture resistance, curability, flexibility and adhesion, and the results are shown in Table 1.

Example 2
(A) Active energy ray hardening-type composition A-2 was obtained like Example 1 except having used 20 g of hydrogenated isoprene frame | skeleton acrylate obtained by the synthesis example 2 as a component. The active energy ray-curable composition A-2 was evaluated for the moisture resistance, curability, flexibility and adhesion, and the results are shown in Table 1.

Example 3
As component (B), 50 g of tricyclodecane dimethylol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., (trade name) Light Acrylate DCP-A) and 1,9-nonane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., (trade name) Light Acrylate 1, 9ND-A) Active energy ray-curable composition A-3 was obtained in the same manner as in Example 1 except that 23 g was used. The active energy ray-curable composition A-3 was evaluated for the moisture resistance, curability, flexibility and adhesion, and the results are shown in Table 1.

Example 4
Example except that 10 g of smectite layered material (trade name: Lucentite SPN, manufactured by Katakura Corp. Aguri Co., Ltd.) produced by ion exchange of smectite with quaternary ammonium salt was used as component (D). In the same manner as in Example 1, an active energy ray-curable composition A-4 was obtained. The active energy ray-curable composition A-4 was subjected to the above moisture resistance, curability, flexibility and adhesion, and the evaluation results are shown in Table 1.

Example 5
As component (D), Example 10 was used except that 10 g of a montmorillonite-based layered material (trade name: Esven NX, manufactured by Hojun Co., Ltd.) produced by ion exchange of montmorillonite with a quaternary ammonium salt was used. Thus, active energy ray-curable composition A-5 was obtained. The active energy ray-curable composition A-5 was evaluated for the moisture resistance, curability, flexibility and adhesion, and the results are shown in Table 1.

Example 6
As component (A), 30 g of the hydrogenated butadiene skeleton acrylate obtained in Synthesis Example 1 was used, and as component (B), 58 g of tricyclodecane dimethylol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., (trade name) Light Acrylate DCP-A) was used. Except that, an active energy ray-curable composition A-6 was obtained in the same manner as in Example 1. The active energy ray-curable composition A-6 was evaluated for the moisture resistance, curability, flexibility and adhesion, and the results are shown in Table 1.

Example 7
Active energy rays in the same manner as in Example 1 except that 25 g of the hydrogenated butadiene skeleton acrylate obtained in Synthesis Example 1 was used as the component (A) and 15 g of the layered material 15 obtained in Production Example 1 was used as the component (D). A curable composition A-7 was obtained. The active energy ray-curable composition A-7 was evaluated for the moisture resistance, curability, flexibility and adhesion, and the results are shown in Table 1.

Comparative Example 1
The active energy ray-curable composition B-1 was obtained in the same manner as in Example 1 except that the component (A) was not used and 88 g of tricyclodecane dimethylol diacrylate was used as the component (B). The active energy ray-curable composition B-1 was evaluated for the moisture resistance, curability, flexibility, and tight adhesion, and the results are shown in Table 1.

Comparative Example 2
(A) Active energy ray-curable composition in the same manner as in Example 1 except that 20 g of liquid polyisoprene (trade name; Claprene LIR-30, number average molecular weight 29000) was used without using the component. Product B-2 was obtained. The active energy ray-curable composition B-2 was evaluated for the moisture resistance, curability, flexibility and adhesion, and the results are shown in Table 1.

Comparative Example 3
The active energy ray-curable composition B-3 was obtained in the same manner as in Example 1 except that the component (B) was not used and 88 g of hydrogenated butadiene skeleton acrylate was used as the component (A). The above-mentioned moisture resistance, curability, flexibility and adhesion were evaluated for the active energy ray-curable composition B-3, and the results are shown in Table 1.

Comparative Example 4
(D) Active energy ray hardening-type composition B-4 was obtained like Example 6 except not using a component. The active energy ray-curable composition B-4 was evaluated for the moisture resistance, curability, flexibility and adhesion, and the results are shown in Table 1.

From Table 1, the component (A) has at least one structural unit derived from a hydrogenated polybutadiene polyol and / or a structural unit derived from a hydrogenated isoprene polyol, and at least one of an acryloyl group and a methacryloyl group. A compound having a group, having at least one of an acryloyl group and a methacryloyl group as the component (B), and having no structural unit derived from a hydrogenated polybutadiene polyol or a structural unit derived from a hydrogenated isoprene polyol The compositions of Examples 1 to 7 using the compound, the photopolymerization initiator as the component (C), and the layered material as the component (D) are excellent in curability, and the cured product obtained from these compositions has a moisture content. It had high moisture resistance with a transmittance value of less than 20 g / m ² · day, and was excellent in flexibility and adhesion. Although the cured product obtained from the composition of Comparative Example 1 containing no component (A) was excellent in moisture resistance and adhesion, it could not be bent because of its low flexibility. The hardened | cured material obtained from the composition of the comparative example 2 containing the component which does not contain a (meth) acryloyl group instead of (A) component had a little tack, and curability was a little inferior. Moreover, although the hardened | cured material of the comparative example 2 had a softness | flexibility, adhesiveness was inferior, the water permeability was high, and moisture-proof property was inferior. Since the composition of Comparative Example 3 containing no component (B) was poor in reactivity, poor curing occurred, and the moisture resistance of the cured product could not be measured. In Comparative Example 4 that does not contain the component (D), the curability of the composition and the flexibility and adhesion of the cured product are excellent, but the moisture resistance extends to the moisture resistance of Example 6 containing the component (D). There wasn't.

  The active energy ray-curable composition of the present invention has very excellent curability, and the cured product of the present invention has very excellent moisture resistance and flexibility. Therefore, the active energy ray-curable composition and the cured product of the present invention can be applied not only to protective films for electronic devices but also to protective films for solar cells and various packaging materials, and can be expected to play an active role in a wide range of fields. .

Claims (9)

5 to 40% by mass of the following component (A), 50 to 85% by mass of component (B), 0.1 to 10% by mass of component (C), and 3 to 30% by mass of component (D) An active energy ray-curable composition.
Component (A): a compound having at least one structural unit of a structural unit derived from a hydrogenated polybutadiene polyol and a structural unit derived from a hydrogenated isoprene polyol, and having at least one of an acryloyl group and a methacryloyl group Component (B): Compound (C) which has at least one of acryloyl group and methacryloyl group and does not have a structural unit derived from hydrogenated polybutadiene polyol and a structural unit derived from hydrogenated isoprene polyol : Photopolymerization initiator (D) component: Layered material (A) Component contains at least 1 sort (s) chosen from following (a-1) and (a-2), The active energy ray hardening-type composition of Claim 1 characterized by the above-mentioned.
(A-1) Reaction product of hydrogenated polybutadiene polyol or hydrogenated isoprene polyol and an acryloyl group-containing isocyanate compound and / or methacryloyl group-containing isocyanate compound (a-2) Hydrogenated polybutadiene polyol or hydrogenated isoprene polyol; Reaction product obtained by transesterification with lower alkyl ester of acrylic acid and / or lower alkyl ester of methacrylic acid   The active energy ray-curable type according to claim 1 or 2, wherein the component (B) contains at least one of an acryloyl group-containing compound having a cycloaliphatic group and a methacryloyl group-containing compound having a cycloaliphatic group. Composition.   The active energy ray-curable composition according to any one of claims 1 to 3, wherein the component (D) is a clay mineral having a crystal structure.   The active energy ray-curable composition according to claim 4, wherein the clay mineral having a crystal structure is a swellable silicate.   6. The active energy ray-curable composition according to claim 5, wherein the swellable silicate is smectite group clay and / or swellable mica.   The active energy ray-curable composition according to any one of claims 1 to 3, wherein the component (D) is an ion exchange reaction product of a swellable silicate and an organic quaternary amine compound.   8. The active energy ray-curable composition according to claim 7, wherein the organic quaternary amine compound is N, N-dimethyl-N-benzyl-N- [2- (acryloyloxy) ethyl] ammonium chloride. .   A cured product obtained by curing the active energy ray-curable composition according to claim 1.