JP2019006994A - Urethane (meth)acrylate, active energy ray-curable resin composition, cured article, and protective film - Google Patents

Abstract

To provide urethane (meth)acrylate, an active energy ray-curable resin composition, a cured article, and a protective film.SOLUTION: There is provided urethane (meth)acrylate containing saturated aliphatic polyisocyanate, saturated aliphatic polyol, polyether polyol and/or polyester polyol and hydroxyl group-containing (meth)acrylate in monomers, obtained by reacting the monomers containing 0.2 to 10 pts.mass of the polyether polyol and/or the polyester polyol based on 100 pts.mass of the monomers, and containing a cycloalkylene group of 19 to 48 pts.mass based on 100 pts.mass of the urethane (meth)acrylate.SELECTED DRAWING: None

Description

  The present disclosure relates to a urethane (meth) acrylate, an active energy ray-curable resin composition, a cured product, and a protective film.

  Plastic is lightweight and has excellent processability and is used in various fields. However, many plastics are highly permeable to moisture. For example, when used for protection of electronic equipment, etc., since moisture easily comes into contact with the electronic equipment, various measures are taken to suppress moisture permeability. Ingenuity has been made. As an example of the above device, a method of forming a protective film on the plastic surface has been proposed.

However, the thinner the protective film is, the easier it is for moisture to permeate the protective film (high moisture permeability), so that there is a problem that the plastic bonded to the protective film is easy to absorb moisture and dehumidify. In recent years, there has been a demand for further thinning and low moisture permeability. For thin films of 20 μm or less, for example, low moisture permeability of 80 g / (m ² · 24 h) or less is required. Further, since there is a problem that it is fragile and easily breaks in a thin layer state, a protective film having toughness, that is, handling property at work and good durability is also required.

The problem to be solved by the present invention is a urethane (meth) acrylate capable of forming a protective film having a low moisture permeability of 80 g / (m ² · 24 h) or less and a toughness with a thin film of 20 μm or less. Will be provided.

  As a result of intensive studies on the above problems, the present inventors have found that a protective film having low moisture permeability and toughness can be formed by using a specific urethane (meth) acrylate.

The present disclosure provides the following items.
(Item 1)
Saturated aliphatic polyisocyanate in the monomer group,
Saturated aliphatic polyols,
Polyether polyol and / or polyester polyol,
And
Including a hydroxyl group-containing (meth) acrylate,
It is a reaction product of the monomer group in which 0.2 to 10 parts by mass of the polyether polyol and / or the polyester polyol is included with respect to 100 parts by mass of the monomer group.
Urethane (meth) acrylate containing 19 to 48 parts by mass of a cycloalkylene group with respect to 100 parts by mass of urethane (meth) acrylate.
(Item 2)
The following structure A derived from the saturated aliphatic polyisocyanate,
—CO—NH—R ¹ —NH—CO— (Structure A)
(Wherein R ¹ is an alkylene group or a cycloalkylene group)
The following structure B derived from the saturated aliphatic polyol
—O—R ² —O— (Structure B)
(Wherein R ² is an alkylene group or a cycloalkylene group)
The following structure C1 derived from the polyether polyol
(Wherein R ³ is an alkylene group or a cycloalkylene group, and n is an integer of 2 or more)
And / or the following structure C2 derived from the polyester polyol,
(Wherein R ⁴ is an alkylene group or a cycloalkylene group, and m is an integer of 2 or more)
And
The following structure D derived from the hydroxyl group-containing (meth) acrylate
—O—R ^5a —O—C (O) —CR ^5b ═CH ₂ (Structure D)
(Wherein R ^5a is an alkylene group or a cycloalkylene group, and R ^5b is hydrogen or a methyl group)
The urethane (meth) acrylate according to any one of the above items, comprising:
(Item 3)
An active energy ray-curable resin composition comprising the urethane (meth) acrylate according to any one of the above items.
(Item 4)
Hardened | cured material of the active energy ray curable resin composition of any one of the said items.
(Item 5)
The protective film containing the hardened | cured material of any one of the said items.

  One or more of the features described above may be provided in further combinations in addition to the express combinations. Those skilled in the art will recognize additional embodiments and advantages other than those described above upon reading and understanding the following detailed description as necessary.

  By coating with the urethane (meth) acrylate according to the present embodiment, a protective film having low moisture permeability and high breaking strength can be obtained. By using the protective film, it is possible to obtain a barrier film, a polarizing plate, a packaging film and the like whose performance does not deteriorate even under high temperature and high humidity.

  Throughout the present disclosure, ranges of numerical values such as each physical property value and content can be set as appropriate (for example, selected from the upper limit and lower limit values described in the following items). Specifically, for the numerical value α, the upper limit of the numerical value α is exemplified as A1, A2, A3, etc., and the lower limit of the numerical value α is exemplified as B1, B2, B3, etc., the range of the numerical value α is A1 or less, A2 or less, A3 or less, B1 or more, B2 or more, B3 or more, A1-B1, A1-B2, A1-B3, A2-B1, A2-B2, A2-B3, A3-B1, A3-B2, A3-B3 Etc. are exemplified.

[Urethane (meth) acrylate]
The present disclosure provides a saturated aliphatic polyisocyanate group of monomers,
Saturated aliphatic polyols,
Polyether polyol and / or polyester polyol,
And
Including a hydroxyl group-containing (meth) acrylate,
It is a reaction product of the monomer group in which 0.2 to 10 parts by mass of the polyether polyol and / or the polyester polyol is included with respect to 100 parts by mass of the monomer group.
Provided is urethane (meth) acrylate containing 19 to 48 parts by mass of a cycloalkylene group with respect to 100 parts by mass of urethane (meth) acrylate.

  In the present disclosure, “(meth) acrylate” means “at least one selected from the group consisting of acrylate and methacrylate”. Similarly, “(meth) acryl” means “at least one selected from the group consisting of acryl and methacryl”.

In one embodiment, the urethane (meth) acrylate is
The following structure A derived from a saturated aliphatic polyisocyanate,
—CO—NH—R ¹ —NH—CO— (Structure A)
(Wherein R ¹ is an alkylene group or a cycloalkylene group)
The following structure B derived from a saturated aliphatic polyol
—O—R ² —O— (Structure B)
(Wherein R ² is an alkylene group or a cycloalkylene group)
The following structure C1 derived from polyether polyol
(Wherein R ³ is an alkylene group or a cycloalkylene group, and n is an integer of 2 or more)
And / or the following structure C2 derived from polyester polyol,
(Wherein R ⁴ is an alkylene group or a cycloalkylene group, and m is an integer of 2 or more)
And
The following structure D derived from a hydroxyl group-containing (meth) acrylate
—O—R ^5a —O—CO—CR ^5b ═CH ₂ (Structure D)
(Wherein R ^5a is an alkylene group or a cycloalkylene group, and R ^5b is hydrogen or a methyl group)
including.

<Saturated aliphatic polyisocyanate>
In the present disclosure, “saturated aliphatic polyisocyanate” means a compound composed of a saturated aliphatic group and two or more isocyanate groups (—N═C═O). In the present disclosure, the “saturated aliphatic group” means a hydrocarbon group that does not have an unsaturated bond such as a double bond or a triple bond. Examples of the saturated aliphatic group include an alkyl group, a cycloalkyl group, an alkylene group, and a cycloalkylene group. Two or more saturated aliphatic polyisocyanates may be used in combination.

In one embodiment, the saturated aliphatic polyisocyanate has the structural formula O═C═N—R ^{1 ′} —N═C═O (Structural Formula A).
(In the formula, R ^{1 ′} is an alkylene group or a cycloalkylene group)
It is represented by

  Examples of the saturated aliphatic polyisocyanate include alkylene polyisocyanate, cycloalkylene polyisocyanate or its adduct, modified product, and the like.

  The carbon number of the saturated aliphatic group is not particularly limited, but the upper limit is exemplified by 30, 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, etc. The lower limit is exemplified by 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. In one embodiment, 1-30 are preferable, as for carbon number of a saturated aliphatic group, 1-20 are more preferable, 1-16 are more preferable, and 1-12 are especially preferable.

  Examples of the alkylene group include a linear alkylene group and a branched alkylene group.

The linear alkylene group can be represented by a general formula of — (CH ₂ ) _n — (n is an integer of 1 or more). Straight chain alkylene groups include methylene, ethylene, propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, n-decamethylene, etc. Is exemplified.

  Examples of linear aliphatic polyisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate and the like. The

  A branched alkylene group is a group in which at least one hydrogen of a linear alkylene group is substituted with an alkyl group. Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutylene group, a trimethylpentylene group, and a trimethylhexylene group.

  Examples of the branched aliphatic polyisocyanate include diethyl pentylene diisocyanate, trimethyl butylene diisocyanate, trimethyl pentylene diisocyanate, and trimethyl hexamethylene diisocyanate.

  Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, and a condensed ring cycloalkylene group. In the cycloalkylene group, one or more hydrogen atoms may be substituted with a linear or branched alkyl group.

  In the present disclosure, a single ring means a cyclic structure having no bridge structure inside formed by a covalent bond of carbon. Further, the condensed ring means a cyclic structure in which two or more monocycles share two atoms (that is, only one side of each ring is shared (condensed) with each other). A bridged ring means a cyclic structure in which two or more monocycles share three or more atoms.

  Examples of the monocyclic cycloalkylene group include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclodecylene group, and a 3,5,5-trimethylcyclohexylene group.

  Examples of the bridged cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornylene group.

  Examples of the fused ring cycloalkylene group include a bicyclodecylene group.

  The cycloalkylene polyisocyanate is a monocyclic cycloalkylene polyisocyanate such as hydrogenated diphenylmethane diisocyanate (H12MDI), hydrogenated xylene diisocyanate (HXDI) or isophorone diisocyanate (IPDI); a bridged ring cycloalkylene polyisocyanate such as norbornene diisocyanate (NBDI); Examples thereof include condensed ring cycloalkylene polyisocyanates such as bicyclodecylene diisocyanate.

  The saturated aliphatic polyisocyanate is preferably a cycloalkylene polyisocyanate, and among them, hydrogenated xylene diisocyanate (HXDI) and norbornene diisocyanate (NBDI) are more preferable from the viewpoint of low moisture permeability.

  The upper limit of the content of the saturated aliphatic polyisocyanate with respect to 100 parts by mass of the monomer group is exemplified by 50, 45, 40, 35 parts by mass, and the lower limit is exemplified by 45, 40, 35, 30 parts by mass. In one embodiment, as for content of saturated aliphatic polyisocyanate with respect to 100 mass parts of monomer groups, 30-50 mass parts is preferable.

  The upper limit of the content of saturated aliphatic polyisocyanate with respect to 100 mol% of the monomer group is exemplified by 50, 45, 40, 35 mol%, and the lower limit is exemplified by 45, 40, 35, 30 mol% or the like. In one embodiment, as for content of saturated aliphatic polyisocyanate with respect to 100 mol% of monomer groups, 30-50 mol% is preferable.

  When the saturated aliphatic polyisocyanate is an alkylene polyisocyanate, the number of carbon atoms of the alkylene group is preferably 6 from the viewpoint of low moisture permeability. When the saturated aliphatic polyisocyanate is a cycloalkylene polyisocyanate, the cycloalkylene preferably has 6 to 7 carbon atoms from the viewpoint of low moisture permeability.

<Saturated aliphatic polyol>
In the present disclosure, “saturated aliphatic polyol” means a compound in which two or more hydroxy groups (hydroxyl groups) are directly bonded to a saturated aliphatic group. Two or more saturated aliphatic polyols may be used in combination. In one embodiment, the aliphatic polyol has the structural formula B
HO—R ^{2 ′} —OH (Structural Formula B)
(Wherein R ^{2 ′} represents an alkylene group or a cycloalkylene group).

  Examples of saturated aliphatic polyols include alkylene polyols, cycloalkylene polyols, adducts thereof, and modified products thereof.

  Examples of the alkylene polyol include linear alkylene polyols and branched alkylene polyols.

  Examples of the linear alkylene polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, and decanediol.

  Branched alkylene polyols are neopentyl glycol, 2,4-diethyl-1,5-pentanediol, 2,4-dibutyl-1,5-pentanediol, 1-methylethylene glycol, 1-ethylethylene glycol, trimethylolpropane And pentaerythritol.

  Examples of the cycloalkylene polyol include monocyclic cycloalkylene polyols and bridged ring cycloalkylene polyols.

  Examples of the monocyclic cycloalkylene polyol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2'-bis (4-hydroxycyclohexyl) propane, and the like.

  Examples of the bridged ring cycloalkylene polyol include tricyclodecane dimethanol.

  When the saturated aliphatic polyol is an alkylene polyol, the alkylene group preferably has 2 to 9 carbon atoms from the viewpoint of low moisture permeability. When the saturated aliphatic polyol is a cycloalkylene polyol, the cycloalkylene preferably has 6 to 10 carbon atoms from the viewpoint of easy availability.

  The upper limit of the content of the saturated aliphatic polyol with respect to 100 parts by mass of the monomer group is exemplified by 40, 30, 20, 15 parts by mass, and the lower limit is exemplified by 35, 30, 20, 10 parts by mass or the like. In one embodiment, as for content of saturated aliphatic polyol with respect to 100 mass parts of monomer groups, 10-40 mass parts is preferable.

  The upper limit of the content of the saturated aliphatic polyol with respect to 100 mol% of the monomer group is exemplified by 40, 30, 20, 15 mol%, and the lower limit is exemplified by 35, 30, 20, 10 mol% or the like. In one embodiment, the content of the saturated aliphatic polyol is preferably 10 to 40 mol% with respect to 100 mol% of the monomer group.

  The upper limit of the content of the saturated aliphatic polyol with respect to 100 parts by mass of the saturated aliphatic polyisocyanate in the monomer group is exemplified by 80, 70, 60, 50, 40, 35 parts by mass, and the lower limit is 75, 70, 60. , 50, 40, 30 parts by mass and the like. In one embodiment, as for content of saturated aliphatic polyol with respect to 100 mass parts of saturated aliphatic polyisocyanate, 30-80 mass parts is preferable.

  The upper limit of the content of the saturated aliphatic polyol with respect to 100 mol% of the saturated aliphatic polyisocyanate in the monomer group is exemplified by 80, 70, 60, 50, 40, 35 mol%, and the lower limit is 75, 70, 60. , 50, 40, 30 mol% and the like. In one embodiment, the content of the saturated aliphatic polyol is preferably 30 to 80 mol% with respect to 100 mol% of the saturated aliphatic polyisocyanate.

<Polyether polyol>
In the present disclosure, the “polyether polyol” means a compound having two or more hydroxy groups and two or more repeating units containing an ether bond. Two or more kinds of polyether polyols may be used in combination. In one embodiment, the polyether polyol has the structural formula C1
HO— (R ^{3 ′} —O—) _n H (Structural Formula C1)
(Wherein R ^{3 ′} is an alkylene group or a cycloalkylene group, and n is an integer of 2 or more).

  Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

  Examples of the upper limit of the weight average molecular weight (Mw) of the polyether polyol include 100,000, 75,000, 50,000, 25,000, 10,000, 5000, 2000, and the lower limit is 90,000, 7.5. 10,000, 5,000, 25,000, 10,000, 5,000, 2000, 1000, etc. are exemplified. In one embodiment, as for the weight average molecular weight (Mw) of polyether polyol, 1000-100,000 are preferable.

  Examples of the upper limit of the number average molecular weight (Mn) of the polyether polyol include 100,000, 75,000, 50,000, 25,000, 10,000, 5000, 2000, and the lower limit is 90,000, 7.5. 10,000, 5,000, 25,000, 10,000, 5,000, 2000, 1000, etc. are exemplified. In one embodiment, the number average molecular weight (Mn) of the polyether polyol is preferably 1000 to 100,000.

  The weight average molecular weight and the number average molecular weight are determined by gel permeation chromatography (for example, product name “HLC-8220” manufactured by Tosoh Corporation, column: product manufactured by Tosoh Corporation, product name “TSKgel superHZ-M”) (The same applies hereinafter).

<Polyester polyol>
In the present disclosure, “polyester polyol” means a compound having two or more hydroxy units and two or more repeating units containing an ester bond in the molecule. Two or more polyester polyols may be used in combination. In one embodiment, the polyester polyol has the structural formula C2
HO— {R ^{4a ′} —OC (O) —R ^{4b ′} —C (O) O} _m —R ^{4a ′} —OH (Structural Formula C2)
(Wherein, R ^{4a ′} and R ^{4b ′} are each independently an alkylene group or a cycloalkylene group, and m is an integer of 2 or more).

  In general, polyether polyols and polyester polyols contain many ether bonds and ester bonds, which are hydrophilic bonds, respectively. Therefore, protection produced using urethane (meth) acrylate produced using polyether polyol and / or polyester polyol. The film has been found to be able to produce a film with low moisture permeability, where moisture is likely to permeate the protective film (high moisture permeability).

  In the present disclosure, a “polyester polyol” is a reaction product of a polycarboxylic acid or an anhydride thereof and a polyol.

  Examples of the polycarboxylic acid include dicarboxylic acid.

  Dicarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipine Acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, Examples thereof include dicarboxylic acids such as trimesic acid and cyclohexanedicarboxylic acid.

  Examples of the polycarboxylic acid anhydride include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, and trimellitic anhydride.

  Examples of the polyol include the alkylene polyol and the cycloalkylene polyol.

  The upper limit of the weight average molecular weight (Mw) of the polyester polyol is exemplified by 100,000, 75,000, 50,000, 25,000, 10,000, 5,000, 2000, etc. The lower limit is 90,000, 75,000. 50,000, 25,000, 10,000, 5000, 2000, 1000, etc. are exemplified. In one embodiment, the polyester polyol preferably has a weight average molecular weight (Mw) of 1,000 to 100,000.

  The upper limit of the number average molecular weight (Mn) of the polyester polyol is exemplified by 100,000, 75,000, 50,000, 25,000, 10,000, 5,000, 2000, etc. The lower limit is 90,000, 75,000. 50,000, 25,000, 10,000, 5000, 2000, 1000, etc. are exemplified. In one embodiment, the number average molecular weight (Mn) of the polyester polyol is preferably 1000 to 100,000.

  The upper limit of the content of the polyether polyol and / or polyester polyol with respect to 100 parts by mass of the monomer group is exemplified by 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5 parts by mass, etc. The lower limit is exemplified by 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.2 parts by mass, and the like. In one embodiment, the content of the polyether polyol and / or polyester polyol with respect to 100 parts by mass of the monomer group is preferably 0.2 to 10 parts by mass from the viewpoint of low moisture permeability.

  The upper limit of the content of the polyether polyol and / or polyester polyol with respect to 100 mol% of the monomer group is exemplified by 1,0.75, 0.5, 0.25, 0.1, 0.05 mol%, etc. Is exemplified by 0.9, 0.75, 0.5, 0.25, 0.1, 0.05, 0.02 mol%, and the like. In one embodiment, the content of the polyether polyol and / or polyester polyol with respect to 100 mol% of the monomer group is preferably 0.02 to 1 mol%.

  The upper limit of the content of the polyether polyol and / or polyester polyol with respect to 100 parts by mass of the saturated aliphatic polyisocyanate in the monomer group is exemplified by 20, 15, 10, 5, 1, 0.5 parts by mass, and the lower limit is 19, 15, 10, 5, 1, 0.5, 0.4 parts by mass and the like. In one embodiment, the content of the polyether polyol and / or the polyester polyol with respect to 100 parts by mass of the saturated aliphatic polyisocyanate is preferably 0.4 to 20 parts by mass.

  The upper limit of the content of the polyether polyol and / or polyester polyol with respect to 100 mol% of the saturated aliphatic polyisocyanate in the monomer group is exemplified by 2, 1, 0.5, 0.1 mol%, etc. The lower limit is 1 .9, 1, 0.5, 0.1, 0.04 mol% and the like. In one embodiment, the content of the polyether polyol and / or the polyester polyol with respect to 100 mol% of the saturated aliphatic polyisocyanate is preferably 0.04 to 2 mol%.

  The upper limit of the content of the polyether polyol and / or polyester polyol with respect to 100 parts by mass of the saturated aliphatic polyol in the monomer group is 100, 90, 75, 50, 25, 10, 5, 1, 0.9 parts by mass or the like. The lower limit is exemplified by 90, 75, 50, 25, 10, 5, 1, 0.9, 0.5 parts by mass, and the like. In one embodiment, the content of the polyether polyol and / or the polyester polyol with respect to 100 parts by mass of the saturated aliphatic polyol is preferably 0.5 to 100 parts by mass.

  The upper limit of the content of the polyether polyol and / or polyester polyol with respect to 100 mol% of the saturated aliphatic polyol in the monomer group is 10, 9, 7.5, 5, 2.5, 1, 0.5, 0.1. , 0.09 mol%, etc., and the lower limit is exemplified by 9, 7.5, 5, 2.5, 1, 0.5, 0.1, 0.09, 0.05 mol%, etc. . In one embodiment, the content of the polyether polyol and / or polyester polyol with respect to 100 parts by mass of the saturated aliphatic polyol is preferably 0.05 to 10 mol%.

<Hydroxyl group-containing (meth) acrylate>
In the present disclosure, “hydroxyl group-containing (meth) acrylate” means a compound having a hydroxyl group and a (meth) acrylate moiety. Two or more kinds of hydroxyl group-containing (meth) acrylates may be used in combination. In one embodiment, the hydroxyl group-containing (meth) acrylate has the structural formula D
(Wherein R ^{5a ′} represents an alkylene group or a cycloalkylene group, and R ^{5b ′} represents a hydrogen atom or a methyl group).

  Hydroxyl group-containing (meth) acrylates are β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) ) Acrylate, 8-hydroxyoctyl (meth) acrylate, ε-caprolactone modified β-hydroxyethyl (meth) acrylate and other hydroxyl group-containing (meth) acrylates; pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. And a hydroxyl group-containing (meth) acrylate having a plurality of ester sites.

  The upper limit of the hydroxyl group-containing (meth) acrylate content with respect to 100 parts by mass of the monomer group is exemplified by 60, 50, 40, 30, 20, 10 parts by mass, and the lower limit is 55, 50, 40, 30, 20, Examples are 10 and 8 parts by mass. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate with respect to 100 parts by mass of the monomer group is preferably 8 to 60 parts by mass.

  The upper limit of the hydroxyl group-containing (meth) acrylate content with respect to 100 mol% of the monomer group is exemplified by 40, 30, 20 mol%, and the lower limit is exemplified by 35, 30, 20, 15 mol% or the like. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate with respect to 100 mol% of the monomer group is preferably 15 to 40 mol%.

  The upper limit of the hydroxyl group-containing (meth) acrylate content with respect to 100 parts by mass of the saturated aliphatic polyisocyanate in the monomer group is exemplified by 240, 200, 150, 100, 50, 25 parts by mass, and the lower limit is 230, 200. , 150, 100, 50, 25, 18 parts by mass and the like. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate with respect to 100 parts by mass of the saturated aliphatic polyisocyanate is preferably 18 to 240 parts by mass.

  The upper limit of the content of the hydroxyl group-containing (meth) acrylate with respect to 100 mol% of the saturated aliphatic polyisocyanate in the monomer group is exemplified by 100, 75, 50, 40 mol%, and the lower limit is 90, 75, 50, 40. , 30 mol% and the like. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate with respect to 100 mol% of the saturated aliphatic polyisocyanate is preferably 30 to 100 mol%.

  The upper limit of the hydroxyl group-containing (meth) acrylate content with respect to 100 parts by mass of the saturated aliphatic polyol in the monomer group is exemplified by 500, 400, 300, 200, 150, 100, 50, 25 parts by mass, etc. Examples include 400, 300, 200, 150, 100, 50, 25, 15 parts by mass. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate with respect to 100 parts by mass of the saturated aliphatic polyol is preferably 15 to 500 parts by mass.

  The upper limit of the content of the hydroxyl group-containing (meth) acrylate with respect to 100 mol% of the saturated aliphatic polyol in the monomer group is exemplified by 300, 200, 150, 100, 50 mol%, and the lower limit is 200, 150, 100, Examples thereof include 50 and 25 mol%. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate with respect to 100 mol% of the saturated aliphatic polyol is preferably 25 to 300 mol%.

  The upper limit of the content of the hydroxyl group-containing (meth) acrylate with respect to 100 parts by mass of the polyether polyol and / or polyester polyol in the monomer group is 125, 100, 90, 75, 50, 25, 10, 5, 1, 0.9. 0.5 parts by mass, and the lower limit is exemplified by 100, 90, 75, 50, 25, 10, 5, 1, 0.9, 0.5, 0.3 parts by mass, and the like. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate with respect to 100 parts by mass of the polyether polyol and / or polyester polyol in the monomer group is preferably 0.3 to 125 parts by mass.

  The upper limit of the content of the hydroxyl group-containing (meth) acrylate with respect to 100 mol% of the polyether polyol and / or polyester polyol in the monomer group is 7, 5, 4, 2, 1, 0.9, 0.5, 0.1 0.09 mol% and the like, and the lower limit is exemplified by 5, 4, 2, 1, 0.9, 0.5, 0.1, 0.09, 0.05 mol% and the like. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate with respect to 100 mol% of the polyether polyol and / or polyester polyol in the monomer group is preferably 0.05 to 7 mol%.

<Other monomers>
Using urethane (meth) acrylate with a monomer that does not fall under any of saturated aliphatic polyisocyanate, saturated aliphatic polyol, polyether polyol, polyester polyol, and hydroxyl group-containing (meth) acrylate (hereinafter also referred to as “other monomer”) Also good. Examples of the other monomers include monofunctional and polyfunctional acrylates having no hydroxyl group such as acryloylmorpholine, isobornyl acrylate, and dicyclopentanyl acrylate.

  As for content of the other monomer with respect to 100 mass parts of monomer groups, 5, 4, less than 1 mass part, 0 mass part, etc. are illustrated.

  Examples of the content of other monomers with respect to 100 mol% of the monomer group include 5, 4, less than 1 mol%, 0 mol%, and the like.

<Physical properties of urethane (meth) acrylate>
The upper limit of the weight average molecular weight (Mw) of urethane (meth) acrylate is exemplified by 100,000, 75,000, 50,000, 25,000, 10,000, 5,000, 2000, etc., and the lower limit is 90, 7 50,000, 5,000, 25,000, 10,000, 5,000, 2000, 1000, etc. In one embodiment, as for the weight average molecular weight (Mw) of urethane (meth) acrylate, 1000-100,000 are preferable.

  The upper limit of the number average molecular weight (Mn) of urethane (meth) acrylate is exemplified by 100,000, 75,000, 50,000, 25,000, 10,000, 5,000, 2000, etc. The lower limit is 90,000, 7 50,000, 5,000, 25,000, 10,000, 5,000, 2000, 1000, etc. In one embodiment, the number average molecular weight (Mn) of urethane (meth) acrylate is preferably 1000 to 100,000.

  The upper limit of the content of the cycloalkylene group with respect to 100 parts by mass of the urethane (meth) acrylate is exemplified by 48, 45, 40, 35, 30, 25, 20 parts by mass, and the lower limit is 45, 40, 35, 30, Examples are 25, 20, 19 parts by mass. In one embodiment, 19-48 mass parts of cycloalkylene groups are included with respect to 100 mass parts of urethane (meth) acrylates. In the present disclosure, “including 100 parts by mass of urethane (meth) acrylate includes A part by mass of a cycloalkylene group” means, for example, urethane (meta) using only 1,4-cyclohexanedimethanol as a monomer having a cycloalkylene group. ) When manufacturing an acrylate, it means that the formula weight of a cyclohexylene group with respect to 100 mass parts of molecular weight (formula weight) of urethane (meth) acrylate is A mass part.

  The method for producing urethane (meth) acrylate is not particularly limited as long as it is a method of reacting saturated aliphatic polyisocyanate, saturated aliphatic polyol, polyether polyol and / or polyester polyol, and hydroxyl group-containing (meth) acrylate. Instead, a known production method is exemplified. The above production method is a method of producing a mixture of saturated aliphatic polyisocyanate, saturated aliphatic polyol, polyether polyol and / or polyester polyol, and hydroxyl group-containing (meth) acrylate, saturated aliphatic polyisocyanate, saturated aliphatic Examples thereof include a method of producing by reacting a hydroxyl group-containing (meth) acrylate after the polyol, polyether polyol and / or polyester polyol are mixed and reacted.

  The molar ratio (OH / NCO) of the total amount of hydroxyl groups and the total amount of isocyanate groups in each monomer in the monomer group is preferably 1.0 to 1.1 from the viewpoints of toxicity and low moisture permeability. .

[Active energy ray-curable resin composition]
The present disclosure provides an active energy ray-curable resin composition containing the urethane (meth) acrylate. The composition can be suitably used in coating applications.

  The upper limit of the urethane (meth) acrylate content in the composition is exemplified by 100, 90, 80, 70, 60, 55 parts by mass, and the lower limit is 95, 90, 80, 70, 60, 55, Examples are 50 parts by mass. In one embodiment, it is preferable that 50-100 mass parts of the above-mentioned urethane (meth) acrylate is included to 100 mass parts of the above-mentioned composition from a viewpoint of low moisture permeability.

  In one embodiment, the composition includes a photopolymerization initiator. Two or more photopolymerization initiators may be used in combination. Photopolymerization initiators are 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl- Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone and the like are exemplified.

  In one embodiment, content of a photoinitiator is 3.0-7.0 mass parts etc. from a sclerosing | hardenable viewpoint with respect to 100 mass parts of compositions, In another embodiment, urethane ( Examples include 3.0 to 14 parts by mass with respect to 100 parts by mass of (meth) acrylate.

  In one embodiment, the composition includes a diluent solvent. Two or more diluent solvents may be used in combination. Dilution solvents are methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, tert-butyl alcohol, diacetone alcohol, acetylacetone, toluene, xylene , N-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, 1,4-dioxane, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc. The In one embodiment, the content of the diluting solvent is exemplified by about 0 to 400 parts by mass or the like from the viewpoint of viscosity suitable for coating with respect to 100 parts by mass of the composition. In another embodiment, about 0-800 mass parts etc. are illustrated with respect to 100 mass parts of urethane (meth) acrylates.

  The composition may contain an additive other than urethane (meth) acrylate, a photopolymerization initiator, and a diluent solvent as an additive. Additives are antioxidants, UV absorbers, light stabilizers, antifoaming agents, surface conditioners, antifouling agents, inorganic fillers, silane coupling agents, colloidal silica, pigments, antistatic agents, metal oxide fine particle dispersions Examples include bodies. In one embodiment, the content of the additive is 5, 4, less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, 0 part by weight, etc. with respect to 100 parts by weight of the composition. In another embodiment, for example, 5, 4, less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, 0 part by weight, etc. with respect to 100 parts by weight of urethane (meth) acrylate Is done.

[Cured product]
The present disclosure provides a cured product of the active energy ray-curable resin composition. The cured product can be obtained by irradiating the active energy ray-curable resin composition with active energy rays such as ultraviolet rays, electron beams, and radiation.

  Examples of the ultraviolet light source include a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED lamp. The amount of ultraviolet rays can be appropriately adjusted according to the thickness of the cured product.

[Protective film]
The present disclosure provides a protective film including the cured product. The said protective film is manufactured by the method of including the process of apply | coating on a base material, and irradiating an active energy ray, making it harden | cure, and laminating | stacking. Moreover, the process of irradiating an active energy ray can be performed during and / or after drying of the coated material.

  Examples of the base material include polyethylene terephthalate (PET), polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, and the like.

  Examples of the coating method include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing.

  The protective film can be used for barrier films, polarizing plates, packaging films, and the like.

  Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, parts and% are based on mass.

<Synthesis Example 1> (Synthesis of urethane acrylate containing a cycloalkylene group)
In a three-necked flask equipped with a stirrer, thermometer, reflux condenser, 31.6 parts of hydrogenated xylene diisocyanate (H-XDI), 16.0 parts of tricyclodecane dimethanol (hereinafter TCDDM), polyether polyol (Product name “Uniol D-2000”, manufactured by NOF Corporation) 3.5 parts, 30.0 parts of butyl acetate and 0.01 g of tin octylate were charged and reacted at 80 ° C. When the residual isocyanate group reached 8.4%, 18.9 parts of 2-hydroxyethyl acrylate (HEA), 0.01 g of tin octylate and 0.07 g of hydroquinone monomethyl ether were added, and the residual isocyanate group was 0.1%. It reacted until it became below, and 100 g (A-1) of urethane acrylate solutions with a resin content of 70% were obtained.

  Synthesis examples other than synthesis example 1 and comparative synthesis examples were performed in the same manner as synthesis example 1, except that the reaction components were changed as shown in the following table.

¹ A′-6 crystallized as the reaction proceeded and could not be synthesized.
H-XDI: hydrogenated xylene diisocyanate NBDI: norbornene diisocyanate HDI: hexamethylene diisocyanate

TCDDM: Tricyclodecane dimethanol DEPD: 2,4-diethyl-1,5-pentanediol CHDM: 1,4-cyclohexanedimethanol

Polyether polyol (trade name “Uniol D-2000”, manufactured by NOF Corporation)
Polyester polyol (trade name “Kuraray polyol P-4010”, manufactured by Kuraray Co., Ltd.)

HEA: 2-hydroxyethyl acrylate PE3A: pentaerythritol triacrylate

Next, the Example as a cured | curing material film of the urethane (meth) acrylate of this invention is shown.
Example 1
Urethane acrylate (A-1) 54.4 parts, photopolymerization initiator IRGACURE 184 (Irg. 184) 1.9 parts, methyl ethyl ketone (MEK) 43.7 parts were stirred uniformly to obtain a solid content of 40 % Active energy ray-curable resin composition was obtained.

Examples 2-5, Comparative Examples 1-5
Hereinafter, the active energy ray-curable resin composition was prepared in the same manner according to the blending ratio in Table 2.

<Creation of dry film>
Using the bar coater No20, the active energy ray-curable resin compositions of Examples 1 to 5 and Comparative Examples 1 to 5 on the triacetyl cellulose film or glass plate were hand-treated so as to have a dry film thickness of 10 μm. Coat was applied and dried at 90 ° C. for 3 minutes.

<Creation of cured film>
From the dry film states of Examples 1 to 5 and Comparative Examples 1 to 5, a cured film was prepared by irradiating an integrated irradiation amount of 300 mJ / cm ² using a high pressure mercury lamp 80 W and one lamp, and the following evaluation was performed.

<Evaluation of moisture permeability of cured film>
Measured according to JIS Z 0208 moisture permeability test method (cup method) using a cured film prepared on a triacetyl cellulose film. In an atmosphere having a temperature of 40 ° C. and a humidity of 90% RH, the number of grams of water vapor passing over 24 hours per 1 m ^{2 of the} test piece area was measured.

<Evaluation of breaking strength of cured film>
Using a single cured film obtained by peeling off a cured film prepared on a glass plate, the measurement was performed according to the test conditions for the film and sheet of JIS K 7127 and the tensile property test method of JIS K 7161.

Table 3 shows the evaluation results of Examples 1 to 5 and Comparative Examples 1 to 5.
* Because the breaking strength is weak, the test piece breaks during measurement.

Claims (5)

Saturated aliphatic polyisocyanate in the monomer group,
Saturated aliphatic polyols,
Polyether polyol and / or polyester polyol,
And
Including a hydroxyl group-containing (meth) acrylate,
It is a reaction product of the monomer group in which 0.2 to 10 parts by mass of the polyether polyol and / or the polyester polyol is included with respect to 100 parts by mass of the monomer group.
Urethane (meth) acrylate containing 19 to 48 parts by mass of a cycloalkylene group with respect to 100 parts by mass of urethane (meth) acrylate. The following structure A derived from the saturated aliphatic polyisocyanate,
—CO—NH—R ¹ —NH—CO— (Structure A)
(Wherein R ¹ is an alkylene group or a cycloalkylene group)
The following structure B derived from the saturated aliphatic polyol
—O—R ² —O— (Structure B)
(Wherein R ² is an alkylene group or a cycloalkylene group)
The following structure C1 derived from the polyether polyol
(Wherein R ³ is an alkylene group or a cycloalkylene group, and n is an integer of 2 or more)
And / or the following structure C2 derived from the polyester polyol,
(Wherein R ⁴ is an alkylene group or a cycloalkylene group, and m is an integer of 2 or more)
And
The following structure D derived from the hydroxyl group-containing (meth) acrylate
—O—R ^5a —O—C (O) —CR ^5b ═CH ₂ (Structure D)
(Wherein R ^5a is an alkylene group or a cycloalkylene group, and R ^5b is hydrogen or a methyl group)
The urethane (meth) acrylate according to claim 1, comprising: An active energy ray-curable resin composition comprising the urethane (meth) acrylate according to claim 1. A cured product of the active energy ray-curable resin composition according to claim 3. A protective film comprising the cured product according to claim 4.