KR20180138190A - Urethane(meth)acrylate, active energy ray curable resin composition, cured product and protective film - Google Patents

Abstract

The present invention provides a urethane (meth) acrylate, an active energy ray curable resin composition, a cured product, and a protective film, and comprises: a saturated aliphatic polyisocyanate in a monomer group; a saturated aliphatic polyol; a polyether polyol and/or polyester polyol; and a hydroxyl group containing (meth) acrylate. The urethane (meth) acrylate is obtained by reacting the monomer group containing the polyether polyol and/or the polyester polyol in an amount of 0.2-10 parts by mass with respect to 100 parts by mass of the monomer group. The urethane (meth) acrylate contains 19-48 parts by mass of a cycloalkylene group per 100 parts by mass of the urethane (meth) acrylate.

Description

TECHNICAL FIELD [0001] The present invention relates to a urethane (meth) acrylate, an active energy ray curable resin composition, a cured product and a protective film,

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

Plastics are light and have excellent processability and are used in various fields. However, many plastics have a high moisture permeability. For example, when used for protection of electronic substrates and the like, various studies have been made to suppress the moisture permeability because the faults easily occur due to moisture contact with the electronic substrate. As an example of the above research, a method of forming a protective film on a plastic surface has been proposed.

However, as the thickness of the protective film becomes thinner, moisture easily permeates through the protective film (because of the high moisture permeability), so that the plastic laminated to the protective film is liable to be subjected to moisture absorption and dehumidification. In recent years, further thinning and low moisture permeation have been required, and a low moisture permeability, for example, a moisture permeability of 80 g / (m ² · 24 h) or less is required in a thin film of 20 μm or less. In addition, since there is a problem that it is easily broken and broken in the state of a thin layer, a protective film having toughness, that is, good handling property and durability in working is also demanded.

The present invention provides a urethane (meth) acrylate capable of forming a protective film having low moisture permeability and toughness at a moisture permeability of 80 g / (m ² · 24 h) or less in a thin film of 20 μm or less.

As a result of intensive studies, 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 following items are provided in accordance with the present disclosure.

(Item 1)

In the monomer group

Saturated aliphatic polyisocyanates,

Saturated aliphatic polyols,

Polyetherpolyol and / or polyester polyol,

And

The hydroxyl group-containing (meth) acrylate

Lt; / RTI >

Wherein the reaction product of the monomer group containing the polyether polyol and / or the polyester polyol in an amount of 0.2 to 10 parts by mass, based on 100 parts by mass of the monomer group,

Urethane (meta) acrylate having 19 to 48 parts by mass of a cycloalkylene group per 100 parts by mass of urethane (meth) acrylate.

(Item 2)

The saturated aliphatic polyisocyanate-derived structures A,

-CO-NH-R < ^{1 >} -NH-CO- (Structure A)

(Wherein R < ¹ > is an alkylene group or a cycloalkylene group)

The saturated aliphatic polyol-derived structure B

-OR < ^{2 >} -O- (Structure B)

(Wherein R ² is an alkylene group or a cycloalkylene group)

The following polyether polyol-derived structure C1

(3)

(Wherein R ³ is an alkylene group or a cycloalkylene group, and n is an integer of 2 or more)

And / or

The following structures C2,

[Chemical Formula 4]

(Wherein R ⁴ is an alkylene group or a cycloalkylene group, and m is an integer of 2 or more)

And

The following structures (D) derived from the hydroxyl group-containing (meth)

-OR ^5a -OC (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)

(Meth) acrylate as set forth in any one of the items above.

(Item 3)

An active energy ray curable resin composition comprising urethane (meth) acrylate as described in any one of the preceding items.

(Item 4)

A cured product of the active energy ray-curable resin composition according to any one of the preceding items.

(Item 5)

A protective film comprising the cured product according to any one of the preceding items.

The one or more features described above may be provided in combination in addition to the specified combination. Skilled artisans may recognize additional embodiments and advantages in addition to the above by reading and understanding the following detailed description as needed.

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

Throughout the present disclosure, the numerical ranges of the respective properties, contents, and the like can be appropriately set (for example, by selecting from the upper limit and the lower limit described in each item below). Specifically, when the upper limit of the value alpha is A1, A2, A3 and the like are exemplified and the lower limit of the value alpha is B1, B2, B3 and the like are exemplified, the range of the value alpha is A1 or less, A2 or less, A3 B2, A2, B2, A2 to B3, A3 to B1, A3 to B2, A3 to B3, and the like are exemplified .

[Urethane (meth) acrylate]

The present invention relates to

Saturated aliphatic polyisocyanates,

Saturated aliphatic polyols,

Polyether polyols and / or polyester polyols,

And

The hydroxyl group-containing (meth) acrylate

Lt; / RTI >

Wherein the reaction product of the monomer group containing the polyether polyol and / or the polyester polyol in an amount of 0.2 to 10 parts by mass, based on 100 parts by mass of the monomer group,

(Meth) acrylate, wherein the cycloalkylene group is contained in an amount of from 19 to 48 parts by mass based on 100 parts by mass of the urethane (meth) acrylate.

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

In one embodiment, the urethane (meth) acrylate

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

-OR < ^{2 >} -O- (Structure B)

(Wherein R ² is an alkylene group or a cycloalkylene group)

The polyether polyol-derived structure C1

[Chemical Formula 5]

(Wherein R ³ is an alkylene group or a cycloalkylene group, and n is an integer of 2 or more)

And / or

The following structures C2,

[Chemical Formula 6]

(Wherein R ⁴ is an alkylene group or a cycloalkylene group, and m is an integer of 2 or more)

And

The following structures (D) derived from the hydroxyl group-containing (meth)

-OR ^5a -OC (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)

.

≪ Saturated aliphatic polyisocyanate >

&Quot; Saturated aliphatic polyisocyanate " means a compound consisting of a saturated aliphatic group and two or more isocyanate groups (-N = C = O). The saturated aliphatic group is exemplified by an alkyl group, a cycloalkyl group, an alkylene group, a cycloalkylene group, etc. The saturated aliphatic polyisocyanate may be used in combination of two or more species.

In one embodiment, the saturated aliphatic polyisocyanate has the structure

O = C = NR ¹ '-N = C = O (formula A)

(Wherein R ¹ 'represents an alkylene group or a cycloalkylene group)

.

Examples of the saturated aliphatic polyisocyanate include alkylene polyisocyanates, cycloalkylene polyisocyanates or adducts thereof, and modified products thereof.

The number of carbon atoms in the saturated aliphatic group is not particularly limited and the upper limit is 30, 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, , 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, In one embodiment, the number of carbon atoms in the saturated aliphatic group is preferably from 1 to 30, more preferably from 1 to 20, still more preferably from 1 to 16, and particularly preferably from 1 to 12.

Examples of the alkylene group include a straight chain alkylene group and a branched alkylene group.

The straight chain alkylene group can be represented by the general formula - (CH2) n- (n is an integer of 1 or more). The straight-chain alkylene group may be a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, n-decamethylene group, and the like.

The straight chain aliphatic polyisocyanate may be at least one member selected from the group consisting of methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, Isocyanate, decamethylene diisocyanate, and the like.

The branched alkylene group is a group in which at least one hydrogen of the straight chain alkylene group is substituted by an alkyl group. Examples of the branched alkylene group include a diethylpentylene group, a trimethylbutyl group, a trimethylpentylene group, and a trimethylhexylene group.

Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, trimethylhexamethylene diisocyanate and the like.

Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, and a condensed ring cycloalkylene group. Further, the cycloalkylene group may be substituted with at least one hydrogen by a linear or branched alkyl group.

In the present disclosure, a monocyclic ring means a cyclic structure having no internally crosslinked structure formed by a covalent bond of carbon. Also, the condensed ring refers to a cyclic structure in which two or more monocycles share two atoms (i.e., only one of them shares (condenses) each other around each ring). A bridged ring means a cyclic structure in which two or more monocyclic rings 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 tricyclodecylene group, adamantylene group, norbornylene group and the like.

Examples of the condensed ring cycloalkylene group include bicyclodecylene group and the like.

The cycloalkylene polyisocyanate is a monocyclic cycloalkylene polyisocyanate such as hydrogenated diphenylmethane diisocyanate (H12MDI), hydrogenated xylene diisocyanate (HXDI), and isophorone diisocyanate (IPDI); Crosslinked cycloalkylene polyisocyanates such as norbornylene diisocyanate (NBDI); And cyclododecene diisocyanate; and condensed ring cycloalkylene polyisocyanates such as cyclododecene diisocyanate.

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

The upper limit of the content of the saturated aliphatic polyisocyanate relative to 100 parts by mass of the monomer group is exemplified by 50, 45, 40, and 35 parts by mass, and the lower limit is exemplified by 45, 40, 35 and 30 parts by mass. In one embodiment, the content of the saturated aliphatic polyisocyanate relative to 100 parts by mass of the monomer group is preferably 30 to 50 parts by mass.

The upper limit of the content of the saturated aliphatic polyisocyanate relative 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% and the like. In one embodiment, the content of the saturated aliphatic polyisocyanate relative to 100 mole percent of the monomer groups is preferably 30 to 50 mole percent.

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

≪ Saturated aliphatic polyol &

&Quot; Saturated aliphatic polyol " in the present disclosure means a compound in which two or more hydroxy groups (a hydroxyl group) are directly bonded to a saturated aliphatic group. Two or more kinds of saturated aliphatic polyols may be used in combination. In one embodiment, the aliphatic polyol has the structure B

HO-R ² '-OH ????? (B)

(Wherein R ² 'is an alkylene group or a cycloalkylene group).

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

The alkylene polyols include straight chain alkylene polyols, branched alkylene polyols and the like.

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

The branched alkylene polyol is preferably selected from the group consisting of neopentylglycol, 2,4-diethyl-1,5-pentanediol, 2,4-butyl- Diol, 1-methylethylene glycol, 1-ethylethylene glycol, trimethylolpropane, pentaerythritol and the like.

Examples of the cycloalkylene polyol include a monocyclic cycloalkylene polyol and a crosslinked cycloalkylene polyol.

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 crosslinked cycloalkylene polyol include tricyclodecane dimethanol and the like.

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

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

The upper limit of the saturated aliphatic polyol content 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% and the like. In one embodiment, the content of the saturated aliphatic polyol relative to 100 mole percent of the monomer groups is preferably 10 to 40 mole percent.

The upper limit of the saturated aliphatic polyol content 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, Mass parts and the like. In one embodiment, the content of the saturated aliphatic polyol relative to 100 parts by mass of the saturated aliphatic polyisocyanate is preferably 30 to 80 parts by mass.

The upper limit of the saturated aliphatic polyol content 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, Mol% and the like are exemplified. In one embodiment, the content of the saturated aliphatic polyol relative to 100 mole% of the saturated aliphatic polyisocyanate is preferably 30 to 80 mole%.

<Polyether Polyol>

In the present invention, " polyetherpolyol " 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 structure C1

HO- (R ³ '-O-) n H (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.

The upper limit of the weight average molecular weight (Mw) of the polyether polyol is 100,000, 75,000, 50,000, 10,000, 5000, and 2000, and the lower limits are 90,000, 75,000, 50,000, 5000, 2000, 1000, and the like are exemplified. In one embodiment, the weight average molecular weight (Mw) of the polyether polyol is preferably from 1,000 to 100,000.

The upper limit of the number average molecular weight (Mn) of the polyether polyol is exemplified by 100,000, 75,000, 50,000, 25,000, 10,000, 5000 and 2000, and the lower limit is 90,000, 10,000, 5000, 2000, 1000 and the like are exemplified. In one embodiment, the number average molecular weight (Mn) of the polyether polyol is preferably from 1,000 to 100,000.

The weight average molecular weight and the number average molecular weight were measured by Gel Permeation Chromatography (trade name: "HLC-8220", manufactured by Tosoh Corporation, column: "TSKgel superHZ-M" Or the like (hereinafter the same).

<Polyester Polyol>

The term " polyester polyol " in the present invention means a compound having two or more hydroxy groups and two or more repeating units containing ester bonds in the molecule. Two or more kinds of polyester polyols may be used in combination. In one embodiment, the polyester polyol has the structure C2

???????? HO- (R ^4a '-OC (O) -R ^4b ' -C (O) O} m R ^4a '-OH ????? (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).

Generally, since the polyether polyol and the polyester polyol each contain a plurality of ether bonds and ester bonds, which are hydrophilic bonds, the polyether polyol and / or the polyester polyol are produced by using urethane (meth) acrylate prepared by using a polyether polyol and / It has been found that the protective film is capable of producing a film having low moisture permeability, while moisture is considered to be easily permeable to the protective film (moisture permeability is high).

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

Examples of the polycarboxylic acid include dicarboxylic acid and the like.

The dicarboxylic acid may be selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methyl succinic acid, 2-methyladipic acid, 3-methyl- 3-methyl pentanedioic acid, 2-methyl octanedioic acid, 3,8-dimethyl decanedioic acid (3-methyl pentanedioic acid) ), Dicarboxylic acids such as 3,7-dimethyldecanedioic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, trimellitic acid, trimesic acid and cyclohexanedicarboxylic acid And the like.

The polycarboxylic acid anhydride may be selected from the group consisting of acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, and the like. .

Examples of the polyol include the alkylene polyols, the cycloalkylene polyols and the like.

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, 5000 and 2000, and the lower limit is 90,000, 10,000, 5000, 2000, 1000 and the like are exemplified. In one embodiment, the weight average molecular weight (Mw) of the polyester polyol is preferably from 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, 5000 and 2000, and the lower limit is 90,000, 10,000, 5000, 2000, 1000 and the like are exemplified. In one embodiment, the number average molecular weight (Mn) of the polyester polyol is preferably from 1,000 to 100,000.

The upper limit of the content of the polyether polyol and / or the polyester polyol with respect to 100 parts by mass of the monomer group is 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 and 0.5 parts by mass, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, and 0.2 parts by mass. In one embodiment, the content of the polyether polyol and / or the polyester polyol relative 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 the polyester polyol in 100 mol% of the monomer group is 1, 0.75, 0.5, 0.25, 0.1 and 0.05 mol% and the lower limit is 0.9, 0.75, 0.5, 0.25, 0.05, 0.02 mol%, and the like. In one embodiment, the content of the polyether polyol and / or the polyester polyol in 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 the polyester polyol with respect to 100 parts by mass of the saturated aliphatic polyisocyanate in the monomer group is 20, 15, 10, 5, 1, 0.5 parts by mass and the lower limit is 19, 10, 5, 1, 0.5, and 0.4 parts by mass. In one embodiment, the content of the polyether polyol and / or the polyester polyol relative 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 the polyester polyol in the monomer group is 2, 1, 0.5, 0.1 mol% and the lower limit is 1.9, 1, 0.5, 0.1, 0.04 Mol% and the like are exemplified. In one embodiment, the content of the polyether polyol and / or the polyester polyol in 100 mole% of the saturated aliphatic polyisocyanate is preferably 0.04 to 2 mol%.

The upper limit of the content of the polyether polyol and / or the polyester polyol with respect to 100 parts by mass of the saturated aliphatic polyol in the monomer group is exemplified by 100, 90, 75, 50, 25, 10, 5, 1 and 0.9 parts by mass, 90, 75, 50, 25, 10, 5, 1, 0.9, 0.5 parts by mass are exemplified. In one embodiment, the content of the polyether polyol and / or the polyester polyol relative 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 the polyester polyol is 10, 9, 7.5, 5, 2.5, 1, 0.5, 0.1 and 0.09 mol% in 100 mol% of the saturated aliphatic polyol in the monomer group, 9, 7.5, 5, 2.5, 1, 0.5, 0.1, 0.09, 0.05 mol%. 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 0.05 to 10% by mole.

&Lt; Hydroxyl group-containing (meth) acrylate &

In the present disclosure, the "hydroxyl group-containing (meth) acrylate" means a compound having a hydroxyl group and a (meth) acrylic acid ester moiety. Two or more hydroxyl group-containing (meth) acrylates may be used in combination. In one embodiment, the hydroxyl group-containing (meth) acrylate has the structural formula D

(7)

(Wherein R ^5a 'is an alkylene group or a cycloalkylene group, and R ^5b ' is a hydrogen atom or a methyl group).

The hydroxyl group-containing (meth) acrylate is preferably at least one selected from the group consisting of? -Hydroxyethyl (meth) acrylate,? -Hydroxypropyl (meth) acrylate, (Meth) acrylate having a single ester moiety such as 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate or caprolactone modified? -Hydroxyethyl A hydroxyl group-containing (meth) acrylate; (Meth) acrylate having a plurality of ester moieties such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate, and the like.

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

The upper limit of the content of the hydroxyl group-containing (meth) acrylate 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 and 15 mol%. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate relative to 100 mol% of the monomer groups is preferably 15 to 40 mol%.

The upper limit of the content of the hydroxyl group-containing (meth) acrylate with respect to 100 parts by mass of the saturated aliphatic polyisocyanate in the monomer group is 240, 200, 150, 100, 50 and 25 parts by mass, and the lower limit is 230, 200, 150, 100, 50, 25, and 18 parts by mass, and the like. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate relative 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, %. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate relative to 100 mol% of the saturated aliphatic polyisocyanate is preferably 30 to 100 mol%.

The upper limit of the content of the hydroxyl group-containing (meth) acrylate 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 and 25 parts by mass, , 200, 150, 100, 50, 25, and 15 parts by mass. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate relative 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, Mol% and the like are exemplified. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate is preferably 25 to 300 mol% based on 100 mol% of the saturated aliphatic polyol.

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 the polyester polyol in the monomer group is 125, 100, 90, 75, 50, 25, 10, 5, And the lower limit thereof is exemplified by 100, 90, 75, 50, 25, 10, 5, 1, 0.9, 0.5, and 0.3 parts by mass. In one embodiment, the content of the hydroxyl group-containing (meth) acrylate relative to 100 parts by mass of the polyether polyol and / or the 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 relative to 100 mol% of the polyether polyol and / or the polyester polyol in the monomer group is 7, 5, 4, 2, 1, 0.9, 0.5, 0.1, 0.09 mol% And the lower limit is 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 relative to 100 mol% of the polyether polyol and / or the polyester polyol in the monomer group is preferably 0.05 to 7 mol%.

<Other monomers>

(Hereinafter, also referred to as " other monomer ") which does not correspond to any of saturated aliphatic polyisocyanate, saturated aliphatic polyol, polyether polyol, polyester polyol and hydroxyl group-containing (meth) Can be used. Other monomers include monofunctional and polyfunctional acrylates having no hydroxyl groups such as acryloyl morpholine, isobornyl acrylate, dicyclopentanyl acrylate and the like.

The content of other monomers relative to 100 parts by mass of the monomer group is 5, 4, 1 part by mass, 0 part by mass and the like.

The content of other monomers relative to 100 mol% of the monomer group is 5, 4, less than 1 mol%, 0 mol%, and the like.

<Physical properties of urethane (meth) acrylate>

Examples of the upper limit of the weight average molecular weight (Mw) of the urethane (meth) acrylate are 100,000, 75,000, 50,000, 25,000, 10,000, 5000 and 2000 and the lower limit is 90,000, 2.5 million, 10,000, 5000, 2000, 1000, etc. are exemplified. In one embodiment, the weight average molecular weight (Mw) of the urethane (meth) acrylate is preferably from 1,000 to 100,000.

The upper limit of the number average molecular weight (Mn) of the urethane (meth) acrylate is 100,000, 75,000, 50,000, 25,000, 10,000, 5000 and 2000. The lower limit is 90,000, 2.5 million, 10,000, 5000, 2000, 1000, etc. are exemplified. In one embodiment, the number average molecular weight (Mn) of the urethane (meth) acrylate is preferably from 1,000 to 100,000.

The upper limit of the content of the cycloalkylene group relative to 100 parts by mass of the urethane (meth) acrylate is 48, 45, 40, 35, 30, 25 and 20 parts by mass and the lower limit is 45, 40, 35, 30, 25, 20, 19 parts by mass, and the like. In one embodiment, 19 to 48 parts by mass of cycloalkylene group is contained relative to 100 parts by mass of urethane (meth) acrylate. In the present disclosure, the term " A mass part of the cycloalkylene group relative to 100 parts by mass of urethane (meth) acrylate " refers to, for example, a monomer having a cycloalkylene group only using 1,4-cyclohexane dimethanol Means that the formula weight of the cyclohexylene group with respect to 100 parts by mass of the molecular weight (chemical formula) of the urethane (meth) acrylate is A mass part when urethane (meth) acrylate is produced.

The method for producing the urethane (meth) acrylate is not particularly limited as long as it is a method of reacting a saturated aliphatic polyisocyanate, a saturated aliphatic polyol, a polyether polyol and / or a polyester polyol, and a hydroxyl group-containing (meth) A known production method is exemplified. The production method is a method of preparing a mixture by mixing a saturated aliphatic polyisocyanate, a saturated aliphatic polyol, a polyether polyol and / or a polyester polyol, and a hydroxyl group-containing (meth) acrylate, a method of producing a saturated aliphatic polyisocyanate, a saturated aliphatic polyol, And / or a polyester polyol are mixed and reacted in a batch, and then reacted with a hydroxyl group-containing (meth) acrylate.

In the monomer group, the molar ratio (OH / NCO) of the sum of the amounts of the hydroxyl groups in the respective monomers and the total amount of the isocyanate groups is preferably from 1.0 to 1.1 in view of toxicity and low moisture permeability.

[Active energy ray curable resin composition]

The present disclosure provides an active energy ray curable resin composition comprising the urethane (meth) acrylate. The composition may be suitably used for coating applications.

The upper limit of the content of the urethane (meth) acrylate in the composition is 100, 90, 80, 70, 60, 55 parts by mass and the lower limit is 95, 90, 80, 70, 60, 55, 50 parts by mass And the like. In one embodiment, it is preferable that the urethane (meth) acrylate is contained in an amount of 50 to 100 parts by mass with respect to 100 parts by mass of the composition from the viewpoint of low moisture permeability.

In one embodiment, the composition comprises a photopolymerization initiator. The photopolymerization initiator may be used in combination of two or more species. Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane- Phenyl-2-methyl-1-propan-1-one, 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and 4-methylbenzophenone.

In one embodiment, the content of the photopolymerization initiator is, for example, from 3.0 to 7.0 parts by mass from the viewpoint of curability with respect to 100 parts by mass of the composition. In another embodiment, the content of the photopolymerization initiator is from 3.0 to 3.0 parts by mass based on 100 parts by mass of the urethane (meth) 14 parts by mass, and the like.

In one embodiment, the composition comprises a diluent solvent. Two or more types of diluting solvents may be used in combination. The diluting solvent is selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, But are not limited to, acetone, toluene, xylene, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isopropyl ether, methyl cellosolve, ethyl cellosolve, , Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like. In one embodiment, the content of the diluting solvent is about 0 to 400 parts by mass in view of viscosity suitable for coating with respect to 100 parts by mass of the composition. In another embodiment, about 0 to about 800 parts by mass based on 100 parts by mass of urethane (meth) acrylate are exemplified.

The composition may contain a substance other than urethane (meth) acrylate, a photopolymerization initiator, and a diluting solvent as an additive. The additive may be at least one selected from the group consisting of antioxidants, ultraviolet absorbers, light stabilizers, antifoaming agents, surface conditioners, antifouling agents, inorganic fillers, silane coupling agents, colloidal silica, pigments, antistatic agents, . In one embodiment, the additive content is less than 5, 4, 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, and 0 parts by mass, etc., relative to 100 parts by mass of the composition. In another embodiment, Less than 0.1 parts by mass, less than 0.01 parts by mass, and 0 parts by mass, based on 100 parts by mass of (meth) acrylate.

[Cured goods]

The present disclosure provides a cured product of the active energy ray-curable resin composition. The cured product is 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.

[Shield]

The present disclosure provides a protective film comprising the cured product. The protective film is prepared by a method including a step of applying on a substrate, a step of irradiating an active energy ray to harden and laminating. Further, the step of irradiating the active energy ray can be performed during and / or after drying the coating.

The base material may be selected from the group consisting of polyethylene terephthalate (PET), polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetylcellulose resin, ABS resin, AS resin, And the like.

Application methods include BarCoater coating, Meyer bar coating, air knife coating, gravure coating, reverse-gravure coating, off set printing, flexo printing, , A screen printing method, and the like.

The protective film may be used for a barrier film, a polarizing plate, a packaging film, or the like.

[Example]

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, parts and% are based on mass unless otherwise specified.

Synthesis Example 1 (Synthesis of urethane acrylate containing cycloalkylene group)

31.0 parts of hydrogenated xylene diisocyanate (H-XDI), 16.0 parts of tricyclodecane dimethanol (hereinafter referred to as TCDDM), 20.0 parts of a polyether polyol (trade name: " ", NOF Corporation), 30.0 parts of butyl acetate and 0.01 g of tin octylate were prepared and reacted at 80 ° C. 18.9 parts of 2-hydroxyethyl acrylate (HEA), 0.01 g of tin octylate, and 0.07 g of hydroquinone monomethyl ether were added at the time when the remaining isocyanate group was found to be 8.4%, and the remaining isocyanate group was added in an amount of 0.1% Or less, to obtain 100 g of a urethane acrylate solution having a resin content of 70% (A-1).

The synthesis examples and comparative synthesis examples other than Synthesis Example 1 were carried out in the same manner as in Synthesis Example 1 except that the reaction components were changed as shown in the following table.

¹ A'-6 could not be synthesized by crystallization as the reaction proceeded.

H-XDI: hydrogenated xylene diisocyanate

NBDI: norbornylene 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 (2-hydroxyethyl acrylate)

PE3A: pentaerythritol triacrylate

Next, examples of the cured film of the urethane (meth) acrylate of the present invention are shown.

Example 1

, 54.4 parts of urethane acrylate (A-1), 1.9 parts of IRGACURE 184 (Irg.184) as photopolymerization initiator, and 43.7 parts of methyl ethyl ketone (MEK) were uniformly stirred to obtain an active energy ray curable resin composition having a solid content of 40%.

Examples 2 to 5 and Comparative Examples 1 to 5

In the same manner, the active energy ray-curable resin composition was produced in accordance with the compounding ratio shown in Table 2 below.

&Lt; Preparation of dry film &

The active energy ray-curable resin compositions of Examples 1-5 and Comparative Examples 1-5 were hand-coated on a triacetyl cellulose film or glass plate to a dry film thickness of 10 μm using Barcoater No. 20, Lt; / RTI &gt; for 3 minutes.

&Lt; Preparation of cured film &

A cured film was formed by irradiating a cumulative irradiation dose of 300 mJ / cm ² using a high-pressure mercury lamp such as 80 W, 1, and the like in the state of the dried film of Example 1-5 and Comparative Example 1-5, and the following evaluation was carried out.

&Lt; Evaluation of moisture permeability of cured film &

Measured according to the moisture permeability test method (cup method) of JIS Z 0208 using a cured film formed on a triacetyl cellulose film. The number of grams of water vapor passing through 24 hours per 1 m ² of the area of the test piece in an environment of a temperature of 40 ° C and a humidity of 90% RH was measured.

<Evaluation of Breaking Strength of Cured Film>

The measurement was carried out in accordance with the test conditions of the film and sheet of JIS K 7127 and the tensile property test method of JIS K 7161 by using a single-cured film obtained by peeling the cured film formed on the glass plate.

Table 3 shows the evaluation results of Examples 1-5 and Comparative Examples 1-5.

※ The breaking strength is weak and the specimen is broken during measurement.

Claims (5)

In the monomer group
Saturated aliphatic polyisocyanates,
Saturated aliphatic polyols,
Polyetherpolyol and / or polyester polyol,
And
The hydroxyl group-containing (meth) acrylate
Lt; / RTI &gt;
Wherein the reaction product of the monomer group containing the polyether polyol and / or the polyester polyol in an amount of 0.2 to 10 parts by mass, based on 100 parts by mass of the monomer group,
Urethane (meta) acrylate having 19 to 48 parts by mass of a cycloalkylene group per 100 parts by mass of urethane (meth) acrylate.
The polyurethane foam according to claim 1, wherein the saturated aliphatic polyisocyanate-derived structure A,
-CO-NH-R &lt; ^{1 &gt;} -NH-CO- (Structure A)
(Wherein R &lt; ¹ &gt; is an alkylene group or a cycloalkylene group)
The saturated aliphatic polyol-derived structure B
-OR &lt; ^{2 &gt;} -O- (Structure B)
(Wherein R ² is an alkylene group or a cycloalkylene group)
The following polyether polyol-derived structure C1
[Chemical Formula 1]

(Wherein R ³ is an alkylene group or a cycloalkylene group, and n is an integer of 2 or more)
And / or
The following structures C2,
(2)

(Wherein R ⁴ is an alkylene group or a cycloalkylene group, and m is an integer of 2 or more)
And
The following structures (D) derived from the hydroxyl group-containing (meth)
-OR ^5a -OC (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)
(Meth) acrylate.
An active energy line curable resin composition comprising the urethane (meth) acrylate of any one of claims 1 or 2.
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.