KR102352868B1 - Urethane(meth)acrylate, active energy ray curable resin composition, cured product and protective film - Google Patents

Abstract

[Problem] To provide a urethane (meth)acrylate, an active energy ray-curable resin composition, a cured product, and a protective film.
[Solutions] The monomer group contains saturated aliphatic polyisocyanate, saturated aliphatic polyol, polyether polyol and/or polyester polyol, and hydroxyl group-containing (meth)acrylate, with respect to 100 parts by mass of the monomer group, the polyether Polyol and/or the polyester polyol is obtained by reacting the monomer group containing 0.2 to 10 parts by mass, urethane containing 19 to 48 parts by mass of a cycloalkylene group with respect to 100 parts by mass of urethane (meth)acrylate ( providing meth)acrylates.

Description

Urethane (meth)acrylate, active energy ray curable resin composition, cured product and 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.

Plastic is light and has excellent processability, and is used in various fields. However, many plastics have high moisture permeability. For example, when used for protection of electronic substrates, etc., failure occurs easily due to contact of moisture with electronic substrates. Therefore, various studies are being conducted to suppress moisture permeability. 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 tends to permeate through the protective film (because the moisture permeability is high), so there is a problem that the plastic laminated to the protective film tends to absorb moisture and dehumidify. In recent years, thin film and low moisture permeability have been demanded, and in a thin film of 20 µm or less, for example, low moisture permeability such as a moisture permeability of 80 g/(m ² ·24h) or less is required. In addition, since there is a problem of being easily broken and destroyed in a thin layer state, there is a demand for a protective film having toughness, that is, handling and durability during operation.

The technical problem to be achieved by the present invention is to provide a urethane (meth) acrylate capable of forming a protective ^{film that combines low moisture permeability and toughness with a moisture permeability of 80 g/(m 2 ·24h) or less in a thin film of 20 μm or less.}

Regarding the said subject, as a result of repeating earnest examination, the present inventors revealed that the protective film which has low moisture permeability and toughness can be formed by using a specific urethane (meth)acrylate.

In accordance with the present disclosure, the following items are provided.

(Item 1)

in the group of monomers

saturated aliphatic polyisocyanate;

saturated aliphatic polyols;

polyetherpolyol and/or polyester polyol;

and,

Hydroxyl group-containing (meth)acrylate

including,

Based on 100 parts by mass of the monomer group, 0.2 to 10 parts by mass of the polyether polyol and/or the polyester polyol is a reactant of the monomer group,

With respect to 100 parts by mass of urethane (meth) acrylate, 19 to 48 parts by mass of a cycloalkylene group, urethane (meth) acrylate (urethane (meta) acrylate).

(Item 2)

The following structure A derived from said 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

-OR ² -O- ... (structure B)

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

The following structure C1 derived from the polyether polyol

[Formula 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 structure C2 derived from the polyester polyol,

[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 structure D derived from the said hydroxyl-containing (meth)acrylate

-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)

A urethane (meth) acrylate according to any one of the above items, including.

(Item 3)

An active energy line curable resin composition comprising the urethane (meth)acrylate according to any one of the above items.

(Item 4)

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

(Item 5)

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

One or a plurality of the above-described features may be provided in combination in addition to the specified combination. A person skilled in the art can recognize additional embodiments and advantages other than the above by reading and understanding the following detailed description as necessary.

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

Throughout the present disclosure, numerical ranges of each physical property value, content, etc. may be appropriately set (eg, by selecting from the upper and lower limits described in each item below). Specifically, for the numerical value α, when the upper limit of the numerical value α is exemplified by A1, A2, A3, etc. and the lower limit of the numerical value α is exemplified by B1, B2, B3, etc., the range of the numerical value α is A1 or less, A2 or less, A3 Hereinafter, B1 or more, B2 or more, B3 or more, A1 to B1, A1 to B2, A1 to B3, A2 to B1, A2 to B2, A2 to B3, A3 to B1, A3 to B2, A3 to B3, etc. are exemplified. .

[Urethane (meth)acrylate]

The present invention relates to a group of monomers.

saturated aliphatic polyisocyanate,

saturated aliphatic polyols,

polyether polyols and/or polyester polyols;

and,

Hydroxyl group-containing (meth)acrylate

including,

Based on 100 parts by mass of the monomer group, 0.2 to 10 parts by mass of the polyether polyol and/or the polyester polyol is a reactant of the monomer group,

Based on 100 parts by mass of urethane (meth)acrylate, 19 to 48 parts by mass of a cycloalkylene group is provided, to provide 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 acrylic and methacryl”.

In one embodiment, the urethane (meth) acrylate is

Structure A from a saturated aliphatic polyisocyanate,

-CO-NH-R ¹ -NH-CO- ... (structure A)

(wherein R ¹ is an alkylene group or a cycloalkylene group)

Structure B from a saturated aliphatic polyol

-OR ² -O- ... (structure B)

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

The following structure C1 from polyetherpolyol

[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 structure C2 derived from the polyester polyol,

[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 structure D derived from the said hydroxyl-containing (meth)acrylate

-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)

includes

<Saturated aliphatic polyisocyanate>

In the present disclosure, "saturated aliphatic polyisocyanate" means a compound consisting of a saturated aliphatic group and two or more isocyanate groups (-N=C=O). In the present disclosure, "saturated aliphatic group" means a compound composed of a double bond, a triple bond, etc. Refers to a hydrocarbon group not having an unsaturated bond.The saturated aliphatic group is exemplified by an alkyl group, a cycloalkyl group, an alkylene group, a cycloalkylene group, etc. The saturated aliphatic polyisocyanate can be used in combination of two or more types.

In one embodiment, the saturated aliphatic polyisocyanate has the structure

O=C=NR ¹ '-N=C=O ... (structure A)

(wherein R ¹ ' is an alkylene group or a cycloalkylene group)

is displayed as

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

Although the carbon number of a saturated aliphatic group is not specifically limited, The upper limit is 30, 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2 etc. are illustrated, The lower limit 29, 25, 20, 15, 12, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, etc. are exemplified. In one embodiment, the saturated aliphatic group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms.

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

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

The straight-chain aliphatic polyisocyanate is methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate. Isocyanate, decamethylene diisocyanate, etc. are illustrated.

A branched alkylene group is a group in which at least one hydrogen of a straight-chain alkylene group is substituted with an alkyl group. The branched alkylene group is exemplified by diethyl pentylene group, trimethyl butyl group, trimethyl pentylene group, trimethyl hexylene group and the like.

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 cycloalkylene group, and a condensed cyclic cycloalkylene group. In addition, in the cycloalkylene group, one or more hydrogens may be substituted with a straight-chain or branched alkyl group.

In the present disclosure, monocyclic refers to a cyclic structure having no cross-linked structure therein formed by covalent bonding of carbon. Also, the condensed ring refers to a cyclic structure in which two or more monocycles share two atoms (ie, only one share (condensed) around each ring). Cross-exchange refers to 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-trimethyl cyclohexylene group.

Examples of the cross-linked cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornylene group.

Examples of the condensed cyclic cycloalkylene group include a bicyclodecylene group.

Cycloalkylene polyisocyanates include monocyclic cycloalkylene polyisocyanates such as hydrogenation diphenylmethane diisocyanate (H12MDI), hydrogenated xylene diisocyanate (HXDI), and isophorone diisocyanate (IPDI); cross-linked cycloalkylene polyisocyanates such as norbornylene diisocyanate (NBDI); Condensed cyclic cycloalkylene polyisocyanate, such as bicyclo decylene diisocyanate, is illustrated.

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

As for the upper limit of the content of saturated aliphatic polyisocyanate with respect to 100 mass parts of monomer groups, 50, 45, 40, 35 mass parts etc. are illustrated, and 45, 40, 35, 30 mass parts etc. are illustrated as for a lower limit. In one embodiment, the content of the saturated aliphatic polyisocyanate with respect 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 with respect to 100 mol% of the monomer group is exemplified by 50, 45, 40, or 35 mol%, and the lower limit is exemplified by 45, 40, 35, 30 mol% or the like. In one embodiment, the content of the saturated aliphatic polyisocyanate with respect to 100 mol% of the monomer group is preferably 30-50 mol%.

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. Moreover, when saturated aliphatic polyisocyanate is cycloalkylene polyisocyanate, 6-7 pieces of carbon number of cycloalkylene are preferable from a low moisture permeability viewpoint.

<Saturated aliphatic polyol>

In the present disclosure, "saturated aliphatic polyol" refers to a compound in which two or more hydroxy groups (hydroxyl groups) are directly bonded to a saturated aliphatic group. Two or more types of saturated aliphatic polyols can be used in combination. In one embodiment, the aliphatic polyol is of structure B

HO-R ² '-OH ... (structural formula 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, an adduct thereof, a modified product, and the like.

Examples of the alkylene polyol include straight-chain 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 include neopentylglycol, 2,4-diethyl-1,5-pentanediol, 2,4-butyl-1,5-pentanediol Diol, 1-methylethylene glycol, 1-ethylethylene glycol, trimethylolpropane, pentaerythritol, etc. are illustrated.

Examples of the cycloalkylene polyol include monocyclic cycloalkylene polyol and cross-linked cycloalkylene polyol.

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

Examples of the cross-linked cycloalkylene polyol include tricyclodecane dimethanol.

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

40, 30, 20, 15 mass parts etc. are illustrated as an upper limit of saturated aliphatic polyol content with respect to 100 mass parts of monomer groups, 35, 30, 20, 10 mass parts etc. are illustrated as a lower limit. In one embodiment, the content of the saturated aliphatic polyol with respect to 100 parts by mass of the monomer group is preferably 10 to 40 parts by mass.

The upper limit of the content of the saturated aliphatic polyol relative to 100 mol% of the monomer group is exemplified by 40, 30, 20, or 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 with respect to 100 mol% of the monomer group is preferably 10 to 40 mol%.

The upper limit of the content of the saturated aliphatic polyol relative 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 like, and the lower limit is 75, 70, 60, 50, 40, 30 A mass part etc. are illustrated. 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.

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

<Polyether polyol>

In the present invention, "polyetherpolyol" refers to a compound having two or more hydroxy groups and two or more repeating units including ether bonds. Two or more types of polyether polyol can be used together. In one embodiment, the polyetherpolyol is of formula C1

^{HO- (R 3 '-O-) nH} ... ( 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 exemplified by 100,000, 75,000, 5025, 10,000, 5000, 2000, etc., and the lower limit is 90,000, 75,000, 50,000, 25,000, 1 However, 5000, 2000, 1000 and the like are exemplified. In one embodiment, the weight average molecular weight (Mw) of the polyether polyol is preferably from 1000 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, 2000, etc., and the lower limit is 90,000, 75,000, 50,000, 25,000, 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 1000 to 100,000.

The weight average molecular weight and the number average molecular weight are determined by gel permeation chromatography (eg, manufactured by Tosoh Corporation, trade name "HLC-8220", column: manufactured by Tosoh Corporation, trade name "TSKgel superHZ-M") It can be measured by a method using the same (hereinafter the same).

<Polyester Polyol>

In the present invention, "polyester polyol" refers to a compound having two or more hydroxyl groups and two or more repeating units including ester bonds in a molecule. A polyester polyol can use 2 or more types together. In one embodiment, the polyester polyol has structure C2

HO-{R ^4a '-OC(O)-R ^4b '-C(O)O}mR ^4a '-OH ... (structure 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 polyol and polyester polyol each contain a number of ether bonds and ester bonds, which are hydrophilic bonds. It has been found that while the protective film is thought to be easy for moisture to permeate through the protective film (higher water vapor permeability), a film with low water vapor permeability can be produced.

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

As for polycarboxylic acid, dicarboxylic acid etc. are illustrated.

Dicarboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sberic acid (sebacic acid), azelaic acid, sebacic acid, dodecanedioic acid, 2-methyl succinic acid, 2-methyl adipic acid, 3-methyl adipic acid Dipic acid, 3-methyl pentanedioic acid, 2-methyl octanedioic acid, 3,8-dimethyl decanedioic acid ), 3,7-dimethyl decanedionic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, trimellitic acid, trimesic acid, cyclohexanedicarboxylic acid, etc. carboxylic acid and the like are exemplified.

Polycarboxylic anhydrides include acetic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc. This is exemplified.

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, 5000, 2000, etc., and the lower limit is 90,000, 75,000, 50,000, 25,000, 10,000, 5000, 2000, 1000 and the like are exemplified. In one embodiment, the polyester polyol preferably has a weight average molecular weight (Mw) of 1000 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, 2000, etc., and the lower limit is 90,000, 75,000, 50,000, 250,000, 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 1000 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 exemplified by 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5 parts by mass, etc., and the lower limit is 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.2 parts by mass and the like are exemplified. In one embodiment, the content of the polyether polyol and/or the 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 polyether polyol and/or polyester polyol in 100 mol% of the monomer group is exemplified by 1, 0.75, 0.5, 0.25, 0.1, 0.05 mol%, etc., and the lower limit is 0.9, 0.75, 0.5, 0.25, 0.1, 0.05, 0.02 mol%, etc. are exemplified. In one embodiment, the content of polyether polyol and/or 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 exemplified by 20, 15, 10, 5, 1, 0.5 parts by mass, etc., and the lower limit is 19, 15, 10, 5, 1, 0.5, 0.4 parts by mass and the like 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 polyisocyanate is preferably 0.4 to 20 parts by mass.

The upper limit of the content of polyether polyol and/or polyester polyol in 100 mol% of saturated aliphatic polyisocyanate in the monomer group is exemplified by 2, 1, 0.5, 0.1 mol%, etc., 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 polyether polyol and/or polyester polyol in 100 mol % of 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, 0.9 parts by mass, etc., and the lower limit Silver 90, 75, 50, 25, 10, 5, 1, 0.9, 0.5 mass parts, etc. are illustrated. 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 in 100 mol% of the saturated aliphatic polyol among the monomer group is exemplified by 10, 9, 7.5, 5, 2.5, 1, 0.5, 0.1, 0.09 mol%, etc., and the lower limit is 9, 7.5, 5, 2.5, 1, 0.5, 0.1, 0.09, 0.05 mol% and the like 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 0.05 to 10 mol%.

<Hydroxy group-containing (meth)acrylate>

In the present disclosure, "hydroxyl group-containing (meth)acrylate" refers to a compound having a hydroxyl group and a (meth)acrylic acid ester moiety. Two or more types of hydroxyl-containing (meth)acrylates can be used together. In one embodiment, the hydroxyl-containing (meth)acrylate is of formula D

[Formula 7]

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

Hydroxyl group-containing (meth)acrylate is β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acryl rate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, ε-caprolactone-modified β-hydroxyethyl (meth) acrylate having one ester moiety hydroxyl group-containing (meth)acrylate; and hydroxyl group-containing (meth)acrylates having a plurality of ester moieties, such as pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

As for the upper limit of content of the hydroxyl-containing (meth)acrylate with respect to 100 mass parts of monomer groups, 60, 50, 40, 30, 20, 10 mass parts etc. are illustrated, The lower limit is 55, 50, 40, 30, 20, 10 , 8 parts by mass, etc. are exemplified. 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.

40, 30, 20 mol% etc. are illustrated as for the upper limit of content of the hydroxyl-containing (meth)acrylate with respect to 100 mol% of monomer groups, 35, 30, 20, 15 mol%, etc. are illustrated as for a lower limit. 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%.

Among the monomer groups, 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 is exemplified by 240, 200, 150, 100, 50, 25 parts by mass, and the like, and the lower limit is 230, 200, 150, 100, 50, 25, 18 mass parts etc. are illustrated. 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 among 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 are exemplified. 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 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, 25 parts by mass, and the like, and the lower limit is 400, 300 , 200, 150, 100, 50, 25, 15 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 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 like, and the lower limit is 200, 150, 100, 50, 25 mol% and the like are exemplified. 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 the polyester polyol in the monomer group is 125, 100, 90, 75, 50, 25, 10, 5, 1, 0.9, 0.5 A mass part etc. are illustrated, and 100, 90, 75, 50, 25, 10, 5, 1, 0.9, 0.5, 0.3 mass parts, etc. are illustrated as for a lower limit. 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 the polyester polyol in the monomer group is preferably 0.3 to 125 parts by mass.

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

<Other monomers>

Urethane (meth)acrylate is a monomer that does not correspond to any of saturated aliphatic polyisocyanate, saturated aliphatic polyol, polyether polyol, polyester polyol, and hydroxyl group-containing (meth)acrylate (hereinafter, also referred to as “other monomers”) can be used Examples of the other monomer include monofunctional and polyfunctional acrylates that do not have a hydroxyl group such as acryloyl morpholine, isobornyl acrylate, and dicyclopentanyl acrylate.

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

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

<Physical properties of urethane (meth)acrylate, etc.>

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

The upper limit of the number average molecular weight (Mn) of the urethane (meth)acrylate is exemplified by 100,000, 75,000, 50,000, 25,000, 10,000, 5000, 2000, etc., and the lower limit is 90,000, 75,000, 50,000, 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 1000 to 100,000.

The upper limit of the content rate 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 like, and the lower limit is 45, 40, 35, 30, 25, 20, 19 mass parts, etc. are illustrated. In one embodiment, with respect to 100 parts by mass of the urethane (meth)acrylate, 19 to 48 parts by mass of a cycloalkylene group is included. In the present disclosure, "with respect to 100 parts by mass of urethane (meth)acrylate, including A part by mass of a cycloalkylene group", for example, uses only 1,4-cyclohexane dimethanol as a monomer having a cycloalkylene group. In the case of producing urethane (meth)acrylate, it means that the formula weight of the cyclohexylene group is A mass part with respect to 100 parts by mass of the molecular weight (chemical formula) of the urethane (meth)acrylate.

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, A well-known manufacturing method is illustrated. The production method includes a method for preparing by mixing saturated aliphatic polyisocyanate, saturated aliphatic polyol, polyether polyol and/or polyester polyol, and hydroxyl group-containing (meth)acrylate, saturated aliphatic polyisocyanate, saturated aliphatic polyol, polyether polyol and/or a method of producing by reacting (meth)acrylate containing a hydroxyl group after mixing and reacting the polyester polyol at once.

In the monomer group, the molar ratio (OH/NCO) of the sum of the amount of the hydroxyl group of each monomer and the amount of the isocyanate group is preferably 1.0 to 1.1 from the viewpoint 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.

In the composition, the upper limit of the content of the urethane (meth)acrylate is exemplified by 100, 90, 80, 70, 60, 55 parts by mass, and the lower limit is 95, 90, 80, 70, 60, 55, 50 parts by mass. etc. are exemplified. In one embodiment, with respect to 100 parts by mass of the composition, it is preferable to include 50 to 100 parts by mass of the urethane (meth)acrylate from the viewpoint of low moisture permeability.

In one embodiment, the composition comprises a photopolymerization initiator. A photoinitiator can use 2 or more types together. The photopolymerization initiator is 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenyl ethan-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-morpholino propan-1-one, 2,4,6-trimethyl benzoyl-diphenyl-phosphine oxide, 4-methyl benzophenone and the like are exemplified.

In one embodiment, the content of the photoinitiator is exemplified by 3.0 to 7.0 parts by mass from the viewpoint of curability with respect to 100 parts by mass of the composition, and in another embodiment, 3.0 to 7.0 parts by mass with respect to 100 parts by mass of urethane (meth)acrylate 14 parts by mass and the like are exemplified.

In one embodiment, the composition includes a diluent. Two or more diluents may be used in combination. Diluents include 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, acetyl Acetone, 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, and the like. In one embodiment, the content of the diluent solvent is exemplified by about 0 to 400 parts by mass from the viewpoint of a suitable viscosity at the time of coating with respect to 100 parts by mass of the composition. In another embodiment, about 0 to 800 parts by mass and the like are exemplified with respect to 100 parts by mass of urethane (meth)acrylate.

The composition may include materials other than urethane (meth)acrylate, a photopolymerization initiator, and a diluting solvent as additives. Additives include antioxidants, ultraviolet absorbers, light stabilizers, defoamers, surface conditioners, antifouling agents, inorganic fillers, silane coupling agents, colloidal silica, pigments, antistatic agents, metal oxide fine particle dispersions, etc. This is exemplified. In one embodiment, the content of the additive is exemplified by 5, 4, less than 1 parts by mass, less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, etc. with respect to 100 parts by mass of the composition, and in another embodiment, urethane With respect to 100 mass parts of (meth)acrylates, 5, 4, less than 1 mass part, less than 0.1 mass part, less than 0.01 mass part, 0 mass part etc. are illustrated.

[Cured material]

The present disclosure provides a cured product of the active energy ray-curable resin composition. The said hardened|cured material is obtained by irradiating active energy rays, such as an ultraviolet-ray, an electron beam, and a radiation, to the said active energy ray-curable resin composition.

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 suitably adjusted according to the thickness of hardened|cured material.

[Shield]

The present disclosure provides a protective film including the cured product. The protective film is manufactured by a method including a step of applying on a substrate, curing by irradiating active energy rays, and lamination. In addition, the process of irradiating active energy rays may be performed during and/or after drying of the coating material.

The base material is polyethylene terephthalate (PET), polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornylene-based resin. etc. are exemplified.

Coating method is bar coater (BarCoater) coating, Meyer bar (Meyer bar) coating, air knife coating, gravure coating, reverse-gravure coating, offset (off set) printing, flexo printing , a screen printing method, and the like are exemplified.

The protective film may be used in a barrier film, a polarizing plate, a packaging film, and the like.

[Example]

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

<Synthesis Example 1> (Synthesis of urethane acrylate containing a cycloalkylene group)

31.6 parts of hydrogenated xylene diisocyanate (H-XDI), 16.0 parts of tricyclodecane dimethanol (hereinafter referred to as TCDDM), polyether polyol (trade name "Uniol D-2000") in a three-necked flask equipped with a stirrer, thermometer and reflux condenser ", NOF Co., Ltd. 3.5 parts, 30.0 parts of butyl acetate, and 0.01 g of tin octylate were prepared and reacted at 80 degreeC. When the residual isocyanate group appeared to be 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%. Reaction was advanced so that it might become the following, and 100 g (A-1) of the urethane acrylate solution of 70% of resin content was obtained.

Synthesis Examples and Comparative Synthesis Examples other than Synthesis Example 1 were performed 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-cyclohexane dimethanol

Polyether polyol (trade name "Uniol D-2000", manufactured by NOF Co., Ltd.)

Polyester polyol (trade name "kuraray polyol P-4010", manufactured by kuraray)

HEA: 2-hydroxyethyl acrylate

PE3A: pentaerythritol triacrylate

Next, the Example as a hardened|cured material film of the urethane (meth)acrylate of this invention is shown.

Example 1

54.4 parts of urethane acrylate (A-1), 1.9 parts of IRGACURE184 (Irg. 184) which is a photoinitiator, and 43.7 parts of methyl ethyl ketone (MEK) were stirred uniformly to obtain an active energy ray-curable resin composition having a solid content of 40%.

Examples 2-5 and Comparative Examples 1-5

Hereinafter, according to the compounding ratio of Table 2, it carried out similarly, and manufacture of the active energy ray-curable resin composition was performed.

<Production 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 a bar coater No20, and then at 90° C. dried for 3 minutes.

<Production of cured film>

In the state of the dry film of Example 1-5 and Comparative Example 1-5, a cured film was made by irradiating an integrated irradiation amount of 300 mJ/cm ² using a high-pressure mercury lamp 80W, 1 lamp, and the following evaluation was performed.

<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 made on a triacetyl cellulose film. In an environment of a temperature of 40°C and a humidity of 90% RH, the number of grams of water vapor passing through per ^{1 m 2 of the area of the test piece in 24 hours was measured.}

<Evaluation of breaking strength of cured film>

Using the single cured film obtained by peeling the cured film made on the glass plate, it was measured according to the test conditions for films and sheets of JIS K 7127 and the tensile property test method of JIS K 7161.

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

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

Claims (5)

in the group of monomers
saturated aliphatic polyisocyanate;
saturated aliphatic polyols;
polyetherpolyol and/or polyester polyol;
and,
Hydroxyl group-containing (meth)acrylate
including,
The monomer group includes only one type of saturated aliphatic polyisocyanate as a polyisocyanate,
Based on 100 parts by mass of the monomer group, 0.2 to 10 parts by mass of the polyether polyol and/or the polyester polyol is a reactant of the monomer group,
With respect to 100 parts by mass of urethane (meth) acrylate, 19 to 48 parts by mass of a cycloalkylene group, urethane (meth) acrylate (urethane (meta) acrylate).
2. The structure according to claim 1, wherein the 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
-OR ² -O- ... (structure B)
(wherein R ² is an alkylene group or a cycloalkylene group)
The following structure C1 derived from the polyether polyol
[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 structure C2 derived from the polyester polyol,
[Formula 2]

(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 said hydroxyl-containing (meth)acrylate
-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)
Including, urethane (meth) acrylate.
Claims 1 or 2 comprising the urethane (meth) acrylate, active energy line (active energy line) curable (curable) resin composition.
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 .