TW201902971A - Urethane (meth) acrylate, active energy ray curable resin composition, cured product and film - Google Patents

Abstract

This invention provides a urethane (meth)acrylate, an active energy ray-curable resin composition, a cured product and a film. The present invention provides a urethane (meth)acrylate which is characterized by comprising a reaction product of a compound group including: a polyisocyanate (A) which is a multimer of xylene diisocyanate and a hydroxyl group-containing (meth)acrylate (B). A film containing a cured product of an active energy ray-curable resin composition containing the urethane (meth)acrylate has high refractive index, high hardness, low curling property and high light resistance.

Description

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

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

A large number of optical films such as prism sheets, refractive index matching (IM) films, and antireflection films are used in liquid crystal displays. Among the above-mentioned films, a high refractive index resin material is required from the viewpoint of adjustment of high brightness, anti-frame visibility, and anti-reflection properties. The high refractive index resin material is, for example, a substance using a polymerizable monomer having a fluorene skeleton (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-007004

The active energy ray-curable resin composition requires various physical properties depending on the application. The technical problem to be solved by the present invention is to provide an active energy ray-curable resin composition for forming a hardened material layer having a high refractive index, high hardness, low curl, and high light resistance on the surface of a base film.

The present inventors conducted intensive research in order to solve the aforementioned technical problems, and found that the aforementioned technical problems can be solved by using a reactant having a specific structure, thereby completing the present invention.

The following items are provided by the present invention.

(Item 1)

A urethane (meth) acrylate, characterized in that it contains the reactants of the following compound groups (A) and (B): polyisocyanate (A), which is a polymer of xylene diisocyanate; And (meth) acrylate (B) containing a hydroxyl group.

(Item 2)

The urethane (meth) acrylate according to the above item, wherein the polyisocyanate (A) is an isocyanurate polymer, a biuret polymer, or an addition of xylene diisocyanate Multimer.

(Item 3)

An active-energy-ray-curable resin composition characterized by containing the urethane (meth) acrylate as described in any one of the above items.

(Item 4)

The active energy ray-curable resin composition according to the above item, wherein the active energy ray-curable resin composition contains a photopolymerization initiator.

(Item 5)

The active energy ray-curable resin composition according to any one of the above items, wherein the active energy ray-curable resin composition contains a polymerizable monomer.

(Item 6)

The active energy ray-curable resin composition according to any one of the above items, wherein the active energy ray-curable resin composition contains an antistatic agent.

(Item 7)

The hardened | cured material of the active-energy-ray-curable resin composition as described in any one of the said items.

(Item 8)

A film characterized by containing the hardened | cured material as described in the said item.

In the present invention, further combinations may be provided for one or more of the above features in addition to the combinations explicitly stated.

By using the active energy ray-curable resin composition provided by the present invention, it is possible to form a hardened material layer (hardened film) having a high refractive index, high hardness, low curl, and high light resistance on the surface of the base film.

Throughout the present invention, ranges of numerical values such as values and contents of physical properties can be appropriately set (for example, selected from the values of the upper and lower limits described in the following items). Specifically, for the numerical value α, when the upper limit of the numerical value α is, for example, A1, A2, A3, etc., and the lower limit of the numerical value α is, for example, B1, B2, B3, etc., the range of the numerical value α is, for example, A1 or lower, A2 or lower, Below A3, above B1, above B2, above B3, A1 ~ B1, A1 ~ B2, A1 ~ B3, A2 ~ B1, A2 ~ B2, A2 ~ B3, A3 ~ B1, A3 ~ B2, A3 ~ B3, etc.

[Urethane (meth) acrylate]

The present invention provides a urethane (meth) acrylate, which is a reactant containing the following compound groups (A) and (B): polyisocyanate (A), which is a polymer of xylene diisocyanate Body; and (meth) acrylate (B) containing a hydroxyl group.

In the present invention, "(meth) acrylic acid" means "at least one selected from the group consisting of acrylic acid and methacrylic acid". Similarly, "(meth) acrylate" means "at least one selected from the group consisting of acrylate and methacrylate". In addition, "(meth) acrylfluorenyl" means "at least one selected from the group consisting of acrylfluorenyl and methacrylfluorenyl".

<Polyisocyanate (A), which is a polymer of xylene diisocyanate: also known as polyisocyanate (A), (A) component>

In the present invention, the "polyisocyanate" means a compound having two or more isocyanate groups (-N = C = O).

The polyisocyanate (A) may be used alone or in combination of two or more kinds. In one embodiment, the polyisocyanate (A) is an isocyanurate polymer, a biuret polymer, or an addition polymer of xylene diisocyanate.

The isocyanurate polymer of xylene diisocyanate is, for example, a compound represented by the following structural formula (A-1).

(In the formula, n1 is an integer of 0 or more. N1 is preferably 0 to 3.)

The biuret polymer of xylene diisocyanate is, for example, a compound represented by the following structural formula (A-2).

(In the formula, n2 is an integer of 0 or more. N2 is preferably 0 to 3.)

The addition polymer of xylene diisocyanate is, for example, an addition product of trimethylolpropane represented by the following structural formula (A-3) and xylene diisocyanate; [Chem. 3]

(In the formula, n3 is an integer of 0 or more. N3 is preferably 0 to 3.)

An addition product of glycerol and xylene diisocyanate, etc. represented by the following structural formula (A-4).

(In the formula, n4 is an integer of 0 or more. N4 is preferably 0 to 3.)

In addition, the above structural formula is only an example, and the present invention is not intended to be limited to the compound represented by the above structural formula.

The "multimer of xylene diisocyanate" in the present invention means a compound having a dimer or higher. The upper limit of the polymerization degree of the polymer of xylene diisocyanate is, for example, 12, 11, 10, 9, 8, 7, 6, 5, 4, etc., and the lower limit is, for example, 11, 10, 9, 8, 7, 6, 5, 4, 3, etc. In one embodiment, the degree of polymerization is preferably 3-12, and more preferably 3-9. In addition, commonly available polymers are a mixture of different polymers, and the degree of polymerization is an average value, that is, expressed as the average degree of polymerization. The preferable value of the average polymerization degree is the same as the above-mentioned preferable value of the polymerization degree. In the present invention, the degree of polymerization of the n-mer is n.

The value of the weight average molecular weight (Mw) of the polyisocyanate (A) is not particularly limited. The upper limit of the weight average molecular weight (Mw) of the polyisocyanate (A) is, for example, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1500, 1000, 600, etc. The lower limits are, for example, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1500, 1000, 600, 500, and so on. In one embodiment, from the viewpoint of the productivity of the urethane (meth) acrylate, the weight average molecular weight (Mw) of the polyisocyanate (A) is preferably 500 to 50,000, and more preferably 600. ~ 50000.

The value of the number average molecular weight (Mn) of the polyisocyanate (A) is not particularly limited. The upper limit of the number average molecular weight (Mn) of the polyisocyanate (A) is, for example, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 600, 500, 500, 300, etc. The lower limit is, for example, 55,000, 50000, 40,000, 35000, 30,000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 500, and so on. In one embodiment, from the viewpoint of the productivity of the urethane (meth) acrylate, the number average molecular weight (Mn) of the polyisocyanate (A) is preferably 500 to 60,000, and more preferably 500. ~ 40000.

The upper limit of the molecular weight distribution (Mw / Mn) of the polyisocyanate (A) is, for example, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, or the like, and the lower limit is, for example, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, 1.0, or the like. In one embodiment, from the viewpoint of the productivity of the urethane (meth) acrylate, the molecular weight distribution (Mw / Mn) of the polyisocyanate (A) is preferably 1.0 to 8.0.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined from polystyrene conversion values measured by gel permeation chromatography (GPC) (the same applies hereinafter).

The ratio of the polyisocyanate (A) to 100 parts by mass of the compound group is not particularly limited as long as a desired effect can be obtained. The upper limit of the proportion of the polyisocyanate (A) with respect to 100 parts by mass of the compound group is, for example, 70, 60, 50, 40, 30, 25, 20, 10 parts by mass, and the like, and the lower limit is, for example, 60, 50, 45, 40, 30. , 20, 10, 5 parts by mass. In one embodiment, from the viewpoint of both high hardness, low curlability, and high refractive index, the ratio of the polyisocyanate (A) to 100 parts by mass of the compound group is preferably 5 to 70 parts by mass, and more preferably It is preferably 20 to 70 parts by mass.

<Hydroxy-containing (meth) acrylate (B): also referred to as (B) component>

In the present invention, the "hydroxy-containing (meth) acrylate" means a compound having a hydroxyl group and a (meth) acrylfluorenyl group.

The hydroxyl group-containing (meth) acrylate may be used alone or in combination of two or more. The hydroxyl-containing (meth) acrylate is, for example, glycerol (meth) acrylate (B-1) containing hydroxyl, (poly) pentaerythritol poly (meth) acrylate (B-2) containing hydroxyl, or hydroxyl-containing (meth) acrylate (Poly) trimethylolpropane poly (meth) acrylate (B-3), a hydroxyl-containing monofunctional (meth) acrylate (B-4), and the like.

(Glycerol (meth) acrylate (B-1) containing hydroxyl group)

The glycerol (meth) acrylate containing a hydroxyl group is a compound represented by a structural formula (B-1).

(Wherein R ^b1 to R ^b3 may be each independently a hydrogen atom, a (meth) acrylfluorenyl group, an alkyl group, an aryl group, or

(In the formula, b is an integer of 1 or more.)

At least one of R ^b1 to R ^{b3 is} a hydrogen atom or

(In the formula, b is an integer of 1 or more.) At the same time, at least one is a (meth) acrylfluorenyl group. )

Glycerol (meth) acrylate containing a hydroxyl group is, for example, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl (meth) Acrylate, 2-hydroxy-3-methoxypropyl (meth) acrylate, 1-hydroxy-2-phenoxypropyl (meth) acrylate, 1-hydroxy-2- (meth) propylene Methoxypropyl (meth) acrylate, 1-hydroxy-2-methoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate caprolactone Adducts, etc.

(Hydroxy-containing (poly) pentaerythritol poly (meth) acrylate (B-2))

The hydroxyl-containing (poly) pentaerythritol poly (meth) acrylate is a compound represented by the structural formula (B-2).

(In the formula, m is an integer of 0 or more, and R ^b4 to R ^b9 may be each independently a hydrogen atom, a (meth) acrylfluorenyl group, or

(In the formula, b is an integer of 1 or more.) In the structural formula (B-2), at least one selected from R ^b4 to R ^b9 is a hydrogen atom, or

(In the formula, b is an integer of 1 or more.) At least one of them is a (meth) acrylfluorenyl group. In addition, R ^b7 and R ^b8 may have different groups for each structural unit. )

In the present invention, "(poly) pentaerythritol poly (meth) acrylate" means "at least one selected from the group consisting of pentaerythritol poly (meth) acrylate and polypentaerythritol poly (meth) acrylate".

In addition, the "group may be different for each structural unit" means that, for example, in the structural formula (B-2), when m is 2,

R ^b7A and R ^b7B may be different groups, and R ^b8A and R ^b8B may be different groups (hereinafter the same).

The pentaerythritol poly (meth) acrylate is, for example, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, or the like.

The polypentaerythritol poly (meth) acrylate is, for example, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate , Tripentaerythritol di (meth) acrylate, Tripentaerythritol tri (meth) acrylate, Tripentaerythritol tetra (meth) acrylate, Tripentaerythritol penta (meth) acrylate, Tripentaerythritol hexa (meth) acrylate , Tripentaerythritol hepta (meth) acrylate and the like.

(Hydroxy-containing (poly) trimethylolpropane poly (meth) acrylate (B-3))

The (poly) trimethylolpropane poly (meth) acrylate containing a hydroxyl group is a compound represented by a structural formula (B-3).

(In the formula, p is an integer of 0 or more, and R ^b10 to R ^b13 are a hydrogen atom, a (meth) acrylfluorenyl group, or [Chemical Formula 13]

(In the formula, b is an integer of 1 or more.) At least one selected from R ^b10 to R ^b13 is a hydrogen atom or

(In the formula, b is an integer of 1 or more.) At the same time, at least one is a (meth) acrylfluorenyl group. In addition, R ^b12 may have different groups for each structural unit. )

In the present invention, "(poly) trimethylolpropane poly (meth) acrylate" means "selected from trimethylolpropane poly (meth) acrylate and polytrimethylolpropane poly (meth) acrylate At least one of the groups of esters. "

Trimethylolpropane poly (meth) acrylate is, for example, trimethylolpropane di (meth) acrylate.

The polytrimethylolpropane poly (meth) acrylate is, for example, bistrimethylolpropane di (meth) acrylate, bistrimethylolpropane tri (meth) acrylate, bistrimethylolpropane tetra (Meth) acrylates and the like.

(Hydroxy-containing monofunctional (meth) acrylate (B-4))

The hydroxyl-containing monofunctional (meth) acrylate is a compound represented by the structural formula (B-4).

( ^Wherein R ^b14 is a hydrogen atom or a methyl group, and R ^b15 is a linear alkylene group, a branched alkylene group, a cycloalkylene group, or

(In the formula, R ^b15a is a hydrogen atom or an alkyl group (for example, methyl).), R ^b16 is a hydrogen atom or [ ^Chem . 17]

(In the formula, b is an integer of 1 or more.)

The compound represented by the structural formula (B-4) is, for example, a linear alkyl (meth) acrylate containing a hydroxyl group, a linear alkyl (meth) acrylate containing a hydroxyl group, a caprolactone adduct, or a hydroxyl group containing Branched alkyl (meth) acrylate, hydroxyl-containing branched alkyl (meth) acrylate caprolactone adduct, hydroxyl-containing cycloalkyl (meth) acrylate, hydroxyl-containing cycloalkyl (Meth) acrylate caprolactone adduct, polyalkylene glycol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate caprolactone adduct, and the like.

The hydroxyl-containing linear alkyl (meth) acrylate is, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Wait.

Hydroxyl-containing linear alkyl (meth) acrylate caprolactone adducts are, for example, 3-hydroxypropyl (meth) acrylate caprolactone adducts, 2-hydroxyethyl (meth) acrylate Caprolactone adduct, 4-hydroxybutyl (meth) acrylate caprolactone adduct, and the like.

The hydroxyl-containing branched alkyl (meth) acrylate is, for example, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate Wait.

The hydroxyl-containing branched chain alkyl (meth) acrylate caprolactone adduct is, for example, 2-hydroxypropyl (meth) acrylate caprolactone adduct, 2-hydroxybutyl (meth) acrylate Caprolactone adduct, 3-hydroxybutyl (meth) acrylate caprolactone adduct, and the like.

The hydroxy-containing cycloalkyl (meth) acrylate is, for example, hydroxycyclohexyl (meth) acrylate and the like.

The hydroxy-containing cycloalkyl (meth) acrylate caprolactone adduct is, for example, a hydroxycyclohexyl caprolactone (meth) acrylate adduct.

The polyalkylene glycol mono (meth) acrylate is, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, or the like.

The polyalkylene glycol mono (meth) acrylate caprolactone adduct is, for example, polyethylene glycol mono (meth) acrylate caprolactone adduct, polypropylene glycol mono (meth) acrylate caprolactone Ester adducts, etc.

The hydroxyl value of the hydroxyl-containing (meth) acrylate (B) is not particularly limited as long as the desired effect can be obtained. The upper limit of the hydroxyl value of the hydroxyl-containing (meth) acrylate (B) is, for example, 500, 490, 450, 400, 350, 300, 250, 200, 150, 100, 80, 75, 70, 65, 60, 55 , 50, 45, 40, 35, 30, 25, 20 mgKOH / g, etc. The lower limit is, for example, 400, 350, 300, 250, 200, 150, 100, 80, 70, 65, 60, 55, 50, 45, 40 , 35mgKOH / g and so on. In one embodiment, from the viewpoints of both high hardness, low curlability, and high refractive index, the polypentaerythritol poly (meth) acrylate (B) preferably has a hydroxyl value of 35 to 500 mgKOH / g, and more preferably It is preferably 35 ~ 490mgKOH / g.

In the present invention, the hydroxyl value refers to a calculated value obtained by the following formula: (hydroxy value) = (potassium hydroxide molecular weight: 56.1) × 1000 / (hydroxyl equivalent); (hydroxyl equivalent) = (molecular weight of 1 molecule) ) / (Number of hydroxyl groups present in 1 molecule).

The (meth) acrylic acid equivalent of the hydroxyl group-containing (meth) acrylate (B) is not particularly limited as long as the desired effect can be obtained. The upper limit of the (meth) acrylic equivalent of the hydroxyl-containing (meth) acrylate (B) is, for example, 500, 450, 400, 350, 300, 250, 200, 150, 140, 130, 120, 110 g / eq, etc., The lower limit is, for example, 140, 130, 120, 110, 100, 99, 95 g / eq, and the like. In one embodiment, from the viewpoint of having both high hardness, low curlability, and high refractive index, the (meth) acrylic equivalent of the hydroxyl-containing poly (meth) acrylate (B) is preferably 95 to 500 g. / eq, more preferably 99 to 150 g / eq.

In the present invention, the "(meth) acrylic group equivalent" refers to the molecular weight per 1 mol of the (meth) acrylic group, and is calculated by the following formula: ((meth) acrylic group equivalent) = (1 molecule Molecular weight) / (number of (meth) acrylic groups present in 1 molecule).

The upper limit of the ratio of the hydroxyl-containing poly (meth) acrylate (B) to 100 parts by mass of the compound group is, for example, 80, 70, 60, 50, 40, 35 parts by mass, and the like, and the lower limit is, for example, 70, 60, 55. , 50, 40, 30 parts by mass. In one embodiment, from the viewpoint of having both high hardness and high refractive index, the ratio of the poly (meth) acrylate (B) containing a hydroxyl group is preferably 30 to 80 masses with respect to 100 mass parts of the compound group. Serving.

<Compounds which are neither (A) component nor (B) component: also referred to as other compounds>

When producing the said urethane (meth) acrylate, the compound which is neither (A) component nor (B) component can be used. That is, the compound group may contain a compound that is neither the (A) component nor the (B) component.

In one embodiment, with respect to 100% by mass of the compound group, the ratio of other compounds is, for example, 0-50% by mass, less than 40% by mass, less than 25% by mass, less than 10% by mass, less than 5% by mass, and less than 1 Mass%, less than 0.1% by mass, less than 0.01% by mass, 0% by mass, etc.

In one embodiment, with respect to 100 mole% of the compound group, the proportion of other compounds is, for example, 0 to 50 mole%, less than 40 mole%, less than 25 mole%, less than 10 mole%, and less than 5 Mole%, less than 1 mole%, less than 0.1 mole%, less than 0.01 mole%, 0 mole%, etc.

The method for producing the urethane (meth) acrylate may be a conventional method, and the component (A) and the component (B) can be contained in a solvent-free or suitable solvent (such as toluene) in a suitable catalyst. In the presence of (tin octoate, etc.), the reaction may be performed at an appropriate reaction temperature (60 to 90 ° C, etc.).

<Relative ratio of each component>

As long as the desired effect can be obtained, the mass ratio of polyisocyanate (A) to hydroxyl-containing (meth) acrylate (B) (polyisocyanate (A) / hydroxyl-containing (meth) acrylate (B)) and No special restrictions. The upper limit of the mass ratio of the polyisocyanate (A) to the hydroxyl-containing (meth) acrylate (B) (polyisocyanate (A) / hydroxyl-containing (meth) acrylate (B)) is, for example, 2.5, 2, 1.9 , 1.5, 1.0, 0.9, 0.5, 0.4, 0.3, and the like, and the lower limit is, for example, 2, 1.9, 1.5, 1.0, 0.9, 0.5, 0.4, 0.3, 0.25, and the like. In one embodiment, the mass ratio of polyisocyanate (A) to hydroxyl-containing (meth) acrylate (B) (polyisocyanate (A ) / (Meth) acrylate (B)) containing a hydroxyl group is preferably 0.25 to 2.5.

The upper limit of the mass ratio of other compounds to the polyisocyanate (A) (other compounds / polyisocyanate (A)) is, for example, 10, 9, 7.5, 5, 2.5, 1, 0.5, etc., and the lower limit is, for example, 9, 7.5, 5, 2.5. , 1, 0.5, 0, etc. In one embodiment, the mass ratio of the other compound to the polyisocyanate (A) (other compound / polyisocyanate (A)) is preferably 0 to 10.

The upper limit of the mass ratio of the other compound to the hydroxyl-containing polypentaerythritol poly (meth) acrylate (B) (other compounds / hydroxyl-containing polypentaerythritol poly (meth) acrylate (B)) is, for example, 1, 0.9, or 0.75. , 0.5, 0.25, 0.1, 0.05, and the like, and the lower limit is, for example, 0.9, 0.75, 0.5, 0.25, 0.1, 0.05, 0, and the like. In one embodiment, the mass ratio of the other compound to the hydroxyl-containing polypentaerythritol poly (meth) acrylate (B) (other compound / hydroxyl-containing polypentaerythritol poly (meth) acrylate (B)) is preferably 0 ~ 1.

The ratio [(OH) / (NCO)] of the amount of the hydroxyl group of the hydroxyl group-containing (meth) acrylate (B) to the isocyanate group of the polyisocyanate (A) is not particularly limited as long as the desired effect can be obtained. The upper limit of the ratio [(OH) / (NCO)] of the hydroxyl group-containing (meth) acrylate (B) to the isocyanate group amount of the polyisocyanate (A) is, for example, 3.0, 2.5, 2.0, 1.5, 1.0, etc. The lower limit is, for example, 2.4, 2.0, 1.5, 1.0, 0.95, and the like. In one embodiment, the ratio [(OH) / (NCO)] of the amount of the hydroxyl group of the hydroxyl group-containing (meth) acrylate (B) to the isocyanate group of the polyisocyanate (A) is preferably 0.95 to 3.0.

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

The weight average molecular weight (Mw) of the urethane (meth) acrylate is not particularly limited. The upper limit of the weight average molecular weight (Mw) of the urethane (meth) acrylate is, for example, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, etc. The lower limits are, for example, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 10,000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1750, 1700, 1500, and the like. In one embodiment, the weight average molecular weight (Mw) of the urethane (meth) acrylate is preferably 1500 from the viewpoint of productivity of the urethane (meth) acrylate and the film. ~ 800,000, more preferably 1700 ~ 80,000.

The number average molecular weight (Mn) of the urethane (meth) acrylate is not particularly limited. The upper limit of the number average molecular weight (Mn) of the urethane (meth) acrylate is, for example, 80,000, 70,000, 60,000, 50,000, 40,000, 30,000, 20,000, 12000, 10,000, 9000, 8100, 8000, 7800, 7000, 6000, 5600, 5000, 4000, 3500, 3100, 3001, 3000, 2900, 2000, etc. The lower limit is, for example, 70,000, 60,000, 50000, 40,000, 30,000, 20000, 12000, 10000, 9000, 8100, 8000, 7800, 7000, 6000, 5600, 5000, 4000, 3500, 3100, 3001, 3000, 2900, 2000, 1500, 1200, 1000, etc. In one embodiment, from the viewpoint of the productivity of the urethane (meth) acrylate and the film, the number average molecular weight (Mn) of the urethane (meth) acrylate is preferably 1,000. ~ 80000, more preferably 1200 ~ 80,000.

The molecular weight distribution (Mw / Mn) of the urethane (meth) acrylate is not particularly limited. The upper limit of the molecular weight distribution (Mw / Mn) of the urethane (meth) acrylate is, for example, 8.0, 7.0, 6.0, 5.0, 4.0, 3.0, 2.0, and the like, and the lower limit is, for example, 8.0, 7.0, 6.0, 5.0, 4.0 , 3.0, 2.0, 1.2, 1.0, etc. In one embodiment, from the viewpoint of the productivity of the urethane (meth) acrylate and the film, the molecular weight distribution (Mw / Mn) of the urethane (meth) acrylate is preferably 1.0 to 8.0, more preferably 1.2 to 6.0.

The (meth) acrylic equivalent of the urethane (meth) acrylate is not particularly limited as long as the desired effect can be obtained. The upper limit of the (meth) acrylic equivalent of the urethane (meth) acrylate is, for example, 400, 350, 300, 290, 150, 140, 130, 120, 110 g / eq, etc., and the lower limit is, for example, 390, 350, 300, 290, 140, 130, 120, 110, 100g / eq, etc. In one embodiment, from the viewpoint of both high hardness and low curlability, the (meth) acrylic equivalent of the urethane (meth) acrylate is preferably 100 to 400 g / eq, and more preferably It is 280 ~ 400g / eq.

[Active energy ray-curable resin composition: also called composition]

The present invention provides an active energy ray-curable resin composition containing the urethane (meth) acrylate.

The content of the urethane (meth) acrylate is not particularly limited as long as the desired effect can be obtained. The upper limit of the content of the urethane (meth) acrylate relative to 100 parts by mass of the composition is, for example, 100, 90, 80, 70, 60, 51, 50, 40, 36, 35, 31, 30 , 29, 20, 15 parts by mass, and the like, and the lower limit is, for example, 90, 80, 70, 60, 51, 50, 40, 36, 35, 31, 30, 29, 20, 15, 10, and so on. In one embodiment, from the viewpoint of having both high hardness, low curlability, and high refractive index, the content of the urethane (meth) acrylate is preferably based on 100 parts by mass of the composition. About 10 to 100 parts by mass.

<Photopolymerization initiator>

In one embodiment, the active energy ray-curable resin composition contains a photopolymerization initiator. As the photopolymerization initiator, various conventional photopolymerization initiators may be used alone, or two or more of them may be used in combination. In addition, a photopolymerization initiator is used when ultraviolet curing is performed, but when an electron beam curing is performed, a photopolymerization initiator is not necessary.

The photopolymerization initiator is, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-cyclohexylphenyl ketone, 2 -Hydroxy-2-methyl-1-phenyl-propane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2,4,6-trimethylbenzyl-diphenyl -Phosphine oxide, 4-methylbenzophenone and the like.

The upper limit of the content of the photopolymerization initiator with respect to 100 parts by mass of the composition is, for example, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, and 1 part by mass, and the lower limit is, for example, 9, 8, 7 , 6, 5, 4, 3, 2, 1, 0.5, 0 parts by mass. In one embodiment, from the viewpoint of the reaction of the (meth) acrylfluorenyl group, the content of the photopolymerization initiator is preferably 0 to 10 parts by mass based on 100 parts by mass of the composition.

The upper limit of the content of the photopolymerization initiator with respect to 100 parts by mass of the urethane (meth) acrylate is, for example, 66.7, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 , 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 part by mass, etc., and the lower limit is, for example, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 , 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0 parts by mass. In one embodiment, the content of the photopolymerization initiator is preferably about 0 with respect to 100 parts by mass of the urethane (meth) acrylate from the viewpoint of the progress of the (meth) acrylfluorenyl group. ~ 30.0 parts by mass.

<Polymerizable monomer>

In one embodiment, the active energy ray-curable resin composition contains a polymerizable monomer. As the polymerizable monomer, various conventional polymerizable monomers may be used alone, or two or more of them may be used in combination.

The polymerizable monomer is, for example, isobornyl (alkylene oxide modified or epoxy modified) (meth) acrylate, tetrahydrofurfuryl (alkylene oxide modified or epoxy modified) (methyl ) Acrylate, hydroxyethyl (alkylene oxide modified or epoxy modified) (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (alkylene oxide modified or (Epoxy modified) (meth) acrylate, lauryl (alkylene oxide modified or epoxy modified) (meth) acrylate, 1,4-butanediol di (alkylene oxide modified or Epoxy modified) (meth) acrylate, 1,6-hexanediol di (alkylene oxide modified or epoxy modified) (meth) acrylate, tetraethylene glycol di (alkylene oxide) (Modified or epoxy modified) (meth) acrylate, tripropylene glycol di (alkylene oxide modified or epoxy modified) (meth) acrylate, trimethylolpropane tri (alkylene oxide modified) (Epoxy modified) (meth) acrylate, pentaerythritol tri (alkylene oxide modified or epoxy modified) (meth) acrylate, pentaerythritol tetra (alkylene oxide modified or epoxy modified) ) (Meth) acrylate, dipentaerythritol penta (alkylene oxide modified or epoxy modified) (meth) acrylate, two Pentaerythritol hexa (alkylene oxide modified or epoxy modified) (meth) acrylate, tripentaerythritol octa (alkylene oxide modified or epoxy modified) (meth) acrylate and the like.

In the present invention, "(alkylene oxide modified or epoxy modified) (meth) acrylate" means "selected from (meth) acrylate, alkylene oxide modified (meth) acrylate And at least one of the groups of epoxy-modified (meth) acrylates. "

The content of the polymerizable monomer is not particularly limited. The upper limit of the content of the polymerizable monomer with respect to 100 parts by mass of the composition is, for example, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 36, 35, 30, 25, 20, 19, 15, 14, 10, 5 parts by mass, and the lower limit is, for example, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 36, 35, 30, 25, 20, 19, 15, 14, 10, 5, 0 parts by mass. In one embodiment, from the viewpoint of both high hardness, low curlability, and high refractive index, the content of the polymerizable monomer is preferably about 0 to 85 parts by mass relative to 100 parts by mass of the composition, and more preferably It is preferably about 0 to 70 parts by mass.

The upper limit of the content of the polymerizable monomer with respect to 100 parts by mass of the urethane (meth) acrylate is, for example, 567, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50 , 25, 10, 5, 1 part by mass, etc., and the lower limit is, for example, 550, 500, 450, 400, 350, 300, 250, 200, 150, 100, 50, 25, 10, 5, 1, 0 parts by mass, and the like. In one embodiment, from the viewpoint of both high hardness, low curlability, and high refractive index, the content of the polymerizable monomer is preferably 100 parts by mass based on the urethane (meth) acrylate. About 0 to 567 parts by mass, more preferably about 0 to 300 parts by mass.

<Antistatic agent>

In one embodiment, the composition contains an antistatic agent. The antistatic agent may be used alone or in combination of two or more.

Examples of the antistatic agent include: anionic antistatic agents such as alkyl phosphate esters; cationic antistatic agents such as quaternary ammonium salts; nonionic antistatic agents such as polyoxyethylene alkyl ether; and alkali metals such as lithium, sodium, and potassium Antistatic agents for salts; antistatic agents for ionic liquids, etc.

The content of the antistatic agent is not particularly limited. The upper limit of the content of the antistatic agent with respect to 100 parts by mass of the composition is, for example, 100, 50, 40, 30, 20, 15, 10, 5 parts by mass, and the like, and the lower limit is, for example, 50, 25, 20, 15, 10, 5 , 2.5, 0 parts by mass. In one embodiment, from the viewpoint of coatability, the content of the antistatic agent is preferably about 0 to 100 parts by mass, and more preferably about 0 to 25 parts by mass, based on 100 parts by mass of the composition.

The upper limit of the content of the antistatic agent with respect to 100 parts by mass of the urethane (meth) acrylate is, for example, 500, 100, 50 parts by mass, and the like, and the lower limit is, for example, 100, 50, 25, 10, 5, 1, 0.5, 0 parts by mass, etc. In one embodiment, the content of the antistatic agent is more preferably 100 parts by mass of the urethane (meth) acrylate from the viewpoint of having both the coatability and the antistatic property of the antistatic agent. About 0 to 500 parts by mass, more preferably about 0 to 100 parts by mass.

<Diluted solvent>

In one embodiment, the composition contains a diluent solvent. As the diluent, various conventional diluents may be used alone, or two or more of them may be used in combination. In addition, the diluent solvent is preferably a solvent that does not react (polymerize) even when irradiated with ultraviolet rays, that is, an ultraviolet non-reactive solvent.

Diluent solvents are, for example: methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butyl Alcohol, diacetone alcohol, acetone 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.

With respect to 100 parts by mass of the above composition, the upper limit of the content of the diluent solvent is, for example, 1900, 1750, 1500, 1250, 1000, 750, 500, 250, 100, 50, and 25 parts by mass, and the lower limit is, for example, 1750, 1500, 1250 , 1000, 750, 500, 250, 100, 50, 25, 0 parts by mass. In one embodiment, from the viewpoint of coatability, the content of the diluent solvent is, for example, 0 to 1900 parts by mass based on 100 parts by mass of the composition.

The upper limit of the content of the diluent solvent with respect to 100 parts by mass of the urethane (meth) acrylate is, for example, 1900, 1750, 1500, 1250, 1000, 750, 500, 250, 100, 50, 25 parts by mass, etc. The lower limit is, for example, 1750, 1500, 1250, 1000, 750, 500, 250, 100, 50, 25, 0 parts by mass, and the like. In one embodiment, from the viewpoint of coatability, the content of the diluent solvent is, for example, 0 to 1900 parts by mass, based on 100 parts by mass of the urethane (meth) acrylate.

<Additives>

The active energy ray-curable resin composition may contain, as additives, agents other than the urethane (meth) acrylate, a photopolymerization initiator, a polymerizable monomer, an antistatic agent, and a diluent.

Additives are, for example, antioxidants, ultraviolet absorbers, light stabilizers, defoamers, surface modifiers, antifouling agents, pigments, metal oxide fine particle dispersions, organic fine particle dispersions, and the like.

In one embodiment, with respect to 100 parts by mass of the composition, the content of the additive is, for example, 0.05 to 50 parts by mass, less than 40 parts by mass, less than 25 parts by mass, less than 10 parts by mass, less than 5 parts by mass, and less than 1 part by mass. , Less than 0.1 parts by mass, less than 0.01 parts by mass, 0 parts by mass, and the like.

In another embodiment, the content of the additive is, for example, 0.05 to 333 parts by mass, less than 300 parts by mass, less than 200 parts by mass, and less than 100 parts by mass relative to 100 parts by mass of the urethane (meth) acrylate. , Less than 50 parts by mass, less than 25 parts by mass, less than 10 parts by mass, less than 5 parts by mass, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, and the like.

The composition is obtained by mixing the urethane (meth) acrylate and, if necessary, a polymerization initiator, a polymerizable monomer, a diluent solvent, an additive, and the like using various conventional methods.

The active energy ray-curable resin composition can be used as a coating agent, a coating agent for a film, a coating agent for a plastic sheet, and the like. Coating agents for films are, for example, coating agents for cellulose triacetate films (TAC films), coating agents for acrylic films, coating agents for cycloolefin resin films (COP films), and the like.

[Hardened matter]

The present invention provides a cured product of the active energy ray-curable resin composition. The hardened material is obtained by irradiating the active energy ray-curable resin composition with active energy rays such as ultraviolet rays, electron beams, and radiation.

The active energy rays used in the hardening reaction are, for example, ultraviolet rays or electron beams. The ultraviolet light source is, for example, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, or a metal halide lamp. In addition, the light quantity, light source configuration, and conveying speed can be adjusted as required. In the case of using a high-pressure mercury lamp, it is preferable to use a conveying speed of about 5 to 50 m / relative to each lamp having a light quantity of about 80 to 160 W / cm. It hardens in minutes. On the other hand, in the case of an electron beam, in an electron beam acceleration device having an acceleration voltage of about 10 to 300 kV, it is preferably hardened at a conveying speed of about 5 to 50 m / min.

[Film]

The present invention provides a film containing the cured product. The said thin film is an article which consists of the said hardened | cured material and various base films as a component.

Various conventional base films can be used for the base film, for example: polycarbonate film, acrylic film (polymethyl methacrylate film, etc.), polystyrene film, polyester film, polyolefin film, epoxy resin film, Melamine resin film, cellulose triacetate film, ABS film, AS film, norbornene-based resin film, cycloolefin film, polyvinyl alcohol film, etc. The thickness of the base film is not particularly limited, but is preferably about 15 to 100 μm.

The above-mentioned film can be produced using various conventional methods. Specifically, the active energy ray-curable resin composition may be coated on at least one surface of the base film, dried if necessary, and then irradiated with active energy rays. Further, the non-coated surface of the obtained base film may be coated with the resin composition of the present embodiment, another base film may be laminated thereon, and active energy rays may be irradiated to produce a laminated film. These films can be used as optical films.

The coating methods are, for example, bar coater coating, wire rod coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, and screen printing. Printing method, etc.

The coating amount is not particularly limited, and the mass after drying is preferably 0.1 to 30 g / m ² , and more preferably 1 to 20 g / m ² .

[Example]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples. However, the description in the above preferred embodiments and the following examples are provided for the purpose of illustration only, and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited by the embodiments and examples specifically described in this specification, but only by the scope of patent applications. In addition, unless otherwise stated, in each Example and a comparative example, numerical values, such as a part and%, are a mass basis.

(Weight average molecular weight)

Measured values were obtained by gel permeation chromatography (TOSOH (Co., Ltd.), trade name "HLC-8220"; column: manufactured by TOSOH (Co., Ltd.), trade name "TSKgel superHZM-M".

Example 1-1

A reaction vessel equipped with a stirring device and a cooling tube was charged with 300 parts (225 parts solids) of octanoic acid modified product of xylene diisocyanate (TAKENATE D-131N, manufactured by Mitsui Chemicals, Inc.), and caprylic acid. After 0.6 parts of tin and 240 parts of 2-hydroxy-3-phenoxypropyl acrylate (epoxy ester M-600A, manufactured by Kyoeisha Chemical Co., Ltd.), the temperature in the system was raised to about 80 after about 1 hour. ℃. Next, the reaction system was kept at the same temperature for 2 hours, and then cooled to obtain a urethane acrylate ((1) -1). The weight average molecular weight was 2900. 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan (trade name "IRGACURE184", hereinafter referred to as HCPK)) was blended with 100 parts of the mixture in accordance with the solid content ratio, using methyl Isobutyl ketone was diluted to prepare an active energy ray-curable resin composition with a non-volatile content of 40%.

Examples and comparative examples other than Example 1-1 were implemented in the same manner as in Example 1-1 except that the components described in Table 1 were changed.

(Manufacture of film)

On a PET film (lumirror 100U483, manufactured by Toray Industries, Ltd.) with a film thickness of 100 μm, each active energy ray-curable resin composition was coated with a # 14 bar coater to make a cured coating film film. The thickness was 7 μm, and the film was dried at 80 ° C. for 1 minute. Next, the obtained film was subjected to an ultraviolet curing device (product name: UBT-080-7A / BM, manufactured by MULTIPLY (Co., Ltd.), high-pressure mercury lamp 600 mJ / cm ² ) to obtain a film providing a cured coating film. The evaluation results of the produced film are shown in Tables 1 and 2.

Hardness (pencil hardness)

In accordance with JIS K5600-5-4, the hardness of the cured product was evaluated by a pencil scratch test with a load of 500 g.

Low curl

When the film was cut out by 10 cm × 10 cm, the film was classified as “○” when the film did not become cylindrical (the end portions of the film overlapped with each other); when the film was cylindrical, it was classified as “×”.

Lightfastness

The film was exposed to a carbon arc lamp for 100 hours in an ultraviolet automatic fading tester (trade name: UV automatic fading tester U48AU, manufactured by Japan's SUGA Tester (Co., Ltd.)). The film after the test was measured by a transmission method of a color difference meter (trade name: ZE 6000, manufactured by Nippon Denshoku Industries Co., Ltd.). If the yellow index value after the exposure is less than 2, it is classified as "○"; if If it is 2 or more, it is classified as "×".

Refractive index

For the film, 1-bromonaphthalene was attached to a prism of an Abbe refractometer, and the refractive index (D-line at 589 nm) was measured at 20 ° C. If the refractive index is 1.550 or more, it is classified as "○"; if it is less than 1.550, it is classified as "×".

Example 2

When the active energy ray-curable resin composition in the present embodiment is further studied, it is found that the cured product (cured film) of the active energy ray-curable resin composition has excellent antistatic properties.

Synthesis example 1 (antistatic agent (4a))

100 parts of a methacryloxyethyl trimethylammonium chloride (hereinafter referred to as DMC) containing a quaternary ammonium salt structure was added to a reaction vessel including a stirring device, a cooling tube, a dropping funnel, and a nitrogen introduction tube. , 60 parts of ε-caprolactone, 10 mol modified hydroxyethyl methacrylate, 40 parts of t-butyl methacrylate (hereinafter referred to as t-BMA), and 800 parts of propylene glycol monomethyl ether (PGME). To 90 ° C. Next, was added 2,2 '- azobis (methylbutyronitrile) (AMBN) 8 parts and PGME 32 parts, the polymerization reaction was cooled after 6 hours maintained at 100 deg.] C, to obtain a copolymer containing a quaternary ammonium salt structure Solution (non-volatile content 20%) ("(4a) component").

Example 2-1

With respect to 100 parts of urethane acrylate ((1) -1), 5 parts of antistatic agent (4a) and 5 parts of HCPK were blended in accordance with the solid content ratio, and diluted with PGME to prepare 40% non-volatile components. Active energy ray-curable resin composition.

Example 2-2, Comparative Example 1-1

Except having changed the component shown in Table 3, it carried out similarly to Example 2-1.

Antistatic

For the film, the active energy ray-curable resin composition (just prepared) of Example 1 was used on a 100 μm thick polyester film (manufactured by Toyobo Co., Ltd. under the trade name “COSMOSHINE A-4100”) # 4 The coating was performed with a bar coater (calculated film thickness: 2 to 3 μm), and dried at 80 ° C. for 1 minute. Next, the obtained film was passed through a high-pressure mercury lamp (200 mJ / cm ² ) twice in the atmosphere, thereby producing an antistatic-treated optical film having a cured film. For the active energy ray-curable resin compositions of the other examples and comparative examples, an antistatic-treated optical film was produced in the same manner. Next, a commercially available resistivity meter (manufactured by Mitsubishi Chemical Corporation, product name "HIRESTA UP MCP-HT450") was used to measure the cured product (cured film) of the film at an applied voltage of 500 V in accordance with JIS K 6911. ) Surface resistance.

Pentaerythritol triacrylate: Viscoat # 260 (Osaka Organic Chemical Industry Co., Ltd.)

2-hydroxy-3-propenyloxypropyl methacrylate: NK ester 701A (Shin Nakamura Chemical Industry Co., Ltd.)

Xylene diisocyanate biuret: Takenate 114N (Mitsui Chemical Co., Ltd.)

Pentaerythritol tetraacrylate: ARONIX M-450 (East Asia Synthesis Co., Ltd.)

Claims (8)

    A urethane (meth) acrylate, characterized in that it contains the reactants of the following compound groups (A) and (B): polyisocyanate (A), which is a polymer of xylene diisocyanate; And (meth) acrylate (B) containing a hydroxyl group.         The urethane (meth) acrylate according to item 1 of the scope of the patent application, wherein the polyisocyanate (A) is an isocyanurate polymer or a biuret polymer of xylene diisocyanate. Polymer or addition polymer.         An active energy ray-curable resin composition, characterized in that it contains a urethane (meth) acrylate as described in item 1 or 2 of the scope of patent application.         The active-energy-ray-curable resin composition as described in Claim 3 of a patent application range, Comprising: The said active-energy-ray-curable resin composition contains a photoinitiator.         The active-energy-ray-curable resin composition as described in claim 3 or 4, wherein the active-energy-ray-curable resin composition contains a polymerizable monomer.         The active energy ray-curable resin composition according to any one of claims 3 to 5, wherein the active energy ray-curable resin composition contains an antistatic agent.         The hardened | cured material of the active-energy-ray-curable resin composition as described in any one of Claims 3-6.         A film characterized in that it contains a hardened substance as described in item 7 of the scope of patent application.