KR102501500B1 - Active energy ray curing type hard coat agent and laminate - Google Patents

Abstract

An active energy ray curable hard coat containing alumina particles (A), an acrylate having a perfluoroalkylene group (B), and a polyfunctional urethane acrylate (C), and satisfying the following (1) and (2) my. (1) The crystal structure of the alumina particles (A) is θ-type and/or α-type, and the primary particle size is 5 to 50 nm. (2) 5-50 mass % of alumina particle (A) and 0.05-5 mass % of acrylate (B) are contained in 100 mass % of solid content of a hard-coat agent. (However, polyfunctional urethane acrylate (C) excludes acrylate (B) having a perfluoroalkylene group.)

Description

Active energy ray curing type hard coat agent and laminate

The present invention relates to an active energy ray-curable hard coat agent and a laminate.

More specifically, it relates to an active energy ray-curable hard coat agent that can be applied to a display such as a TV, a notebook PC, a mobile phone, a smart phone, or a rear light body thereof, and a laminate using the same. .

The image display surface of a display such as a TV, notebook PC, mobile phone, smart phone or the like, or its rear surface is required to be imparted with a hard coat property so as not to be damaged during handling. Accordingly, the hard coat laminate is disposed on the surface of the device. This laminate has a structure in which a hard coat layer is laminated on a translucent substrate such as polyethylene terephthalate or triacetyl cellulose.

The hard coat laminate has each desired property. For example, a laminate in which a microrelief structure is formed on the surface of the laminate can be used as a hard coat layer and can also be used as an anti-glare film provided with an anti-glare layer. In addition, a light diffusion layer or a low refractive index layer may be used by laminating them. Development of an optical laminate having a desired function is progressing by using a single layer of functional layers such as a hard coat layer or an anti-glare layer or by combining a plurality of layers.

On the other hand, the outermost surface of the display or its rear light body is expected to be subjected to difficult handling due to loads such as physical, mechanical, or chemical stimuli. For example, by wiping contamination such as dust and fingerprints adhering to the surface of the device with a rag impregnated with a glass cleaner (surfactant-based, organic solvent-based, etc.). In addition, the surface of the device is easily distorted by sweat, fingerprints, etc., or there is a problem of poor appearance quality, and when using a conventional general surface treatment agent, contamination such as fingerprints is not easily removed, but rather spreads. Because of this, it becomes a device problem. Accordingly, the surface of the hard coat film mounted on the device is required to have high scratch resistance and antifouling properties. Furthermore, in the case of manufacturing or using the hard coat laminate, troubles such as cracks may occur during processing and use. Accordingly, in addition to antifouling properties, hard coat laminates require bending resistance as crack prevention.

Conventionally, the hard coat agent constituting the hard coat layer is a coating agent that is cured with active energy rays, and various methods have been proposed as a method of realizing a surface treatment that imparts scratch resistance and stain resistance. For example, a coating hard coat agent containing a fluorine-based UV-curable functional group-containing compound is proposed to improve fingerprint resistance (Patent Document 1). Further, in order to improve antistatic properties and antifouling properties, a hard coat agent containing an ionizing radiation curable fluoroacrylate and a conductive metal oxide has been proposed (Patent Document 2). Furthermore, as a method of separately forming a coating layer imparting fouling resistance on the abrasion-resistant coating layer, a method of separately coating a copolymer of acrylate and silica having a perfluoro group on a low-reflection layer mainly composed of silica has been proposed ( Patent Document 3).

However, there is still no active energy ray-curable hard coat agent for forming a hard coat layer having high scratch resistance (friction) property, antifouling property, and further bending resistance.

Japanese Patent Publication No. 2011-505452 Japanese Unexamined Patent Publication No. 2011-84048 Japanese Unexamined Patent Publication No. H07-16940

An object of the present invention is to provide an active energy ray-curable hard coat agent for producing a hard coat layer capable of achieving both high scratch resistance, antifouling properties and further bending resistance.

As a result of intensive research on the above problems, the present inventors have found that they can be solved by using the active energy ray-curable hard coat agent described below, and have reached the present invention.

The present invention contains an alumina particle (A), an acrylate (B) having a perfluoroalkylene group, and a polyfunctional urethane acrylate (C), and satisfies the following (1) and (2), the activation energy It relates to a pre-curing type hard coat agent.

(1) The crystal structure of the alumina particles (A) is θ-type and/or α-type, and the primary particle size is 5 to 50 nm.

(2) 5-50 mass % of alumina particle (A) and 0.05-5 mass % of acrylate (B) are contained in 100 mass % of solid content of a hard-coat agent.

(However, polyfunctional urethane acrylate (C) excludes acrylate (B) having a perfluoroalkylene group.)

This invention relates to the said hard-coat agent whose functional group number of the said polyfunctional urethane acrylate (C) is 4-15, and molecular weight is 500-15000.

This invention relates to the said hard-coat agent which further contains polyfunctional ester acrylate (D).

This invention relates to the said hard-coat agent in which the said polyfunctional ester acrylate (D) has an ester structure derived from carboxylic acid which has a ring structure of 6 or more carbon atoms.

The present invention relates to a laminate having a base material and a hard coat layer made of the above hard coat agent.

According to the present invention, it is possible to provide an active energy ray-curable hard coat agent for producing a hard coat layer capable of achieving both high scratch resistance, antifouling property, and further bending resistance.

The embodiments of the present invention will be described in detail below, but the description of the constituent requirements described below is an example (a representative example) of the embodiments of the present invention, and the present invention does not deviate from the gist of these contents. not limited to

Hereinafter, each element constituting the present invention will be described in detail.

The present invention contains an alumina particle (A), an acrylate (B) having a perfluoroalkylene group, and a polyfunctional urethane acrylate (C), and satisfies the following (1) and (2), the activation energy It relates to a pre-curing type hard coat agent.

(1) The crystal structure of the alumina particles (A) is θ-type and/or α-type, and the primary particle size is 5 to 50 nm.

(2) 5-50 mass % of alumina particle (A) and 0.05-5 mass % of acrylate (B) are contained in 100 mass % of solid content of a hard-coat agent.

(However, polyfunctional urethane acrylate (C) does not contain acrylate (B) having a perfluoroalkylene group.)

In the hard coat agent of the present invention, high scratch resistance is realized because the crystal structure of the alumina particles (A) is θ-type and/or α-type. Moreover, flexibility is given to the hard-coat layer by using urethane acrylate (C) at the same time, and flexibility improves. Furthermore, antifouling property is improved by using the acrylate (B) having a perfluoroalkylene group. Even if these are used simultaneously, there is no deterioration of each characteristic and characteristic.

<Active energy ray curing type hard coat agent>

An active energy ray-curable hard coat agent refers to a composition containing a resin that is cured through a crosslinking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams. After application of the active energy ray-curable hard coat agent, it is cured by irradiation with active energy rays such as ultraviolet rays or electron beams to form a hard coat layer. Typical examples of this resin include ultraviolet curable resins and electron beam curable resins, and resins that are cured by irradiation with ultraviolet rays are preferable in terms of excellent mechanical film strength (scratch resistance and pencil hardness). Examples of such a resin include a resin having a plurality of acrylate groups, an acrylate monomer, and the like.

In the following description, (meth)acrylate means methacrylate and acrylate, and (meth)acryl means a combination of methacryl and acryl.

<Alumina Particles (A)>

In the present invention, the crystal structure of the alumina (Al ₂ O ₃ ) particles (A) is θ-type and/or α-type, and the primary particle size is 5 to 50 nm. By doing in this way, haze (turbidity) and coloration of the hard coat layer are reduced. In addition, the primary particle size refers to a value obtained by measurement with a transmission electron microscope. As a value, it is preferable to measure the value of 5 points or more in order to take the average value, and to take the average value.

In addition, the alumina particles (A) preferably have a BET specific surface area of 10 to 100 m ² /g. Also, the Al ₂ O ₃ purity is preferably 99.5% or higher. Depending on the range, the friction resistance of the hard coat layer is improved. It is necessary to contain 5-50 mass % of alumina particle (A) in the solid content total mass of a hard-coat agent, and it is preferable to contain 10-40 mass %. On the other hand, the solid content refers to the total mass of non-volatile components in the hard coat agent.

<Acrylate (B) having a perfluoroalkylene group>

The acrylate (B) having a perfluoroalkylene group can impart antifouling properties to the hard coat layer through fluorine atoms, and the acrylate group contributes to hard coat properties by taking charge of curability. Accordingly, it is necessary to contain 0.05 to 5% by mass of the acrylate (B) having a perfluoroalkylene group in the total solid mass of the hard coat agent. The acrylate (B) having a perfluoroalkylene group is one containing a perfluoroalkylene group and having a (meth)acrylate group. Meanwhile, a perfluoroalkylene group refers to an alkylene group substituted with a fluorine atom.

It is preferable to contain 0.3-3 mass % of acrylate (B) in the total mass of solid content of a hard-coat agent. The number of (meth)acrylate groups (referred to as the number of functional groups) of the acrylate (B) in its molecular structure is preferably 1 to 6, more preferably 2 to 6. Moreover, it is preferable that it is 400-5000, and, as for a weight average molecular weight, it is more preferable that it is 500-2000. Moreover, it is preferable that acrylate (B) is urethane acrylate which has a urethane bond. By doing in this way, it contributes to the flexibility or scratch resistance of the hard coat layer. Moreover, as for carbon number of a perfluoroalkylene group, 1-10 are preferable. Moreover, it is preferable to have a perfluoroalkyleneoxy structural unit represented by the following formula (1).

chemical formula (1)

-(CF ₂ -CF ₂ -O) _n - (n is an integer from 1 to 10.)

Examples of the acrylate (B) include Megafac RS-75, Megafac RS-76-E, and Megafac RS-90 manufactured by DIC Co., Ltd., and KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd. can

<Multifunctional Urethane Acrylate (C)>

Polyfunctional urethane acrylate (C) refers to an oligomer having a urethane bond and having a (meth)acrylate group. However, those having a perfluoroalkylene group are excluded. The content of the urethane acrylate resin is preferably 5 to 95% by mass, more preferably 50 to 95% by mass, based on 100% by mass of the solid content of the hard coat agent. Moreover, it is preferable that the weight average molecular weight is 500-15000 from a viewpoint of coatability. It is preferable that polyfunctional urethane acrylate (C) is 4-15 functional groups. In addition, a functional group number is synonymous with the above. Moreover, it is preferable that it is 600-15000, and, as for a weight average molecular weight, it is more preferable that it is 1000-5000. The weight average molecular weight refers to a value measured by gel permeation chromatography (GPC). The mass ratio ((A)/(C)) of the alumina particles (A) and the polyfunctional urethane acrylate (C) is preferably 10/90 to 90/10, and more preferably 10/90 to 50/50. desirable.

The polyfunctional urethane acrylate (C) is, for example, one obtained by reacting diisocyanate and (meth)acrylates having a hydroxyl group, and an isocyanate group-containing urethane obtained by reacting a polyol and a polyisocyanate under conditions of excess isocyanate groups. There exist the thing obtained by making a prepolymer react with (meth)acrylates which have a hydroxyl group. Alternatively, it can also be obtained by reacting a hydroxyl group-containing urethane prepolymer formed by reacting a polyol and polyisocyanate under conditions of excess hydroxyl group with (meth)acrylates having an isocyanate group.

Although it shows about the manufacturing method of urethane acrylate below, it is an example, and it is not limited to these. For example, urethane acrylate can be obtained by stirring diisocyanate and hydroxyl group-containing (meth)acrylate in the presence of an appropriate urethanization catalyst under oxygen atmosphere at 60 to 100° C. for 4 to 8 hours. .

Specific examples of the urethanization catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, and 2,6 ,7-trimethyl-1,4-diazabicyclo[2.2.2]octane and the like. Among these, dibutyl tin dilaurate and the like are particularly preferred.

Examples of the diisocyanate include aliphatic diisocyanate and aromatic diisocyanate, and examples of the aliphatic diisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane. diisocyanate and the like, and examples of the aromatic diisocyanate include toluene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate, and the bonding position of the isocyanate group with the aromatic ring is ortho, meta Any of above and para-wih may be sufficient. In addition, this diisocyanate may form an isocyanurate ring as a trimer.

Among these, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isocyanurate substance of hexamethylene diisocyanate are preferable.

As the hydroxyl group-containing (meth)acrylate, trimethylolpropanedi(meth)acrylate, trimethylolethanedi(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate (meth)acrylate ) 2-hydroxyethyl acrylate, 1-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, (meth)acrylate ) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, cyclohexane Dimethanol mono(meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, ethyl (meth)acrylate-α-(hydroxymethyl), monofunctional (meth)acrylic acid Glycerol or (meth)acrylates thereof, (meth)acrylic acid esters having a hydroxyl group at the terminal by ring-opening addition of ε-caprolactone, and ethylene oxide, propylene oxide, and hydroxyl group-containing (meth)acrylic acid esters such as alkylene oxide-added (meth)acrylic acid esters obtained by repeatedly adding alkylene oxides such as butylene oxide.

Among them, at least one selected from trimethylolpropanedi(meth)acrylate, trimethylolethanedi(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate. it is desirable

The following can be illustrated as a commercial item of the said functional group number is 4-15 and molecular weight is 500-15000 polyfunctional urethane acrylate.

Shin-Nakamura Chemical Industry Co., Ltd.: NK oligo U6LPA, NK oligo U10PA, NK oligo U10HA, NK oligo UA-33H, NK oligo UA-53H, Negami Industry Co., Ltd.: Art Resin UN-3320HA, Art Resin UN -3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin UN-904, Art Resin UN-905, Art Resin UN-952, Art Resin HDP, Art Resin Resin HDP-3, Artresin H61, manufactured by Japan Synthetic Chemical Industry Co., Ltd.: UV-7600B, UV-7610B, UV-7620EA, UV-7630B, UV-1700B, UV-6300B, UV -7640B, Zakwang UT-5670, Zakwang UV-5671, manufactured by Kyoeisha Chemical Co., Ltd.: UA-306H, UA-306T, UA-306I, manufactured by MIWON: PU610, PU620, MU9800.

<Multifunctional ester acrylate (D)>

It is preferable that the active energy ray-curable hard coat agent further contains a polyfunctional ester acrylate (D). The polyfunctional ester acrylate (D) refers to an oligomer containing a (poly)ester structure and having a (meth)acrylate group. However, those having a perfluoroalkylene group and a urethane bond are excluded. Among these, it is preferable that the number of functional groups is 4 to 15 and the molecular weight is 600 to 15000.

Preferred examples of the polyfunctional ester acrylate (D) include a condensate of a polybasic acid, a polyhydric alcohol, and a hydroxyl group-containing (meth)acrylate, and a polybasic acid and a hydroxyl group-containing (meth)acrylate condensate, for example. .

Examples of the polybasic acid include aliphatic, alicyclic, and aromatic acids, and each may be used without particular limitation. Examples of aliphatic polybasic acids include oxalic acid, malonic acid, succinic acid, succinic anhydride, adipic acid, sebacic acid, azelaic acid, maleic acid, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, and glutaric acid. , itaconic acid, succinic acid anhydride, maleic anhydride, and the like are preferred.

Examples of the polyhydric alcohol include dihydric alcohol and trihydric or higher alcohol. -pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, butylethylpentanediol, 2-ethyl-1, Those in which two or more hydroxyl groups are introduced into branched alkanes such as 3-hexanediol and trimethylolpropane are preferred from the standpoint of adhesion to substrates and heat resistance.

On the other hand, as a trihydric or higher alcohol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. are suitable, and you may use it together with dihydric alcohol.

As a method for producing polyfunctional ester acrylate (D), a polybasic acid and a polyhydric alcohol are polycondensed by a known method to obtain polyester, and a carboxyl group residue is subjected to a condensation reaction with the hydroxyl group of the hydroxyl group-containing (meth)acrylate. polyfunctional ester acrylate (D) to be obtained. Alternatively, the desired polyfunctional ester acrylate (D) can be obtained by subjecting a polybasic acid to a condensation reaction of the hydroxyl group of the hydroxyl group-containing (meth)acrylate. However, aspects of the manufacturing method are not limited to these.

Examples of the hydroxyl group-containing (meth)acrylate include the same ones as above, and among these, trimethylolpropane di(meth)acrylate, trimethylolethanedi(meth)acrylate, pentaerythritol tri(meth)acrylate, and It is preferable to contain at least 1 sort(s) chosen from dipentaerythritol penta (meth)acrylate.

It is preferable that the polyfunctional ester acrylate (D) contains an ester structure derived from carboxylic acid having a ring structure of 6 or more carbon atoms. Although a cyclohexane structure, a cyclohexene structure, and a benzene structure etc. can be given as a C6 or more ring structure, it is not limited to these. Examples of the carboxylic acid having a ring structure of 6 or more carbon atoms include cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, phthalic acid, benzene tetracarboxylic acid, and biphenyl tetracarboxylic acid.

It is preferable that the number of functional groups is 5-10, and, as for polyfunctional ester acrylate, it is preferable that it is 500-15000 as a weight average molecular weight. On the other hand, the polyfunctional ester acrylate (D) is the mass ratio (C)/(D) of the above-mentioned polyfunctional urethane acrylate (C) and the polyfunctional ester acrylate (D) in the total solid content of the active energy ray-curable hard coat agent. It is preferable to contain in 10/90 - 99/1, and it is more preferable that it is 70/30 - 98/2.

<Other monomers>

The active energy ray-curable hard coat agent of the present invention may contain, as other monomers, a hexafunctional or lower (meth)acrylate monomer having a molecular weight of less than 600. For example, as a 5-6 functional (meth)acrylate monomer, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. are mentioned, for example, and a 3-4 functional (meth)acrylic acid. Examples of the rate monomer include ditrimethylolpropane tetraacrylate, trimethylolpropane tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, and ethoxylated trimethylolpropane triacryl. rate, and propoxylated trimethylolpropane triacrylate.

Examples of the bifunctional (meth)acrylate monomer include trimethylolpropane di(meth)acrylate, dicyclopentanyldimethylene di(meth)acrylate, and 5-ethyl-2-(2-hydroxy- 1,1-dimethylethyl)-5-(hydroxymethyl)-1,3-dioxadi(meth)acrylate, neopentylglycoldi(meth)acrylate, 1,6-hexanedioldi(meth)acrylate rate, 1,3-butanedioldi(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,9-nonanedioldi(meth)methacrylate, ethylene glycol di(meth)acrylate, di Ethylene glycol di(meth)acrylate, triethylene glycol di(meth)methacrylate, polyethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene Glycol di(meth)acrylate, glycerin dimethacrylate, hexanediol di(meth)acrylate, and dimethylol tricyclodecane di(meth)acrylate, etc. are mentioned. Preferred specific examples include trimethylolpropane tri(meth)acrylate, EO-modified trimethyloltriacrylate, and PO-modified trimethyloltri(meth)acrylate. These (meth)acrylates may be used individually or may be used in mixture of 2 or more types.

Examples of the monofunctional (meth)acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and n-stere Aryl (meth) acrylate, n-butoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl ( meth)acrylate, and 2-hydroxybutyl (meth)acrylate; and the like.

<Organic solvent>

The active energy ray-curable hard coat agent of the present invention may contain an organic solvent as a liquid medium. As the organic solvent used, use as a mixed solvent is preferable, and aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, and acetic acid Ester-based organic solvents such as isopropyl and isobutyl acetate, alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, and n-butanol, and glycol ether-based organic solvents such as propylene glycol monomethyl ether, etc. Known organic Solvents can be used. In particular, it is preferable to include a glycol ether-based organic solvent.

Examples of the glycol ether organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol monoisopropyl. Ether, ethylene glycol dipropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethylene glycol mono2-ethylhexyl ether, ethylene glycol ethers such as oxyethoxyethanol and ethylene glycol monoallyl ether; and

propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and butoxypropanol;

are mentioned, and among these, methyl propylene glycol and 3-methoxy-1-butanol are preferable.

<Photoinitiator>

It is preferable that the active energy ray-curable hard coat agent further contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization of a (meth)acryloyl group for forming an active energy ray cured film by photoexcitation. For example, a monocarbonyl compound-based initiator; It is preferable to contain at least one kind selected from dicarbonyl compound type initiator, acetophenone compound type initiator, benzoin ether compound type initiator, acylphosphine oxide compound type initiator, and aminocarbonyl compound type initiator.

Commercially available photopolymerization initiators include Omnirad73, 481, 659, 248, 264, 4817, BDK, TPO, TPO-L, 380, Omnipol910, BP, 2702, Esacure ONE, 1001M, A198, and KIP150 from IGM Resins. can be heard

The photopolymerization initiator is not limited to the compounds described above, and any photopolymerization initiator may be used as long as it has the ability to initiate polymerization with ultraviolet light. These photopolymerization initiators may be used alone or in combination of two or more. The amount of the photopolymerization initiator used is not particularly limited, but is 1 to 20% by mass relative to the total mass of solids excluding metal oxides in the active energy ray curable hard coat agent forming the hard coat layer in the present invention. It is preferable to use within the range of. On the other hand, a well-known organic amine etc. can also be added as a sensitizer. In addition, an initiator for cationic polymerization may be used in combination in addition to the above radical polymerization initiator.

<Other combined resins>

The active energy ray curable hard coat agent in the present invention may contain other resins, but is not limited to the following, photocurable resins other than the above, such as epoxy acrylate, chlorinated polypropylene resins, polyolefin resins, ethylene-vinyl acetate Copolymer resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, rosin-based resin, rosin-modified maleic acid resin, terpene resin, phenol-modified terpene resin, ketone resin, cyclized rubber, chlorinated rubber, butyral, petroleum resin, and These modified resins, etc. are mentioned. These resins can be used alone or in combination of two or more, and the content thereof is not particularly limited as long as the effect of the present invention is not impaired. 1 to 20% by weight is preferred.

<Additives>

The active energy ray-curable hard coat agent of the present invention may further contain various additives within a range that does not impair the objects and effects of the present invention. Specifically, polymerization inhibitor, photosensitizer, leveling agent, surfactant, antibacterial agent, antiblocking agent, plasticizer, ultraviolet absorber, infrared absorber, antioxidant, silane coupling agent, conductive polymer, conductive surfactant, inorganic filler, pigment , or dyes, and the like are exemplified.

<Manufacture of active energy ray curable hard coat agent>

The active energy ray-curable hard coat agent of the present invention is not a problem as long as it can be stirred, mixed or dispersed uniformly. For example, alumina particles (A), perfluoroalkylene constituting the active energy ray-curable hard coat agent Group-containing acrylate (B), polyfunctional urethane acrylate (C), and furthermore, polyfunctional ester acrylate (D) and other monomers as needed are mixed with a predetermined stirrer disper, homogenizer, 3 rolls, sand mill, Alternatively, it can be prepared by uniformly stirring using a gamma mill or the like.

On the other hand, the alumina particles (A) may be blended with pentaerythritol acrylate-based compounds or acrylate resins such as urethane acrylate and polyester acrylate, organic solvents, etc., and previously dispersed ones may be blended, and commercially available organic solvents You may mix|blend and use the dispersion etc. of

<Preparation of hard coat layer>

Next, a method for producing a hard coat layer obtained by curing an active energy ray-curable hard coat agent will be described. The method for producing the hard coat layer includes, for example, a step of applying an active energy ray-curable hard coat agent to a substrate, and a step of curing the active energy ray-curable hard coat agent on the substrate by irradiating with active energy rays. . More specifically, this active energy ray-curable hard coat agent can be applied to a substrate so that the film thickness after drying is preferably 0.1 to 30 μm, more preferably 1 to 10 μm, and then cured.

As the coating method, a known method can be used, for example, a method using a lot or wire bar, or various coating methods such as microgravure, gravure, die, curtain, lip, slot, spin, or spray can be used. there is.

As a curing method, it can be performed by irradiating active energy rays, such as an ultraviolet-ray, an electron beam, or visible light with a wavelength of 400-500 nm, using a well-known technique, for example. As a source (light source) of ultraviolet light and visible light having a wavelength of 400 to 500 nm, for example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, or a carbon arc lamp can be used. As the electron beam source, a thermoelectron emission gun, an electrolytic emission gun, or the like can be used. The cumulative amount of active energy rays to be irradiated is preferably in the range of 50 to 1000 mJ/cm ² from the viewpoint of easy management in terms of the process. Heat treatment by infrared rays, far infrared rays, hot air, or high-frequency heating can be used in combination with these active energy ray irradiation.

The hard coat layer may be formed by coating an active energy ray-curable hard coat agent on a substrate, drying it naturally or forcibly, and then curing it, or coating it, curing it, and then drying it naturally or forcibly. It is more preferable to perform hardening treatment after forced drying. In particular, in the case of curing with an electron beam, it is more preferable to perform a curing treatment after natural or forced drying in order to prevent curing inhibition by water or a decrease in strength of the coating film due to the residual organic solvent. The timing of the curing treatment may be simultaneous with coating or may be after coating.

<Description>

Examples of the substrate of the present invention include, but are not limited to, a polyester film, a triacetyl cellulose film, a polyolefin film, a cycloolefin film, an acrylic film, and a polycarbonate film. For the display surface, a polyester film, especially a polyethylene terephthalate (PET) film, is preferably used. The thickness of the base material may be appropriately selected depending on the intended use, and is preferably in the range of 20 μm to 300 μm, preferably in the range of 50 μm to 250 μm, and more preferably in the range of 50 μm to 200 μm. In addition, for the backlight body, an acrylic/polycarbonate sheet is particularly preferably used. The thickness of the base material may be appropriately selected depending on the intended use, but the range of 200 μm to 800 μm is suitable, and the range of 200 μm to 500 μm is preferable.

The substrate may further have a layer composed of organic and/or inorganic materials on its surface, and specific examples thereof include an easily adhesive layer for improving adhesion to other layers. Examples of the easily bonding layer include various ones treated with corona discharge treatment, UV-ozone treatment, plasma treatment, or primer treatment, and may be treated in combination.

Example

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these examples. On the other hand, parts and % in the present invention represent parts by weight and % by weight when there is no tin in particular.

(average particle diameter)

The average value of 10 randomly selected primary particle diameters was measured from transmission electron microscope measurements. On the other hand, as the transmission electron microscope, H-9500 manufactured by Hitachi High-Technologies was used.

(specific surface area)

It was obtained according to the method described in JIS Z 8830:2001.

(acid value)

It was performed by the potentiometric titration method of JIS K 0070, and it was set as the acid value (mgKOH/g) in solid content.

(weight average molecular weight)

The weight average molecular weight was obtained as a reduced molecular weight by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220 manufactured by Tosoh Corporation) and using polystyrene as a standard substance. Measurement conditions are shown below.

Column: The following columns were connected in series and used.

TSKgel SuperAW2500 manufactured by Tosoh Corporation

TSKgel SuperAW3000 manufactured by Tosoh Corporation

TSKgel SuperAW4000 manufactured by Tosoh Corporation

TSKgel guardcolumn SuperAWH manufactured by Tosoh Corporation

Detector: RI (Differential Refractometer)

Measurement conditions: Column temperature 40 ℃

Eluent: tetrahydrofuran

Flow rate: 1.0 mL/min

(Synthesis Example 1) <Multifunctional Urethane Acrylate PU3>

120 parts of polyester polyol having a molecular weight of 3000, which is a condensate of adipic acid and neopentyl glycol, and 18 parts of isophorone diisocyanate were mixed in a flask equipped with a stirring blade, a thermometer, a reflux condenser, and an air introduction tube. In addition, normal propyl acetate as a solvent was added so that the solid content was 80%, and reacted at 80 ° C. for 5 hours under a nitrogen atmosphere to synthesize a urethane prepolymer. Thereafter, air was purged in the flask, methoxyhydroquinone was blended so as to be 200 ppm, and a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate in a weight ratio of 70:30 (trade name: "Aronix M306" manufactured by Dong-A Synthetic Co., Ltd.) ) 34 parts were added and heated and stirred for 4 hours under an air atmosphere at a temperature of 80°C to obtain urethane acrylate PU3. PU3 had a functional group number of 6 and a weight average molecular weight of 6000.

(Synthesis Example 2) <Multifunctional Urethane Acrylate PU4>

In a flask equipped with a stirring blade, a thermometer, a reflux condenser, and an air introduction tube, 100 parts of an isocyanurate form of hexamethylene diisocyanate (NCO groups: 3) and 69 parts of hydroxyethyl acrylate were mixed. Additionally, normal propyl acetate as a solvent was mixed so that the solid content was 60%. Thereafter, methoxyhydroquinone was blended so as to be 200 ppm, and heated and stirred for 6 hours while blowing air at a temperature of 90°C to obtain urethane acrylate PU4. PU4 had a functional group number of 3 and a weight average molecular weight of 1000.

(Synthesis Example 3) <Multifunctional polyester acrylate PE1>

In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction tube, and a thermometer, 80.0 parts of 3,3',4,4'-biphenyltetracarboxylic dianhydride and a hydroxyl value of 122 mgKOH/g were added. 250.0 parts of pentaerythritol triacrylate (trade name of pentaerythritol triacrylate manufactured by Nippon Kayaku Co., Ltd.: KAYARAD PET-30, containing pentaerythritol tetraacrylate as a by-product), 0.24 part of methylhydroquinone, and 217.8 parts of cyclohexanone were added , and the temperature was raised to 60°C. Subsequently, 1.65 parts of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and the mixture was stirred at 90°C for 8 hours. Then, 78.3 parts of methacryl glycidyl ether and 54.0 parts of cyclohexanone were added. Next, as a catalyst, 2.65 parts of dimethylbenzylamine was added, stirred at 100°C for 6 hours, and the acid value of the reactant was measured periodically while continuing the reaction. When the acid value reached 5.0 mgKOH/g or less, the reaction was cooled to room temperature has stopped The resulting resin varnish was light yellow and transparent, and polyester acrylate PE1 having a solid content of 60% (solid mass ratio of polyester acrylate:pentaerythritol tetraacrylate = 76:24) was obtained. PE1 was functional group number 8 and weight average molecular weight 3500.

(Synthesis Example 4) <Multifunctional polyester acrylate PE2>

In a four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction tube, and a thermometer, 100 parts of polyester diol having a number average molecular weight of 1000, which is a condensate of adipic acid and neopentyl glycol, and pentaerythritol triol having a hydroxyl value of 122 mgKOH/g 92 parts of an acrylate (pentaerythritol triacrylate trade name: KAYARAD PET-30 manufactured by Nippon Kayaku Co., Ltd., containing pentaerythritol tetraacrylate as a by-product) and 0.01 part of tetrabutyl titanate were mixed. Further, methylhydroquinone was added so as to be 250 ppm, and toluene was added and stirred so as to have a solid content of 70%. The temperature was raised to 105°C, and a dehydration reaction was performed through a drain pipe while performing oxygen bubbling. When the acid value became 5.0 mgKOH/g or less, toluene as a solvent was removed under reduced pressure, and then cooled to 40°C to obtain polyester acrylate PE2 (polyester acrylate: pentaerythritol tetraacrylate = 83:17 in solid mass ratio). PE2 had a functional group number of 6 and a weight average molecular weight of 2300.

(Example 1) <Production of active energy ray curable hard coat agent S1>

20 parts of alumina particles (4) (alumina particle θ-type crystal manufactured by Sumitomo Chemical Co., Ltd., primary particle size 10 nm BET specific surface area 73 m ² /g), PU1 (product name UA-510H manufactured by Kyoeisha Chemical Co., Ltd.) as polyfunctional urethane acrylate 70 4 parts of PE1 shown in Synthesis Example 3 as polyfunctional polyester acrylate and 200 parts of propylene glycol monomethyl ether as an organic solvent were mixed, and after disper stirring, dispersion treatment was performed with a sand mill to obtain a uniform slurry. got it Furthermore, as a photopolymerization initiator, Esacure ONE (IGM Resins oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone]) 5 parts, acrylate having a perfluoroalkylene group (RS-90 manufactured by DIC Co., Ltd. "-(CF ₂ -CF ₂ -O) _n -" having a structure of 2 functional groups of urethane acrylate (n = 4 to 6) weight average molecular weight 1000) 1 part, and propylene as an organic solvent The glycol monomethyl ether was adjusted to have a solid content of 40%, and active energy ray-curable hard coat agent S1 was obtained.

(Examples 2 to 13) <Production of active energy ray curable hard coat agents S2 to 13>

An active energy ray-curable hard coat agent was prepared in the same procedure as in Example 1 except for using the raw materials and composition ratios shown in Table 1. On the other hand, the abbreviation in the table indicates the following.

(alumina particle (A))

Alumina particle (1): Sumitomo Chemical Co., Ltd. alumina particle α-type crystal primary particle diameter 30 nm

Alumina particle (2): Sumitomo Chemical Co., Ltd. alumina particle α-type crystal primary particle diameter 50 nm

(Acrylate (B) having a perfluoroalkylene group)

FA1: Daikin 3-perfluorohexyl-2-hydroxypropyl methacrylate (weight average molecular weight: 500)

(Multifunctional Urethane Acrylate (C))

PU1: Kyoeisha Chemical Co., Ltd. product name UA-510H Urethane acrylate composed of hexamethylene diisocyanate and dipentaerythritol pentaacrylate Functional group number 10 Weight average molecular weight 1800

PU2: Kyoeisha Chemical Co., Ltd. product name UA-306I Urethane acrylate composed of isophorone diisocyanate and pentaerythritol triacrylate Functional group number 6 Weight average molecular weight 900

PU5: Kyoeisha Chemical Co., Ltd. product name UF8001-G urethane acrylate functional group number 2 weight average molecular weight 4500

(Comparative Examples 1 to 9) <Production of active energy ray curable hard coat agents R1 to R9>

An active energy ray-curable hard coat agent was prepared in the same procedure as in Example 1 except for using the raw materials and composition ratios shown in Table 1. On the other hand, the abbreviation in the table indicates the following.

(alumina particle)

Alumina particle (3): Sumitomo Chemical Co., Ltd. alumina particle α-type crystal primary particle diameter 70 nm

Alumina particle (5): Sumitomo Chemical Co., Ltd. alumina particle γ-type crystal primary particle diameter 20 nm

Alumina particle (6): alumina particle amorphous crystal primary particle size 20 nm manufactured by Dagi Chemical Co., Ltd.

(Inorganic particles such as other metal oxide particles)

Zirconia: zirconia particle primary particle diameter 20nm manufactured by I-Tech

Silica particle: Silica particle primary particle size 10 nm manufactured by CIK Nanotech Co., Ltd.

(Multifunctional Urethane Acrylate)

PU5: Kyoeisha Chemical Co., Ltd. product name UF-8001-G difunctional urethane acrylate weight average molecular weight 4500

(Example 14) <Production of Laminate SS1>

Active energy ray-curable hard coat agent S1 was applied to a 125 μm-thick adhesion-facilitating polyester (PET) film ("Lumiror U483" manufactured by Toray Co., Ltd.) using a bar coater #4, and the film thickness after drying was 4.5 After the coating was applied so as to be μm, 500 mJ/cm ² ultraviolet rays were irradiated with a high-pressure mercury lamp to prepare a laminate SS1.

(Examples 15 to 26) <Production of Laminates SS2 to SS13>

Laminates SS2 to SS13 were produced in the same procedure as in Example 1 except for using the active energy ray-curable hard coat agents S2 to S13 described in Table 1.

(Comparative Examples 10 to 18) <Production of Laminates RR1 to RR9>

Laminates RR1 to RR9 were produced in the same procedure as in Example 1 except for using the active energy ray-curable hard coat agents R1 to R9 described in Table 1.

[evaluation]

Using the laminates SS1 to SS13 (Examples) and RR1 to RR9 (Comparative Examples) obtained above, the following evaluation was performed. Meanwhile, the evaluation results are shown in Tables 2 and 3.

<Scratch resistance>

Using the laminates SS1 to SS13 (Examples) and RR1 to RR9 (Comparative Examples), each was set in a tester and scratched 5000 times at a load of 1 kg/cm ² using steel wool No.0000. . With respect to the laminated body taken out, the damaged state was judged according to the following five-step visual evaluation.

[Evaluation standard]

5: No scratches at all. (Very good)

4: There are 1 or 2 scratches. (Good)

3: 3 to 10 scratches (slightly bad)

2: There are 11 or more scratches. (Defective)

1: The coating film is peeled off and the base film is exposed. (Extremely bad)

On the other hand, levels 4 and 5 are practically satisfactory levels.

<Water contact angle (initial)>

Using laminates SS1 to SS13 (Examples) and RR1 to RR9 (Comparative Examples), water contact angles were measured using a fully automatic contact angle meter DM-701 manufactured by Kyowa Interface Chemical Co., Ltd., and the contact angle values obtained were as follows It was judged according to the five-step visual evaluation. On the other hand, this evaluation was performed as an alternative evaluation of antifouling property. It is interpreted that the larger the contact angle, the easier it is to repel water and the less likely it is to be contaminated.

[Evaluation standard]

5: contact angle of 105° or more (very good)

4: Contact angle of 100° or more and less than 105° (good)

3: contact angle greater than or equal to 90° and less than 100° (slightly poor)

2: contact angle greater than or equal to 80° and less than 90° (poor)

1: contact angle less than 80° (extremely poor)

On the other hand, levels 4 and 5 are practically satisfactory levels.

<Water contact angle (after scratch resistance test)>

Using laminates SS1 to SS13 (Examples) and RR1 to RR9 (Comparative Examples), water contact angles were measured for each of the samples after the scratch resistance test, and the obtained contact angle values were visually evaluated in the following five stages It was judged accordingly. On the other hand, this evaluation was performed as an alternative evaluation of antifouling property. It is understood that the larger the contact angle, the easier it is to repel water and the less likely it is to be contaminated.

[Evaluation standard]

5: Contact angle of 100° or more (very good)

4: Contact angle greater than or equal to 90° and less than 100° (good)

3: contact angle greater than or equal to 80° and less than 90° (slightly poor)

2: Contact angle of 70° or more and less than 80° (poor)

1: contact angle less than 70° (extremely poor)

On the other hand, levels 4 and 5 are practically satisfactory levels.

<Bending resistance>

Using laminates SS1 to SS13 (Examples) and RR1 to RR9 (Comparative Examples), a bending resistance test when each of the laminates was bent with the laminated surface of the active energy ray curable hard coat material facing outward , It was evaluated using a film bending tester (PI-801 manufactured by Tester Industrial Co., Ltd.). The diameter of the mandrel at which cracks did not occur was judged according to the following five-step visual evaluation.

[Evaluation standard]

5: Mandrel diameter less than φ10 mm (very good)

4: The mandrel diameter is φ10 mm or more and less than 15 mm (good)

3: The mandrel diameter is φ15 mm or more and less than 20 mm (slightly poor)

2: The mandrel diameter is φ20 mm or more and less than 25 mm (defective)

1: Mandrel diameter of φ25 mm or more (extremely poor)

On the other hand, levels 4 and 5 are practically satisfactory levels.

<transparency>

The transparency of each of the laminates SS1 to SS13 (Examples) and RR1 to RR9 (Comparative Examples) was evaluated by haze (turbidity) of the coating film. The haze value was measured using a haze meter SH7000 manufactured by Nippon Denshoku Kogyo Co., Ltd. Based on the obtained haze value, transparency was judged according to visual evaluation in the following 5 stages.

[Evaluation standard]

5: haze value less than 0.5 (very good)

4: Haze value is 0.5 or more and less than 1.0 (good)

3: haze value of 1.0 or more and less than 2.0 (slightly poor)

2: haze value of 2.0 or more and less than 3.0 (defective)

1: haze value of 3.0 or more (extremely poor)

On the other hand, levels 4 and 5 are practically satisfactory levels.

From the results of Table 2, in the examples, scratch resistance, antifouling property, flexibility, and transparency were all excellent. In particular, as for the scratch condition, the basic condition is usually about 100 scratches, and even 5000 scratches are good, and a remarkable effect was exhibited. Furthermore, flexibility was also compatible, and unexpected performance was shown.

On the other hand, in the comparative example, any one of scratch resistance, stain resistance, flexibility, and transparency is in a trade-off relationship, and the results of Table 3 show that performance is insufficient in at least one item.

[Table 1]

[Table 2]

[Table 3]

Claims (5)

Containing alumina particles (A), acrylate (B) having a perfluoroalkylene group, and polyfunctional urethane acrylate (C),
An active energy ray curable hard coat agent that satisfies the following (1) and (2).
(1) The crystal structure of the alumina particles (A) is θ-type or α-type, and the primary particle diameter is 5 to 50 nm.
(2) 5-50 mass % of alumina particle (A) and 0.05-5 mass % of acrylate (B) are contained in 100 mass % of solid content of a hard-coat agent.
(However, polyfunctional urethane acrylate (C) excludes acrylate (B) having a perfluoroalkylene group.) According to claim 1,
The number of functional groups of the said polyfunctional urethane acrylate (C) is 4-15, and the hard-coat agent whose weight average molecular weight is 500-15000. According to claim 1 or 2,
A hard coat agent further containing polyfunctional ester acrylate (D). According to claim 3,
The hard-coat agent in which the said polyfunctional ester acrylate (D) has an ester structure derived from carboxylic acid which has a ring structure of 6 or more carbon atoms. A laminate comprising a base material and a hard coat layer made of the hard coat agent according to claim 1 or 2.