JP2013209516A - Active energy ray-curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition capable of forming a hardcoat layer having sufficient antiblocking properties and having a high hardness.SOLUTION: The problem is solved by adding a specific copolymer to a curable composition. Concretely, the active energy ray-curable composition containing a (meth)acryloyl copolymer having a hydrogen-bonding group and an unsaturated double bond on the side chain, and a polyfunctional (meth)acrylate having two or more unsaturated double bonds in one molecule is regulated so that the SP value of the (meth)acryloyl copolymer may not be lower than the SP value of the polyfunctional (meth)acrylate.

Description

  The present invention relates to an active energy ray-curable composition that can provide a cured product having good antiblocking properties. The present invention also relates to a hard coat film obtained by curing the active energy ray curable composition and a film laminate obtained by laminating the hard coat film.

A hard coating excellent in hardness and slipperiness is applied to the surface of a thermoplastic film typified by a PET film. The film after such hard coating is performed may be wound into a roll and stored. Such a storage method is used because it is advantageous in terms of storage location by winding in a roll.
However, if the PET film after hard coating is wound in a roll shape in this way, the hard coating surfaces will contact each other or the hard coating surface and another film surface, and this contact may cause unexpected blocking There is.

As a method for preventing such blocking, a method is disclosed in which inorganic fine particles are mixed into the hard coat layer to make the layer surface have a specific roughness, thereby preventing blocking (see Patent Document 1).
In addition, by containing a specific unsaturated double bond group-containing monomer containing a resin and an alkylene oxide unit having 2 to 4 carbon atoms in the composition, the resin contained in the composition is precipitated by phase separation after coating. A method for preventing blocking by forming irregularities on the surface is disclosed (see Patent Document 2).

JP 2004-42653 A JP 2010-163535 A

In the technique disclosed in Patent Document 1, since particles are mixed, it is necessary to reduce the film thickness for forming irregularities on the surface, and the film hardness tends to decrease and the scratch resistance tends to be insufficient.
On the other hand, in the technique disclosed in Patent Document 2, the SP value of the resin separately contained is set lower than the SP value of the specific unsaturated double bond group-containing monomer containing an alkylene oxide unit having 2 to 4 carbon atoms. By doing so, the resin is deposited by phase separation after coating. However, as a result of investigations by the present inventors, the technique disclosed in Patent Document 2 includes an alkylene oxide unit in the unsaturated double bond group-containing monomer, so that the hardness of the hard coat layer when cured is low, and antiblocking It has been found that the resistance and scratch resistance tend to be low.

  The present invention solves such problems of the prior art and provides a curable composition capable of forming a hard coat layer having sufficient anti-blocking performance and high hardness. And

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by adding a specific copolymer to the curable composition. The present invention is as follows.

(1) a (meth) acryloyl copolymer having a hydrogen bonding group and an unsaturated double bond in the side chain;
An active energy ray-curable composition containing a polyfunctional (meth) acrylate having two or more unsaturated double bond groups in one molecule,
An active energy ray-curable composition, wherein the SP value of the (meth) acryloyl copolymer is equal to or higher than the SP value of the polyfunctional (meth) acrylate.
(2) The active energy ray-curable composition according to (1), wherein the surface roughness Ra when a cured product is obtained with a film thickness of 3 μm is 1 nm or more.
(3) The active energy ray-curable composition according to (1) or (2), further comprising inorganic particles having an average primary particle diameter of 1 μm or less.
(4) 1 to 20 parts by weight of the (meth) acryloyl copolymer is included with respect to 100 parts by weight of the active energy ray-curable composition, and 75 to 98.5 parts by weight of the polyfunctional (meth) acrylate is included. The active energy ray-curable composition according to (3), which contains 0.5 to 5 parts by weight of inorganic particles.
(5) The active energy ray-curable composition according to any one of (1) to (4), wherein the (meth) acryloyl copolymer has a weight average molecular weight of 1000 or more and 100,000 or less.
(6) The active energy ray-curable composition according to any one of (1) to (5), wherein the hydrogen bonding group of the (meth) acryloyl copolymer is a hydroxyl group.
(7) The origin of the hydroxyl group of the (meth) acryloyl copolymer is due to the ring-opening / addition reaction of a monomer having an oxirane skeleton, and out of the total amount of monomers constituting the (meth) acryloyl copolymer The active energy ray-curable composition according to (6), wherein the monomer having an oxirane skeleton is 80% by weight or more.
(8) The active energy ray-curable composition according to (7), wherein the ring-opening / addition reaction of the monomer having the oxirane skeleton is an addition reaction of (meth) acrylic acid.
(9) The activity according to any one of (1) to (8), wherein the polyfunctional (meth) acrylate includes a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule. Energy ray curable composition.
(10) A hard coat film obtained by curing the active energy ray-curable composition according to any one of (1) to (9).
(11) A film laminate obtained by laminating the hard coat film according to (10) with another resin film.
(12) A roll-shaped film laminate obtained by winding the film laminate according to (11) into a roll.

  The hard coat obtained by curing the composition of the present invention is designed to form irregularities on the surface, and does not cause blocking even when the hard coats are in close contact with each other, and has high hardness. According to the present invention, an active energy ray-curable composition capable of forming such a hard coat can be provided.

  The present invention is a composition suitably used for forming a hard coat on the surface of a substrate such as a film, and is cured by irradiation with active energy rays.

  In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate, and means either one or both. Similarly, “(meth) acrylic acid” is a generic term for acrylic acid and methacrylic acid, meaning either one or both, and “(meth) acryloyl group” is a generic term for acryloyl group and methacryloyl group, Means either or both.

The composition of the present invention comprises a (meth) acryloyl copolymer having a hydrogen bonding group and an unsaturated double bond in the side chain, and a polyfunctional compound having two or more unsaturated double bond groups in one molecule ( And (meth) acrylate, wherein the SP value of the (meth) acryloyl copolymer is equal to or higher than the SP value of the polyfunctional (meth) acrylate. It is an active energy ray-curable composition.

<(Meth) acryloyl copolymer>
The (meth) acryloyl copolymer used in the present invention has a hydrogen bonding group and an unsaturated double bond in the side chain. The hydrogen bonding group means a functional group containing an element capable of hydrogen bonding with an element present in another functional group, specifically, a hydroxyl group, an amino group, a thiol group, a carboxyl group, a sulfonic acid group, an amide group. And a phosphate group, and a hydroxyl group is preferred. The amount of the hydrogen bonding group is not particularly limited, but is preferably 3.0 mmol / g or more. In the present invention, it is preferable that the (meth) acryloyl copolymer has a hydrogen bonding group, so that the SP value of the (meth) acryloyl copolymer can be easily made higher than that of the polyfunctional (meth) acrylate.

  The (meth) acryloyl copolymer used in the present invention has an unsaturated double bond. The (meth) acryloyl copolymer having such an unsaturated double bond includes, for example, a resin copolymerized with a (meth) acryloyl monomer, a (meth) acryloyl monomer and another monomer having an ethylenically unsaturated double bond, , A resin obtained by reacting a (meth) acryloyl monomer with a monomer having another ethylenically unsaturated double bond and an epoxy group, a (meth) acryloyl monomer and another ethylenically unsaturated double bond, and Examples thereof include a resin obtained by reacting an isocyanate group-containing monomer.

When the (meth) acryloyl copolymer has a hydroxyl group as a hydrogen bonding group, the hydroxyl group is preferably derived from a ring-opening / addition reaction of a monomer having an oxirane skeleton. Examples of the monomer having an oxirane skeleton include an aromatic epoxide having an epoxy group, an alicyclic epoxide, and an aliphatic epoxide.
Examples of the aromatic epoxide include di- or polyglycidyl ethers and novolac-type epoxy resins produced by the reaction of a polyhydric phenol having at least one aromatic nucleus or an alkylene oxide adduct thereof and epichlorohydrin.
As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is mentioned.

  Preferred examples of the aliphatic epoxide include di- or polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. For example, diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or 1,6 -Diglycidyl ether of alkylene glycol such as diglycidyl ether of hexanediol, polyglycidyl ether of polyhydric alcohol such as di- or triglycidyl ether of glycerin or its alkylene oxide adduct, diglycidyl of polyethylene glycol or its adduct of alkylene oxide Diglycidyl of polyalkylene glycol such as diglycidyl ether of ether, polypropylene glycol or its alkylene oxide adduct Ether and the like.

  The monomer having an oxirane skeleton is preferably 80% by weight or more, more preferably 90% by weight or more, and more preferably 95% by weight or more, based on the total amount of monomers constituting the (meth) acryloyl copolymer. Is more preferable. When the monomer composition ratio having an oxirane skeleton is large, the amount of hydroxyl groups that can be introduced and the amount of unsaturated double bonds are preferably increased.

  The ring opening / addition reaction of the monomer having an oxirane skeleton is preferably an addition reaction of acrylic acid. By making the reaction of acrylic acid, unsaturated double bonds can be introduced while achieving a high SP value by introducing a hydroxyl group, which is preferable because photocurability can be improved.

The (meth) acryloyl copolymer used in the present invention preferably has a weight average molecular weight (Mw) of 1,000 or more, more preferably 5,000 or more, and 10,000 or more. Further preferred. Moreover, it is preferable that it is 100,000 or less, It is more preferable that it is 70,000 or less, It is still more preferable that it is 50,000 or less. Within this range, gelation based on the (meth) acryloyl copolymer is unlikely to occur.
In addition, the weight average molecular weight (Mw) of a (meth) acryloyl copolymer can be determined as a conversion value by a polystyrene standard using GPC.

The (meth) acryloyl copolymer used in the present invention is preferably contained in an amount of 1 part by weight or more, more preferably 3 parts by weight or more, based on 100 parts by weight of the active energy ray-curable composition of the present invention. More preferably, it is 5 parts by weight or more. Further, it is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less.
In the active energy ray-curable composition of the present invention, these (meth) acryloyl copolymers may be contained singly or in combination of two or more.

<Multifunctional (meth) acrylate>
The polyfunctional (meth) acrylate used in the present invention is a polyfunctional (meth) acrylate having two or more unsaturated double bond groups in one molecule. As such polyfunctional (meth) acrylate, for example, polyfunctional (having two or more unsaturated double bond groups in one molecule, which is a dealcoholization reaction product of polyhydric alcohol and (meth) acrylate) And (meth) acrylate. Among polyfunctional (meth) acrylates, polyfunctional (meth) acrylates having 3 or more (meth) acryloyl groups in one molecule are preferable. Specifically, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, nanoethylene glycol di (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, neopentyl glycol di (meth) acrylate, and the like.
These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

The polyfunctional (meth) acrylate used in the present invention is preferably contained in an amount of 75 parts by weight or more, more preferably 85 parts by weight or more, based on 100 parts by weight of the active energy ray-curable composition of the present invention. More preferably, it is 90 parts by weight or more. Moreover, it is preferable that it is 98.5 weight part or less, It is more preferable that it is 97 weight part or less, It is still more preferable that it is 95 weight part or less.
In the active energy ray-curable composition of the present invention, these polyfunctional (meth) acrylates may be contained singly or in combination of two or more.
Moreover, it is preferable that the polyfunctional (meth) acrylate used for this invention does not contain the monomer which contains an ethylene oxide (EO) unit in a molecule | numerator substantially, and it is more preferable not to contain. By not containing a monomer containing an ethylene oxide (EO) unit in the molecule, sufficient hardness can be ensured when a hard coat is formed. The term “substantially” used herein means less than 3 parts by weight based on 100 parts by weight of the entire polyfunctional (meth) acrylate.

In the active energy ray-curable composition of the present invention, the SP value of the (meth) acryloyl copolymer is not less than the SP value of the polyfunctional (meth) acrylate. Preferably, the SP value of the (meth) acryloyl copolymer is 0.5 or more higher and 1.0 or more higher than the SP value of the polyfunctional (meth) acrylate.
Further, the SP value of the (meth) acryloyl copolymer used in the present invention is preferably 14.0 or more, more preferably 16.0 or more, and preferably 20.0 or less, 18 More preferably, it is 0.0 or less.
On the other hand, the SP value of the polyfunctional (meth) acrylate used in the present invention is preferably 8.0 or more, more preferably 10.0 or more, and preferably 14.0 or less. More preferably, it is 0 or less.
The SP value is an abbreviation for solubility parameter (solubility parameter) and is a measure of solubility. The SP value indicates that the polarity is higher as the numerical value is larger, and the polarity is lower as the numerical value is smaller.
For example, the SP value can be measured by the following method [references: SUH, CLARKE, J. et al. P. S. A-1, 5, 1671-1681 (1967)].

In the present invention, the SP value of the (meth) acryloyl copolymer is preferably equal to or higher than the SP value of the polyfunctional (meth) acrylate, which is preferable because phase separation is easily generated.
In order to set the SP value of the (meth) acryloyl copolymer to be equal to or higher than the SP value of the polyfunctional (meth) acrylate, for example, the side chain of the (meth) acryloyl copolymer includes a large number of highly polar groups. What is necessary is just to design, for example, the method of preparing a copolymer by ring-opening the monomer which has an oxirane skeleton by addition of (meth) acrylic acid etc. are mentioned. In addition, the polyfunctional (meth) acrylate may be designed to have a low SP value. For example, a method of adding a bifunctional or higher acrylate having an alicyclic skeleton may be used.

  The (meth) acryloyl copolymer and the polyfunctional (meth) acrylate included in the present invention preferably each have a functional group that reacts with each other. By reacting such functional groups with each other, the resistance of the layer obtained by curing the active energy ray-curable composition of the present invention can be increased. As a combination of such functional groups, for example, a functional group having active hydrogen (hydroxyl group, amino group, thiol group, carboxyl group, etc.) and an epoxy group, a functional group having active hydrogen and an isocyanate group, and an ethylenically unsaturated group Ethylenically unsaturated group (polymerization of ethylenically unsaturated group occurs), silanol group and silanol group (condensation polymerization of silanol group occurs), silanol group and epoxy group, functional group having active hydrogen and functional group having active hydrogen Groups, active methylene and acryloyl groups, oxazoline groups and carboxyl groups.

  In addition, as "functional groups that react with each other" here, the reaction does not proceed only by mixing the (meth) acryloyl copolymer and the polyfunctional (meth) acrylate, but the polymerization initiator is mixed together. Also included are those that react with each other. The polymerization initiator that can be used here is a photopolymerization initiator, and details will be described later.

<Inorganic particles>
The active energy ray-curable composition of the present invention preferably contains inorganic particles having an average primary particle size of 1 μm or less. Curability capable of forming a hard coat having good anti-blocking property while maintaining high hardness by containing inorganic particles having an average primary particle size of 1 μm or less and a highly polar (meth) acryloyl copolymer. A composition can be provided.
In the present invention, in addition to being able to phase-separate the copolymer by adding a highly polar (meth) acryloyl copolymer together with the polyfunctional (meth) acrylate, it is cured by adding inorganic particles together. In this case, inorganic particles are also present in the vicinity of the surface together with the phase-separated copolymer. The curable composition of the present invention, due to the presence of this copolymer and inorganic particles, forms appropriate irregularities on the surface when used as a hard coat layer, and has excellent antiblocking properties. It is preferable to do.

  Examples of inorganic particles include silica (including organosilica sol), alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide) / Tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, antimony oxide and the like. These inorganic particles may be contained alone or in combination of two or more.

  The average primary particle diameter of the inorganic particles is 1 μm or less, preferably 200 nm or less, and more preferably 100 nm or less. Although a lower limit is not specifically limited, Usually, 5 nm or more, Preferably it is 10 nm or more. Use of inorganic particles having a particle size of 1 μm or more is not preferable because sedimentation occurs due to the weight of the particles, and the storage stability of the hard coat liquid tends to decrease.

On the other hand, since the movement of inorganic particles in the above range is governed by thermal diffusion rather than sedimentation by gravity, it becomes possible to disperse particles stably in the hard coat liquid, and when the hard coat film is formed, the surface is effectively exposed to the surface. Inorganic particles can be present. Moreover, there exists a tendency for an optical characteristic to become favorable, so that the average primary particle diameter of an inorganic particle is small.
The average primary particle diameter of the inorganic particles in the present invention refers to a diameter obtained by averaging the particle sizes observed with an electron microscope such as TEM.

  The inorganic particles used in the present invention are preferably contained in an amount of 0.5 parts by weight or more, more preferably 0.7 parts by weight or more, based on 100 parts by weight of the active energy ray-curable composition of the present invention. More preferably, it is 1 part by weight or more. Further, it is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 2 parts by weight or less.

<Polymerization initiator>
The active energy ray-curable composition of the present invention preferably contains a polymerization initiator in order to be cured by active energy. The polymerization initiator is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, and usually 20 parts by weight or less, preferably 100 parts by weight or more based on the curable composition. 10 parts by weight or less can be added.
The polymerization initiator may be any photopolymerization initiator, such as 2-hydroxy-2methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1 and the like.

  The method for preparing the active energy ray-curable composition of the present invention is not particularly limited. For example, a (meth) acryloyl copolymer and a polyfunctional (meth) acrylate are optionally mixed with a solvent, a polymerization initiator, and an additive. It can prepare by mixing together.

The solvent used in the preparation of the active energy ray-curable composition of the present invention is not particularly limited, and is a (meth) acryloyl copolymer, a polyfunctional (meth) acrylate, or a material for a base material for coating. , And a method for applying the composition, and the like. Specific examples of the solvent that can be used include aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, and cyclohexanone; diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, and ethylene glycol. Ether solvents such as dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, anisole, and phenetol; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; dimethylformamide, Amide solvents such as diethylformamide and N-methylpyrrolidone; methyl Cellosolve, ethyl cellosolve, cellosolve solvents such as butyl cellosolve; methanol, ethanol, propanol, isopropanol, alcohol solvents such as butanol; and the like; dichloromethane, halogenated solvents such as chloroform.
These solvents may be used alone or in combination of two or more. Of these solvents, ester solvents, ether solvents, alcohol solvents and ketone solvents are preferably used.

  Various additives can be added to the active energy ray-curable composition of the present invention as necessary. Examples of such additives include conventional additives such as antistatic agents, plasticizers, surfactants, antioxidants and ultraviolet absorbers.

<Hard coat film>
The hard coat film of this invention is obtained by apply | coating the active energy ray curable composition of this invention on a base material etc., and making it harden | cure to a film form. Moreover, the film laminated body which has a hard-coat layer is obtained by shape | molding a hard-coat film by apply | coating and hardening the composition of this invention on another resin film as a base material.

  As the base material for molding the hard coat film, various plastic films and plastic plates can be used. Examples of plastic films include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic resin film, polyurethane resin film, polyester film Polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyether ketone film, (meth) acrylonitrile film, cycloolefin polymer (COP) film and the like can be used. Examples of plastic plates include acrylic plates, triacetyl cellulose plates, polyethylene terephthalate plates, diacetylene cellulose plates, acetate butyrate cellulose plates, polyethersulfone plates, polyurethane plates, polyester plates, polycarbonate plates, polysulfone plates, polyethers. Examples include a plate, a polymethylpentene plate, a polyetherketone plate, and a (meth) acrylonitrile plate. In addition, although the thickness of a base material can be selected timely according to a use, it is generally used at about 25-1000 micrometers.

  The application method of the active energy ray-curable composition of the present invention is not particularly limited. For example, dip coating method, air knife coating method, curtain coating method, spin coating method, roller coating method, bar coating method, wire bar coating method. It can be applied by a gravure coating method or an extrusion coating method (US Pat. No. 2,681,294).

  The thickness of the hard coat layer is not particularly limited, and can be set in a timely manner in consideration of various factors. The active energy ray-curable composition is usually adjusted so that the film thickness is 0.01 to 20 μm. Can be applied.

The hard coat formed on the substrate may be phase-separated at room temperature, or may be phase-separated in advance by drying the composition before curing. When drying or heating the applied composition before curing, it is dried at 30 to 200 ° C., more preferably 40 to 150 ° C. for 0.01 to 30 minutes, more preferably 0.1 to 10 minutes. , Phase separation can be performed in advance. Drying before curing and phase separation in advance is preferable because the solvent in the coating film having fine irregularities can be effectively removed and irregularities of a desired size can be provided on the hard coat.

As another method of phase separation before curing, a method of irradiating the coating film with light and causing phase separation can also be used. As light to irradiate, for example, light with an exposure amount of 0.1 to 3.5 J / cm ² ,
Preferably, light of 0.5 to 1.5 J / cm ² can be used. The wavelength of the irradiation light is not particularly limited, and for example, irradiation light having a wavelength of 360 nm or less can be used. For example, when 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one or the like is used as the polymerization initiator, the irradiation light is irradiated with light having a wavelength near 310 nm. Further, it is more preferable to irradiate light having a wavelength near 360 nm. Such light can be obtained using a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like. By irradiating light in this way, phase separation and curing will occur. By irradiating light to cause phase separation, unevenness of the surface shape due to drying unevenness of the solvent contained in the curable composition can be avoided, which is preferable.

A coating film having fine irregularities is formed by curing a coating film obtained by applying the antiblocking curable resin composition or a dried coating film. Curing can be performed by irradiating light using a light source that emits light having a wavelength as required. In addition, the light irradiation for hardening has an integrated light quantity of 100 mJ / cm ² or more and 20,000.
Irradiation is preferably performed so as to be mJ / cm ² or less. As the light source, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used.

  The hard coat of the present invention thus formed has a good blocking property. The good blocking property of the present invention is that the (meth) acryloyl copolymer is phase-separated in the hard coat layer and the contained inorganic particles are present in the vicinity of the surface, thereby imparting good irregularities to the hard coat layer surface. This is due to that.

Therefore, the active energy ray-curable composition of the present invention preferably has a surface roughness Ra of 1 nm or more, more preferably 3 nm or more when a cured product is obtained with a film thickness of 3 μm. Although an upper limit is not specifically limited, Usually, it is 200 nm or less.
The surface roughness Ra means arithmetic average roughness (Ra), and is a parameter defined in JIS B 0601-2001. For example, a high-precision fine shape measuring instrument manufactured by Kosaka Laboratory Ltd., or Keyence Corporation. It can be measured according to JIS B 0601-2001 using a manufactured color 3D laser microscope or the like.

In the active energy ray-curable composition of the present invention, Sm is preferably 0.001 μm or more and 10 μm or less when a cured product is obtained with a film thickness of 3 μm, and is 0.005 μm or more and 5 μm or less. It is more preferable that it is 0.01 μm or more and 3 μm or less. Here, Sm is the average length of the roughness curve elements on the surface, and is generally referred to as the average interval between the peaks and valleys of the roughness curve or the average interval between the irregularities.
Sm can be measured in accordance with JIS B0633 using, for example, a high-precision fine shape measuring instrument manufactured by Kosaka Laboratories or a color 3D laser microscope manufactured by Keyence Corporation.

Moreover, the hard coat which hardened the active energy ray curable composition of this invention has favorable hardness. In the active energy ray-curable composition of the present invention, the pencil hardness measured according to JIS-K5600 when a cured product is obtained with a film thickness of 3 μm is preferably H or more, more preferably 2H or more. preferable.

In addition, the hard coat obtained by curing the active energy ray-curable composition of the present invention has good transparency. The active energy ray-curable composition of the present invention has a total light transmittance and haze of 85% or more, preferably 90% or more when the cured product is obtained with a film thickness of 3 μm. Is 2.0% or less, preferably 1.8% or less, more preferably 1.5% or less, and still more preferably less than 1.0%.
The total light transmittance (Tt (%)) is calculated by the following equation by measuring the incident light intensity (T0) with respect to the cured product and the total transmitted light intensity (T1) transmitted through the cured product.
Tt (%) = (T ₁ / T ₀ ) × 100
The total light transmittance can be measured using, for example, a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd.).

The haze can be calculated from the following formula in accordance with JIS K7136.
H (%) = (Td / Tt) × 100
H: Haze (cloudiness value) (%)
Td: Diffuse light transmittance (%)
Tt: Total light transmittance (%)
In addition, the measurement of haze can be measured, for example using a turbidimeter (made by Nippon Denshoku Industries Co., Ltd.).

<Roll film laminate>
The film laminate of the present invention exhibits good antiblocking properties when wound into a roll and is preferably applied to such an embodiment.
Such a roll-shaped film laminate is produced by forming the hard coat of the present invention on a substrate film and winding it in a roll shape.

<Display device>
The present invention further relates to a display device including the laminate film of the present invention and a light source. In this case, the base material included in the laminate film is preferably a light-transmitting base material. Moreover, it is preferable that a light source is arrange | positioned on the back surface of a base material, ie, the surface on the opposite side to the fine uneven | corrugated layer of a base material, and irradiates light toward a base material there.

  As the translucent substrate, a translucent plastic film and a plastic plate are preferable among the above-described substrates, and glass or the like may be used as necessary. As translucent plastic films, triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyethersulfone film, polyacrylic resin film, polyurethane resin Film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth) acrylonitrile film, and cycloolefin polymer (COP) film are preferred. In particular, acrylic plates, triacetyl cellulose plates, polyethylene terephthalate plates, diacetylene cellulose plates, acetate plates Rate cellulose plates, polyether sulfone plate, polyurethane plate, polyester plate, polycarbonate plate, polysulfone plates, polyether board, polymethyl pentene plate, polyetherketone plate, (meth) acrylonitrile plate preferable. It is preferable to use a PET film as the translucent substrate from the viewpoint of strength. In addition, although the thickness of a translucent base material can be selected timely according to a use, generally it is used at about 25-1000 micrometers.

  The light source that can be combined with the film laminate is not particularly limited as long as it can emit light. Examples of the light source include a light emitting diode, a cold cathode tube, a hot cathode tube, and an EL. It is done. The display device of the present invention may further include a retardation plate, a brightness enhancement film, a light guide plate, a light diffusing plate, a light diffusing sheet, a light collecting sheet, a reflecting plate, and the like. Further, a liquid crystal module, a backlight unit, or the like may be used as the light source.

  As the light transmissive member, various light transmissive plates, light transmissive films, and the like can be used. For example, tempered glass, acrylic plate, triacetyl cellulose plate, polyethylene terephthalate plate, diacetylene cellulose plate, acetate butyrate cellulose plate, polyethersulfone plate, polyurethane plate, polyester plate, polycarbonate plate, polysulfone plate , Polyether plate, polymethylpentene plate, polyether ketone plate, (meth) acrylonitrile plate and the like. Examples of the light transmissive film include triacetyl cellulose (TAC) film, polyethylene terephthalate (PET) film, diacetylene cellulose film, acetate butyrate cellulose film, polyether sulfone film, polyacrylic resin film, polyurethane resin film, Examples include a polyester film, a polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyether ketone film, a (meth) acrylonitrile film, and a cycloolefin polymer (COP) film. As the light transmissive member, an acrylic plate, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a cycloolefin polymer (COP) film, and tempered glass are more preferably used. In addition, although the thickness of a light transmissive member can be selected timely according to a use, it is generally used at about 25-1000 micrometers.

In the case of a liquid crystal module, the light source is included, and a polarizing plate / liquid crystal cell / polarizing plate is arranged in this order on the light source. The liquid crystal cell is not particularly limited as long as it is generally used in a liquid crystal display device. For example, TN (Twisted Ne
magic) type liquid crystal cell, STN (Super Twisted Nematic) type liquid crystal cell, HAN (Hybrid Alignment Nematic) type liquid crystal cell, IPS (In Plane Switching) type liquid crystal cell, VA (Vertical Ali)
and a liquid crystal cell such as a multiple vertical alignment liquid crystal cell and an OCB (optically compensated bend) liquid crystal cell.

  The display device of the present invention is applied to a flat panel display such as a liquid crystal display device (liquid crystal display), LED (light emitting diode display), ELD (electroluminescence display), VFD (fluorescent display), PDP (plasma display panel), etc. can do. Moreover, since the active energy ray-curable composition of the present invention that can be used for the production of the display device of the present invention has weather resistance in addition to anti-blocking properties, the display device can be used outdoors. Is possible. For example, it can be installed outdoors or semi-outdoors as a panel display for the purpose of posting information such as advertisements.

  In addition, the outdoor or semi-outdoor use of the display device of the present invention includes a touch panel, which has a mechanism for operating equipment by holding down the display on the screen, for example, bank ATM, vending Machines, personal digital assistants (PDAs), copiers, facsimiles, game machines, information displays installed in facilities such as museums and department stores, car navigation systems, multimedia stations (multifunctional terminals installed in convenience stores), This is useful in mobile phones, railway vehicle monitoring devices, and the like.

Hereinafter, the present invention will be described in detail by way of specific embodiments, but it goes without saying that the present invention is not limited to only the embodiments.
<Synthesis Example 1>
(A-1) Synthesis method of (meth) acryloyl copolymer A In a flask equipped with a thermometer, a stirrer and a reflux condenser, 157.3 g of propylene glycol monomethyl ether, 98.0 g of glycidyl methacrylate, 1.0 g of methyl methacrylate, 1.0 g of ethyl acrylate, 1.9 g of mercaptopropyltrimethoxysilane, and 1.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours.
Thereafter, 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours, and then 138.1 g of propylene glycol monomethyl ether and 0.45 g of p-methoxyphenol were added to 100 ° C. Heated.
Next, 50.7 g of acrylic acid and 3.08 g of triphenylphosphine were added and reacted at 110 ° C. for 6 hours, whereby an acryloyl equivalent having an acryloyl group and a methoxysilyl group and a weight average molecular weight of 20,000 ( (Amount of introduction of acryloyl group) 4.47 mmol / g A (meth) acryloyl copolymer (A-1) containing a secondary hydroxyl group of 4.47 mmol / g was obtained. The SP value of the (meth) acryloyl copolymer (A-1) was 17.8.

<Synthesis Example 2>
(A-2) Method for synthesizing colloidal silica surface-modified with (meth) acryloyl copolymer A-1 (Meth) acryloyl copolymer (A-1) obtained in Synthesis Example 1 in a four-necked flask 3.75 parts by weight of (C-1) colloidal silica (Nissan Chemical: MEK-ST (average primary particle size 1
0 to 15 nm))) 1.25 parts by weight were added, 0.005 part by weight of acetylacetone aluminum was added as a catalyst for the silane coupling reaction, and the reaction was carried out at 70 ° C. for 4 hours to obtain a (meth) acryloyl copolymer (A- Colloidal silica surface-modified in 1) was prepared.

<Synthesis Example 3>
(AD-1) Synthesis Method of (Meth) acryloyl Copolymer as Additive Material Into a four-necked flask, 50 g of methyl methacrylate, 33 g of stearyl methacrylate, 17 g of PEO-modified methacrylate, and 233.3 g of methyl ethyl ketone are added. 1.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted at 65 ° C. for 3 hours to obtain a (meth) acryloyl copolymer (AD-1).
Moreover, LC-915 of the PEO modified silicone made from Enomoto Kasei was prepared as an additive (AD-2).

<Example 1>
In a four-necked flask, 1 part by weight of colloidal silica surface-modified with (A-2) (meth) acryloyl copolymer A-1, then (O-1) dipentaerythritol hexaacrylate (SP value of 12. 1) 19.0 parts by weight of (AD-1) as an additive and 0.1 part by weight of (AD-2) as an additive in 99.0 parts by weight, and then 1-hydroxy-cyclohexyl-phenyl- as a polymerization initiator An active energy ray-curable composition was obtained by adding 5 parts by weight of ketone (Irgacure 184) and 157.5 parts by weight of methyl ethyl ketone.

<Example 2>
(A-2) Same as Example 1 except that 3 parts by weight of colloidal silica surface-modified with (meth) acryloyl copolymer A-1 and 97 parts by weight of (O-1) dipentaerythritol hexaacrylate Thus, an active energy ray-curable composition was obtained.

<Example 3>
(A-2) Same as Example 1 except that 5 parts by weight of colloidal silica surface-modified with (meth) acryloyl copolymer A-1 and 95 parts by weight of (O-1) dipentaerythritol hexaacrylate Thus, an active energy ray-curable composition was obtained.

<Example 4>
(A-2) Same as Example 1 except 20 parts by weight of colloidal silica surface-modified with (meth) acryloyl copolymer A-1 and 80 parts by weight of (O-1) dipentaerythritol hexaacrylate Thus, an active energy ray-curable composition was obtained.

<Example 5>
Active energy ray curing was carried out in the same manner as in Example 1 except that (O-1) dipentaerythritol hexaacrylate was 94 parts by weight, and (O-2) isocyanuric acid EO-modified di and 5 parts by weight of triacrylate were newly added. Sex composition was obtained.

<Example 6>
(A-2) The same as Example 5 except that 3 parts by weight of colloidal silica surface-modified with (meth) acryloyl copolymer A-1 and 92 parts by weight of (O-1) dipentaerythritol hexaacrylate were used. Thus, an active energy ray-curable composition was obtained.

<Example 7>
(A-2) Same as Example 5 except that 5 parts by weight of colloidal silica surface-modified with (meth) acryloyl copolymer A-1 and 90 parts by weight of (O-1) dipentaerythritol hexaacrylate Thus, an active energy ray-curable composition was obtained.

<Example 8>
(A-2) Same as Example 5 except that the colloidal silica surface-modified with (meth) acryloyl copolymer A-1 was 20 parts by weight and (O-1) dipentaerythritol hexaacrylate was 75 parts by weight. Thus, an active energy ray-curable composition was obtained.

<Example 9>
(A-2) In place of colloidal silica surface-modified with (meth) acryloyl copolymer A-1, (A-1) 0.75 parts by weight of (meth) acryloyl copolymer, (C-1) An active energy ray-curable composition was obtained in the same manner as in Example 1 except that colloidal silica (Nissan Chemical: MEK-ST, average primary particle size: 10 to 15 nm) was changed to 0.25 parts by weight.

<Example 10>
(A-1) Except that (meth) acryloyl copolymer was 2.25 parts by weight, (C-1) colloidal silica was 0.75 parts by weight, and (O-1) dipentaerythritol hexaacrylate was 97 parts by weight. Obtained an active energy ray-curable composition in the same manner as in Example 1.

<Example 11>
(A-1) Except for (meth) acryloyl copolymer 3.75 parts by weight, (C-1) colloidal silica 1.25 parts by weight, (O-1) dipentaerythritol hexaacrylate 95 parts by weight Obtained an active energy ray-curable composition in the same manner as in Example 1.

<Example 12>
Example 1 except that (A-1) (meth) acryloyl copolymer was 15 parts by weight, (C-1) colloidal silica was 5 parts by weight, and (O-1) dipentaerythritol hexaacrylate was 80 parts by weight. In the same manner as above, an active energy ray-curable composition was obtained.

<Example 13>
(A-1) Except that (meth) acryloyl copolymer was 3.75 parts by weight, (O-1) dipentaerythritol hexaacrylate was 96.25 parts by weight, and (C-1) colloidal silica was not blended. Obtained an active energy ray-curable composition in the same manner as in Example 1.
<Example 14>
(A-1) 3.75 parts by weight of (meth) acryloyl copolymer, 95 parts by weight of (O-1) dipentaerythritol hexaacrylate, and (C-1) instead of colloidal silica, (C-2 ) An active energy ray-curable composition was obtained in the same manner as in Example 1 except that 1.25 parts by weight of acrylic fine particles (manufactured by Soken Chemical Co., Ltd .: Chemisnow 8H3WT, average primary particle size 0.8 μm) were blended.

<Comparative Example 1>
(O-1) 100 parts by weight of dipentaerythritol hexaacrylate, 1 part by weight of (AD-1) and 0.1 part by weight of (AD-2) as additives, and then 1 as a polymerization initiator An active energy ray-curable composition was obtained by adding 5 parts by weight of -hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184) and 157.5 parts by weight of methyl ethyl ketone.

Next, with respect to the active energy ray-curable compositions obtained in Examples 1 to 14 and Comparative Example 1, a molded body was obtained through the following coating process and curing process.
<Application process>
The active energy ray-curable composition is dried on a transparent biaxially stretched polyethylene terephthalate film having a thickness of 188 μm (haze value: 0.8%; trade name: Diafoil T300E, manufactured by Mitsubishi Chemical Polyester) using a bar coater. It apply | coated so that the coating film thickness after that might be 2-3 micrometers, and it heat-dried at 80 degreeC for 1 minute.
<Curing process>
Using a PET film coated with the active energy ray-curable composition, a high-pressure mercury lamp with an output density of 120 W / cm as a light source, using an eye graphic EYE UV METER UVPF-A1, PD365 at a position of 15 cm under the light source. Integrated light quantity 200mJ / cm ²
The cured film was obtained by irradiating with UV.

An evaluation test was performed on the obtained cured film. The results are shown in Table 2. The evaluation method is as follows.
<Total light transmittance>
The obtained cured film was allowed to stand in a temperature-controlled room at 23 ° C. and 60% relative humidity for 12 hours, and then the transparency of the cured film was evaluated with a haze meter according to JIS K-7105.
<Transparency (haze value)>
The obtained cured film was allowed to stand in a temperature-controlled room at 23 ° C. and a relative humidity of 60% for 12 hours, and then the transparency of the cured film was evaluated in terms of haze value (H%) according to JIS K-7105. By subtracting (H%), the haze value (H%) of the cured film was obtained and evaluated according to the following criteria.
Less than 0.5: ○
0.5 to less than 1.0: Δ
1.0 or more: ×
<Pencil hardness>
Pencil hardness was measured with respect to the obtained cured film in accordance with JIS-K5600.
<Surface roughness Ra>
The obtained cured film was left in a temperature-controlled room at 23 ° C. and a relative humidity of 60% for 12 hours, and then the surface roughness Ra of the cured film was measured by AFM. Only Example 3 and Comparative Example 1 were measured.

<Abrasion resistance>
The surface of the obtained cured film was visually observed for flaws when Bonster steel wool (# 0000) was reciprocated 20 times with a load of 500 g, and the wear resistance was evaluated according to the following criteria. The smaller the number of scratches, the better the wear resistance.
No scratch: ◎
Some scratches: ○
Innumerable scratches: △
Scratches are severe and the film whitens: ×
<Blocking resistance>
After preparing two substrates coated with the active energy ray-curable composition after curing, the coated surfaces were overlapped at 23 ° C. and a relative humidity of 60%, and a load of about 1 kg was applied with finger pressure. It was confirmed whether the coated surfaces had slipperiness, and blocking resistance was evaluated according to the following criteria. Easy to shift: ○
Can be shifted, but it sounds: △
When the coated surfaces are in close contact with each other and cannot be shifted: ×

  The film coated with the active energy ray-curable composition of the present invention can suppress the occurrence of blocking that occurs when the films contact each other. For this reason, damage to the film due to unexpected blocking can be avoided, which is advantageous when storing with a winding roll.

Claims (12)

Contains a (meth) acryloyl copolymer having a hydrogen bond group and an unsaturated double bond in the side chain, and a polyfunctional (meth) acrylate having two or more unsaturated double bond groups in one molecule. An active energy ray curable composition comprising:
An active energy ray-curable composition in which the SP value of the (meth) acryloyl copolymer is not less than the SP value of the polyfunctional (meth) acrylate.   The active energy ray-curable composition according to claim 1, wherein the surface roughness Ra when a cured product is obtained with a film thickness of 3 μm is 1 nm or more.   The active energy ray-curable composition according to claim 1 or 2, further comprising inorganic particles having an average primary particle diameter of 1 µm or less.   1 to 20 parts by weight of the (meth) acryloyl copolymer, 75 to 98.5 parts by weight of the polyfunctional (meth) acrylate, and 100 to 100 parts by weight of the active energy ray-curable composition, The active energy ray-curable composition according to claim 3, comprising 0.5 to 5 parts by weight.   The active energy ray-curable composition according to any one of claims 1 to 4, wherein the (meth) acryloyl copolymer has a weight average molecular weight of 1,000 or more and 100,000 or less.   The active energy ray-curable composition according to any one of claims 1 to 5, wherein the hydrogen-bonding group of the (meth) acryloyl copolymer is a hydroxyl group.   The hydroxyl group of the (meth) acryloyl copolymer is derived from the ring-opening / addition reaction of a monomer having an oxirane skeleton, and the oxirane skeleton out of the total amount of monomers constituting the (meth) acryloyl copolymer. The active energy ray-curable composition according to claim 6, wherein the monomer having a content of 80% by weight or more.   The active energy ray-curable composition according to claim 7, wherein the ring-opening / addition reaction of the monomer having an oxirane skeleton is an addition reaction of (meth) acrylic acid.   The active energy ray curing according to any one of claims 1 to 8, wherein the polyfunctional (meth) acrylate includes a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule. Sex composition.   The hard coat film formed by hardening | curing the active energy ray hardening composition of any one of Claims 1-9.   The film laminated body formed by laminating | stacking the hard coat film of Claim 10 with another resin film.   The roll-shaped film laminated body formed by winding the film laminated body of Claim 11 in roll shape.