JP5713528B2 - Active energy ray-curable resin composition, hard coat cured film and laminate - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition substantially free of a solvent, a cured film for hard coat obtained by curing the composition, and a laminate having the same.

  Plastic products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile butadiene styrene copolymer (ABS), methyl methacrylate-styrene copolymer (MS resin), acrylonitrile styrene copolymer (AS resin), etc. Resin materials such as styrene resin, vinyl chloride resin, and cellulose acetate such as triacetyl cellulose are particularly excellent in lightness, ease of processing, impact resistance, etc. Display for outer panels, skylights, window materials, roofing materials, solar cell panels, packaging materials, various housing materials, optical disk substrates, plastic lenses, liquid crystal displays, plasma displays, organic EL displays, projection TVs, etc. Vessels of the substrate, etc., are used in various applications.

However, since these plastic products have low surface hardness, they are easily damaged. In the case of transparent resins such as polycarbonate and polyethylene terephthalate, once they are damaged, the original transparency or appearance of the resin is significantly impaired. This makes it difficult to use plastic products in fields that require wear resistance.
For this reason, there is a need for an active energy ray-curable hard coat material (coating material) that imparts wear resistance to the surface of these plastic products, and these are generally applied to active energy ray-curable resin compositions. A cured film obtained by polymerizing by irradiation (hereinafter sometimes simply referred to as “cured film”) is used.

  For example, polyfunctional acrylates having three or more acryloyl groups in one molecule and derivatives thereof (urethane acrylate, ester acrylate, epoxy acrylate, etc.) are widely used as suitable for these. However, a cured film of an active energy ray-curable hard coat material using only such a compound as a curing component has large shrinkage, warpage, peeling, and cracking, so that it is difficult to apply thickly. As a result, there are limits to the hardness and scratch resistance that can be achieved.

In addition, except for some compounds, polyfunctional acrylates generally have a very high viscosity at room temperature (5,000 to 1,000,000 mPa · s), which causes restrictions on the coating method, coating with a uniform film thickness, and smoothness. It is difficult to apply such a surface, and it has been necessary to reduce the viscosity at the time of application by diluting with a solvent or using an aqueous emulsion.
On the other hand, in recent years, active energy ray curing that can be used at high concentration or without solvent is used as much as possible from various viewpoints such as reduction of environmental burden, improvement of productivity, and ease of liquid recycling. The need for reactive coatings is increasing.

Among these problems, various approaches have been proposed and implemented for methods for reducing cure shrinkage. For example, the method of using the compound which has a 1-2 functional acrylic group as a reactive diluent can be mentioned.
However, this method generally has a problem that the inherent hardness and scratch resistance are lowered because the crosslinking density is lowered, and its use as a hard coat material is limited.
As the solventless active energy ray-curable resin composition, an improved product has been proposed limited to a specific application. For example, Patent Document 1 discloses an active energy ray-curable resin for in-line hard coating of a polyester film. The composition, Patent Document 2, describes an active energy ray-curable resin composition for an adhesive for laminating an optical disk.

In the case of an active energy ray-curable composition containing an organic-inorganic composite that provides high hardness and excellent scratch resistance (abrasion resistance), the inorganic components aggregate when solvent-free and thicken or become transparent. Therefore, it is difficult to obtain a solvent-free active energy ray-curable composition. On the other hand, Patent Documents 3 and 4 describe active energy ray-curable compositions containing an organic-inorganic composite without solvent.
In optical articles such as next-generation optical information media and optical displays with touch panel functions, fingerprint contamination has recently become a problem not only in appearance but also in performance and safety, especially in optical information media. The next-generation optical information medium has come to be regarded as a serious problem that directly affects performance, such as an increase in recording / reproducing errors. Depending on the usage environment as well as fingerprint smudges, contamination with other contaminants such as dust and dust may occur, which also cause serious errors such as recording failure and reproduction failure.

In particular, as a high-density optical information medium, the aperture diameter (N / A) of the objective lens is increased and / or the recording / reproducing wavelength is shortened to 400 nm, thereby reducing the beam condensing spot diameter. A medium having a recording density per density higher than that of the conventional DVD (DVD) has been proposed. For example, a new optical information medium such as Blu-Ray Disc or HD-DVD has appeared.
When the recording density is increased in this way, the diameter of the focused spot of the recording / reproducing beam on the surface of the recording / reproducing beam incident side of the medium becomes smaller, so that the influence of dirt such as fingerprints, dust, and dust becomes particularly large. Especially for dirt containing organic substances such as fingerprints, if the dirt adheres to the surface on the laser beam incident side of the medium, it will cause serious effects such as recording / playback errors and it will be difficult to remove them. Necessary.
The inventors of the present invention have already used a specific copolymer containing a specific polysiloxane group and an epoxy group in Patent Documents 5 and 6, or a (meth) acrylic acid reaction product as a stain resistance imparting agent. The active energy ray-curable resin composition containing such a stain resistance imparting agent has been shown to be extremely effective, and the hard coat material for optical display laminates such as next-generation optical disks or high-performance touch panels It is found that it is extremely excellent.
JP 2001-301095 A Japanese Patent Laid-Open No. 2005-196888 JP-A-6-299088 JP 2007-177194 A JP 2006-160802 A WO2006-059702

However, the active energy ray-curable resin composition described in Patent Document 1 is suitable for a coating process at a temperature higher than room temperature because it is used for in-line hard coating, but such a composition has a viscosity at room temperature. Due to its high cost, it is not necessarily suitable for the usual offline coating process.
The active energy ray-curable resin composition described in Patent Document 2 has been proposed with respect to viscosity and curability, which is suitable for the coating process. Hardness is insufficient and not practical.

The active energy ray-curable resin compositions described in Patent Documents 3 and 4 have insufficient curability, and the resulting cured film has insufficient hardness. Furthermore, the compatibility with a hydrophobic material such as a stain resistance imparting component is poor, and there are many problems with transparency, which are not practically satisfactory.
Conventional hard coat agents such as the active energy ray-curable resin compositions described in Patent Documents 5 and 6 contain an organic solvent, and when considering the reduction of the impact on the environmental load / recycling of the unreacted liquid, A drastic improvement was necessary.

The present invention aims to solve the above-mentioned problems, and can set a wide range of viscosities according to the coating method, and is excellent in curability even though it contains substantially no solvent. Therefore, the amount of photopolymerization initiator is small, it can be cured with active energy rays under moderate conditions, and the cured film obtained has good hardness, scratch resistance (wear resistance) and stain resistance, An object is to provide an active energy ray-curable resin composition.
In addition, a laminate having a cured film obtained by curing such a composition and / or a hard coat layer comprising the cured film on the surface, has high hardness, wear resistance, and lasts for a long time on the surface. It is another object of the present invention to provide a laminate having a cured film and / or a hard coat layer made of the cured film having excellent stain resistance and stain resistance durability.

  As a result of intensive studies to achieve the above object, the present inventor used an active energy ray-curable compound having a specific structure having stain resistance, and used a 1-4 functional (meth) acrylate or (meth) acrylamide. And a specific combination of photopolymerization initiators that can be cured with a relatively small addition amount, and a polyfunctional (meta) containing an organic-inorganic composite in which the polyfunctional (meth) acrylate is covalently bonded. ) Active energy ray-curable resin composition formulated with acrylate derivatives has higher curability, higher hardness, and scratch resistance than those conventionally known, and can be set to a viscosity that can be applied to various coating methods. The present inventors have found that the coating property is excellent and have reached the present invention.

Sunawa Chi invention, the following (A), the total amount of (B), (C) and comprise (D-2), the content of (A) and (B), (A) and (B) (A) is 35 to 90 parts by weight, and the content of (C) is 2 to 5 parts by weight with respect to 100 parts by weight of the total amount of (A) and (B). The content of (D-2) is 0.1 to 15 parts by weight with respect to 100 parts by weight of the total amount of (A) and (B), and the viscosity at 25 ° C. is 10 to 500 mPa · s. It is an active energy ray curable resin composition, and characterized in that it contains no organic solvent exceeds 5% by weight in the composition, related to the active energy ray curable resin composition.
(A) Multifunctional (meth) acrylate derivative containing an organic-inorganic composite in which a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule is bonded to inorganic oxide fine particles by covalent bonds body (B) 1-4 (meth) acryloyl groups and / or in one molecule containing (meth) acrylamide group, a 1-4-functional (meth) acrylate and / or (meth) acrylamide <br / > (C) Photopolymerization initiator (D-2) A monomer containing one or more groups selected from a polydimethylsiloxane group, a perfluoroalkyl group, and a perfluoroalkylene group, and a monomer containing a (meth) acrylate having an epoxy group And a carboxylic acid having one or more (meth) acryloyl groups in one molecule is reacted with at least a part of the epoxy groups of the radical polymer in the mixture. The active energy ray-curable polymer also present invention having the corresponding structure is related to the (B) at least one including, the active energy ray curable resin composition having the following (i) ~ (iii).
(I) a (meth) acrylate having one (meth) acryloyl group in one molecule, directly or directly to an oxygen atom bonded to the (meth) acryloyl group, an α-position carbon or a β-position A (meth) acrylate (ii) to which one selected from (poly) cycloalkyl group, (poly) cycloalkenyl group, hydroxyalkyl group, cyclic ether group, and (poly) alkylene oxide group is bonded via carbon. ) A (meth) acrylate having 2 to 4 (meth) acryloyl groups in one molecule, directly or directly to the oxygen atom bonded to at least one (meth) acryloyl group or the α-position carbon Alternatively, via a β-position carbon, (poly) cycloalkylene group, (poly) cycloalkenylene group, hydroxyalkylene group, cyclic ether group, (poly) (Meth) acrylate (iii) to which one selected from a ruxylene oxide group is bonded is a (meth) acrylamide having 1 to 4 (meth) acryloyl groups in one molecule, and a (meth) acryloyl group (Meth) acrylamide in which the amino group bonded to is substituted with two alkyl groups (however, the two alkyl groups may be bonded directly or through a hetero atom)
Moreover, this invention relates to the active energy ray-curable resin composition whose 1/3 or more of the total weight of said (B) is said (i)-(iii).

Moreover, this invention relates to the said active energy ray curable resin composition whose said (B) contains 1-4 acryloyl groups in 1 molecule.
In the present invention, (A) is a modified colloidal silica in which a reaction product of pentaerythritol triacrylate and triethoxysilylpropyl isocyanate is bonded to colloidal silica, and a reaction product of dipentaerythritol pentaacrylate and triethoxysilylpropyl isocyanate. A modified colloidal silica bonded to colloidal silica, a modified product of these modified colloidal silica with polyalkylene oxide, or a modified product of these modified colloidal silica with polycaprolactone. The present invention relates to a functional resin composition.

The present invention also relates to the active energy ray-curable resin composition, wherein (C) includes one or more selected from α-aminophenyl ketones, benzophenones, benzoylformic acid (esters), and oxime esters. .

The present invention also relates to the active energy ray-curable resin composition for optical materials.
Furthermore, this invention relates also to the cured film formed by irradiating the said active energy ray curable resin composition with an active energy ray.
Moreover, this invention relates also to the laminated body which has the hard-coat layer which consists of the said cured film on the surface.
Moreover, this invention applies the said active energy ray curable resin composition, forms a coating film, and irradiates an active energy ray without passing through the process of drying this coating film, and forms a cured film. It relates to the manufacturing method.

  The active energy ray-curable resin composition of the present invention is capable of setting a wide range of viscosities in accordance with the coating method, and is excellent in curability even though it contains substantially no solvent. Therefore, the cured film can be cured with active energy rays under mild conditions, and the resulting cured film has good hardness and scratch resistance (abrasion resistance). As a result, the active energy ray-curable resin composition is applied to a substrate for an optical recording medium or the surface of an optical display and cured to have excellent curability, scratch resistance, and transparency. The durability of the performance can be increased. In particular, since the active energy ray-curable resin composition of the present invention has good curability, it is possible to provide a hard coat layer with high surface hardness.

In addition, since it does not substantially contain a solvent, it is easy to recycle uncured liquid, and since it does not contain an organic solvent that is substantially volatile, the environmental load is small.
It also has excellent anti-contamination (particularly anti-fingerprint stains, easy to wipe off in the unlikely event that the effect lasts for a long time and is excellent in durability), and durability of product performance Can be increased.

In the following, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents. .
In the present specification, the (meth) acryloyl group is a general term for an acryloyl group and a methacryloyl group. The same applies to (meth) acryl and (meth) acrylate.
Further, in the present specification, “to” is used in the sense of including the numerical values described before and after it as a lower limit value and an upper limit value.
[I] Active energy ray-curable resin composition The active energy ray-curable resin composition of the present invention comprises (A) a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in one molecule, A polyfunctional (meth) acrylate derivative containing an organic-inorganic composite bonded to inorganic oxide fine particles by covalent bond, (B) 1 to 4 (meth) acryloyl groups and / or (meth) acrylamide groups in one molecule 1 to 4 functional (meth) acrylate and / or (meth) acrylamide, (C) a photopolymerization initiator, and (D-1) a polydimethylsiloxane group, a perfluoroalkyl group, or a perfluoroalkylene group. And an active energy ray-curable compound containing one or more groups having a viscosity of 10 to 500 mPa · s at 25 ° C., and an organic solvent exceeding 5% by weight in the composition. It is those which do not contain Te.

First, each component of (A)-(D-1) is demonstrated.
(A) Polyfunctional (meth) acrylate derivative The polyfunctional (meth) acrylate derivative which is the component (A) in the present invention is a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule. And an organic-inorganic composite (hereinafter sometimes referred to as (Ai)) bonded to inorganic oxide fine particles by a covalent bond.
In addition to component (Ai), component (A) is a compound in which polyfunctional (meth) acrylate is bonded to inorganic oxide fine particles by a bond other than a covalent bond, or polyfunctional (meth) not bonded to inorganic oxide fine particles. An acrylate or the like may be included.

The content of the component (Ai) in the component (A) is preferably 5% by weight or more, more preferably 10% by weight or more, preferably 80% by weight or less, more preferably 70% in the component (A). % By weight or less.
The organic-inorganic composite (Ai) that can be used in the present invention is usually a polysiloxane having three or more (meth) acryloyl groups in one molecule through —O—Si—R— bonds to the inorganic oxide fine particles. It is preferable that the functional (meth) acrylate is bonded. Here, R represents a linear or branched alkylene group having 2 to 10 carbon atoms.

(A-1) Silane coupling agent having a (meth) acryloyl group For the production of the organic-inorganic composite (Ai) that can be used in the present invention, for example, a silane coupling agent having a (meth) acryloyl group (hereinafter referred to as “a”). , (Sometimes referred to as (a-1)).
An -O-Si-R- bond (R represents a linear or branched alkylene group having 2 to 10 carbon atoms), more preferably an -O-Si-R-S- bond, is formed on the surface of the inorganic oxide fine particles. Therefore, in order to bond a group having a (meth) acryloyl group, it is preferable to use a silane coupling agent (a-1) having a (meth) acryloyl group.
A preferred example of such a component (a-1) is a silane coupling agent having a molecular weight of 300 or more and containing three or more acryloyl groups or methacryloyl groups as radically polymerizable functional groups. The number of acryloyl groups or methacryloyl groups is not particularly limited, but preferably 3 to 5 (meth) acryloyl groups per molecule. Further, the position is not particularly limited, but it is preferably at the end of the molecule.

  In addition, the component (a-1) is more preferably an organic compound having a structure represented by the following formula (1).

(Chemical formula 1)
-X-C-NH- (1)
‖
Y
(In formula (1), X and Y each independently represents an oxygen atom, a sulfur atom or an imino group).

  The structure represented by the formula (1) increases the mechanical strength by generating a strong cohesive force due to hydrogen bonds between molecules, and improves the adhesion of the resulting cured film to the substrate and the heat resistance. And also serves as a spacer between the surface of the inorganic oxide fine particles and the radical polymerizable functional group, and is effective in suppressing excessive aggregation. Specific examples include -OCONH-, -SCON-, -SCSNH-, -OCSNH-, -NHCONH-, and -NHCSNH- (hereinafter, these may be collectively referred to as Formula (2)). it can. Of these structures, —OCONH— and —SCONH— are particularly preferable from the viewpoints of thermal stability and ease of synthesis.

Component (a-1) may be an organic compound having a thioether group. A thioether group is also preferable because it acts as a spacer between the silica surface and a radical polymerizable functional group or a specific polar functional group, and has an effect of suppressing excessive aggregation.
As the functional group capable of forming a silanol group of the silane coupling agent (a-1) capable of binding to the inorganic oxide fine particles, an alkoxysilyl group is particularly preferable. Examples of alkoxysilyl groups include monoalkoxysilyl groups, dialkoxysilyl groups, trialkoxysilyl groups, etc. Among them, trialkoxysilyl groups of lower alcohols such as trimethoxysilyl groups and triethoxysilyl groups are reactive. This is particularly preferable. The position of these groups in the molecule is preferably at the end of the molecule opposite to the (meth) acryloyl group. Moreover, it is preferable that the number of groups in 1 molecule is 1-3, and it is more preferable that it is one.

A silanol group or a functional group capable of generating a silanol group (silanol group-generating unit) is a generated unit that can be combined with inorganic oxide fine particles by a condensation reaction or a condensation reaction subsequent to hydrolysis. Some preferred examples of compounds having such a generated unit are:
1) a compound in which an OH group of a (meth) acrylate compound having an OH group and an NCO group of a trialkoxysilane having an NCO group are combined to form -OCONH-;
2) The SH group of the trialkoxysilane compound having an SH group and one NCO group of the diisocyanate are combined to form -NHCOS-, and the remaining NCO group is allowed to act on the (meth) acrylate compound having an OH group, A compound bonded to form -NHCOO-,
3) A compound in which an NCO group of a (meth) acrylate compound having an NCO group and an SH group of a trialkoxysilane having an SH group are combined to form -NHCOS-,
4) A compound containing two or more (meth) acryloyl groups in the molecule and a trialkoxysilane having an SH group formed by a Michael addition reaction of an SH group to an unsaturated group ((meth) acryloyl group). And a compound obtained by reacting a mono (meth) acrylate of α, ω-hydroxy-terminated polyalkylene glycol with a silane coupling agent having an NCO group,
However, it is not limited to these.

Examples of the (meth) acrylate having an OH group include tri (meth) acrylates such as pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, and ditrimethylolpropane tri (meth) acrylate; dipentaerythritol pentaacrylate Poly (meth) acrylates are preferred.
Examples of trialkoxysilane compounds having an NCO group include triethoxysilylpropyl isocyanate (such as KBE9007 manufactured by Shin-Etsu Chemical Co., Ltd.), trimethoxysilylpropyl isocyanate, and trimethoxysilylpropyl mercaptan (KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicon). Trialkoxysilylalkyl mercaptan such as SH6062 manufactured by the company and one NCO group of diisocyanate (such as isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate (MDI) and toluene diisocyanate (TDI)) have a thiourethane bond. Examples thereof include compounds formed and bound.

  The production method of -OCONH- by reaction of OH group and NCO group is blended in such a ratio that the number of NCO groups of each compound / number of OH groups ≦ 1, and at 60 to 100 ° C. for 1 to 20 hours. It is obtained by mixing and stirring. In this reaction, it is preferable to use a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol and phenothiazine in order to prevent polymerization due to the acryloyl group during the reaction. The blending amount is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the reaction mixture. In order to accelerate the reaction, for example, a known reaction catalyst such as di-n-butyltin dilaurate and diazabicyclooctane (DABCO) may be added. Furthermore, this reaction is carried out, for example, with a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an ether solvent such as ethylene glycol diethyl ether and diethylene glycol dimethyl ether, a carboxylic acid ester solvent such as ethyl acetate and butyl acetate, and xylene and toluene. In a solvent that does not contain a group capable of reacting with an isocyanate group, such as an aromatic hydrocarbon solvent, or in the presence of a polyfunctional acrylate having three or more (meth) acryloyl groups in the molecule. Can do.

  1) (meth) acrylates having OH groups because the resulting active energy ray-curable resin composition has good viscosity, curability, affinity with other components in the composition, and good physical properties of the cured product. As the compound in which the OH group of the compound and the NCO group of the trialkoxysilane having an NCO group are combined to form -OCONH-, a reaction product of pentaerythritol triacrylate and triethoxysilylpropyl isocyanate, or dipentaerythritol penta A reaction product of acrylate and triethoxysilylpropyl isocyanate is particularly preferred.

Examples of trialkoxysilane compounds having an SH group include trimethoxysilylpropyl mercaptan (KBM803 manufactured by Shin-Etsu Chemical Co., Ltd., SH6062 manufactured by Toray Dow Corning Silicon Co., etc.), and the like.
The production method of -NHCOS- by the reaction of the NCO group and the SH group can be performed in the same manner as the production of -NHCOO- by the reaction of the NCO group and OH group.
As the (meth) acrylate compound having an NCO group, β-isocyanatoethyl (meth) acrylate (Karenz MOI manufactured by Showa Denko KK), or having an OH group in one molecule and three or more ( Examples include compounds in which (meth) acrylates having a (meth) acryloyl group and one NCO group of diisocyanate (such as isophorone diisocyanate, hexamethylene diisocyanate, MDI and TDI) are bonded by forming a urethane bond. .

  Examples of mono (meth) acrylic acid ester compounds of α, ω-hydroxy-terminated polyalkylene glycol include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, and poly (ethylene / Propylene) glycol mono (meth) acrylate and poly (ethylene / tetramethylene) glycol mono (meth) acrylate.

  The reaction of a mono (meth) acrylate compound of an α, ω-hydroxy-terminated polyalkylene glycol and a trialkoxysilyl compound having an NCO group is carried out in the same manner as in the production of —NHCOO— by the reaction of an NCO group and an OH group. be able to.

(A-2) Inorganic oxide fine particles The inorganic oxide fine particles (hereinafter sometimes referred to as (a-2)) that can be used in the present invention are not particularly limited as long as they do not depart from the gist of the present invention. Preferred are oxides of silicon, aluminum, zirconium, titanium, zinc, lead, germanium, indium, tin, antimony, cerium, lithium, or composite oxides thereof. Specifically, silicon oxide (silica), aluminum Oxide (alumina), silicon-aluminum composite oxide, zirconium oxide (zirconia), titanium oxide (titania), zinc oxide, tin oxide, antimony-doped tin oxide, indium-tin composite oxide (ITO ), Cerium oxide, silica-lithium oxide composite oxide and the like. Of these, silica, particularly colloidal silica, as the main component is particularly preferable.

Here, “main component” means that it accounts for 50% by weight or more of the whole, and also includes only itself. For example, “main component is colloidal silica” In addition, when the colloidal silica is contained in an amount of 50% by weight or more of the whole inorganic oxide fine particles, it is intended to include that the colloidal silica is composed only of the colloidal silica.
The shape of the inorganic oxide fine particles is preferably spherical, hollow, porous, rod-like, fibrous or plate-like, or indefinite, and more preferably spherical. The term “spherical” as used in the present invention includes not only a strict sphere but also a substantially spherical one.

The primary particle diameter of the inorganic oxide fine particles is preferably 1 to 100 nm. By making the primary particle diameter 1 nm or more, it is more effective for mechanical properties, and by making it 100 nm or less, secondary aggregation is more effectively prevented, and loss of transparency is more effectively prevented. Can do.
The inorganic oxide fine particles of the present invention are usually available in a dry powder state or dissolved or dispersed in water or an organic solvent. A sol dissolved or dispersed in water or an organic solvent (hereinafter sometimes referred to as an inorganic oxide fine particle sol) is preferable because it exhibits excellent dispersibility.

Specifically, an aqueous silica sol dissolved or dispersed in water, an organic solvent having an OH group, or an organosilica sol dissolved or dispersed in a polar organic solvent having an ester group or a ketone group is preferably used as a main component.
As the aqueous silica sol, basic aqueous silica sol (ST-20 manufactured by Nissan Chemical Industries, Ltd.), acidic aqueous silica sol (ST-O manufactured by Nissan Chemical Industries, Ltd.), weak acidic aqueous silica-alumina sol (ST manufactured by Nissan Chemical Industries, Ltd.) -AK) and basic silica / lithium oxide sol (manufactured by Nissan Chemical Industries, Ltd.) can be mentioned as preferable examples.

  Further, as the organosilica sol, isopropanol (IPA) dispersed organosilica sol (IPA-ST, IPA-ST-ZL manufactured by Nissan Chemical Industries, Ltd.), methyl ethyl ketone (MEK) dispersed organosilica sol (MEK-ST, MEK- manufactured by Nissan Chemical Industries, Ltd.) ST-MS), methyl isobutyl ketone (MIBK) dispersed organosilica sol (manufactured by Nissan Chemical Industries, MIBK-ST), propylene glycol monomethyl ether acetate (PMA) dispersed organosilica sol (manufactured by Nissan Chemical Industries, Ltd., PMA-ST), and these As a preferred example, a sol (for example, propylene glycol monomethyl ether (PGM) -dispersed organosilica sol) in which a solvent is substituted with an organic solvent having another OH group.

Examples of the organic solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, ethyl cellosolve, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, dimethylacetamide. And xylene, and mixed solvents thereof.
The solid content in the dispersion is preferably 5 to 50% by weight and more preferably 10 to 40% by weight from the viewpoint of easy handling and availability.

(A-3) Specific production method of component (Ai) The bond between the inorganic oxide fine particles (a-2) and the silane coupling agent (a-1) having a (meth) acryloyl group is this kind of compound. The production can be achieved by various commonly used methods. Basically, the alkoxysilyl group of (a-1) is hydrolyzed to form a silanol group, which is condensed and bonded with the alkoxy group and hydroxy group on the surface of the inorganic oxide fine particles (a-2). The method is common.

The amount of water used is within a range that does not impair the performance of the membrane and the stability of the coating solution. The amount of water added may be an amount that is at least an amount capable of hydrolyzing 100% of the alkoxy group of component (a-1) as a theoretical amount, and preferably 100 to 300% equivalent to the number of alkoxy groups, Preferably, an amount equivalent to 100 to 200% is added.
Examples of the water used include distilled water, ion exchange water, industrial water and soft water.

  Furthermore, an acid or alkali, or other suitable compound may be added as a catalyst in order to accelerate this hydrolysis condensation reaction. Any of these can be used as long as the performance of the cured film obtained is not impaired and the performance of the coating liquid is not impaired. For example, the acid catalyst includes inorganic acids such as hydrogen chloride solution, phosphoric acid solution and boric acid; organic acids such as citric acid, maleic acid, acetic acid and paratoluenesulfonic acid. Examples of the alkali catalyst include alcoholic potassium hydroxide, ammonia, trialkylamines; heterocycle-containing amines such as dimethylaminopyridine. In addition, metal acetylacetone complexes such as aluminum triacetylacetonate are also effective.

The amount of these used is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the silane coupling agent (a-1).
The reaction between the component (a-1) and the component (a-2) is preferably 20 to 100 ° C., 1 hour to 100 hours (more preferably 20 ° C. to 25 ° C., 4 hours or more), and then 40 to Heat at 70 ° C. for 1-10 hours to allow the reaction to proceed. Moreover, in order to suppress a side reaction, you may dilute a reaction liquid with a solvent. As the solvent to be used, those having good compatibility with water or catalyst to be used are preferable. For example, alcohols such as methanol, ethanol, isopropanol and isobutanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran, dioxane and the like Ethers; hydroxyl group-containing ethers such as propylene glycol monomethyl ether can be mentioned.

The weight ratio of the inorganic oxide fine particles (a-2) (solid content) to the silane coupling agent (a-1) is preferably 100 / 0.1 to 100/10, more preferably 100/1 to 100/5. By setting it within such a range, an appropriate amount of the silane coupling agent (a-1) can be introduced into the inorganic oxide fine particles (a-2).
Apart from the above, among the components capable of synthesizing the component (a-1), an alkoxysilyl compound having a functional group capable of generating a bonding group represented by the formula (1) or the formula (2) in advance is first oxidized with inorganic oxidation. It is also possible to employ a method in which after reacting with the fine particle sol, another compound is reacted and a (meth) acryloyl group and a linking group represented by formula (1) or formula (2) are introduced thereto. Of the formula (1), as a compound having an alkoxysilyl group, a trialkoxysilane compound having an SH group can be reacted in advance with the inorganic oxide fine particles (a-2).

For example, a trialkoxysilane having an SH group is reacted with the component (a-2), and then the SH group is reacted with a diisocyanate compound, and one NCO group is used to connect via an NHCOS bond, and the remaining NCO group A structure similar to the previous method can be obtained by a method in which a (meth) acrylate compound having an OH group is allowed to act on and is connected via an NHCOO bond.
Moreover, the trialkoxysilane which has SH group is made to react with a component (a-2), and is made to react with the (meth) acrylate compound and / or (meth) acrylamide compound which have NCO group after that, and is the same as the previous method A structure can be obtained.

  In this case, the reaction ratio between the trialkoxysilane having an SH group and the component (a-2) is usually 0.1 / 99.9 to 95/5, preferably 2/98 to 90/10, by weight. Preferably it is 10 / 90-80 / 20. By setting it in such a range, the surface of the inorganic oxide fine particles (a-2) can be more sufficiently protected, and further, the dispersion state by the polymerization and crosslinking of the alkoxysilane itself is further stabilized, and the viscosity is increased. Is more preferable. Further, the molecular weight of the trialkoxysilane having an SH group is desirably 150 or more. By setting it to 150 or more, the effect of producing a protective colloid is enhanced, and aggregation and gelation due to condensation, crosslinking, etc. of the trialkoxysilane itself having an SH group can be more effectively suppressed, which is preferable. More preferably, it is 300 or more.

  The reaction is preferably carried out at room temperature to 100 ° C. for 1 hour to 100 hours, more preferably at room temperature for 4 hours or more, followed by heating at room temperature to 70 ° C. for 1 to 10 hours. In order to suppress side reactions, the reaction solution may be diluted with a solvent. The solvent used is preferably a hydrolyzate silane alkoxide, water or a catalyst compatible with water, for example, alcohols such as methanol, ethanol, isopropanol and isobutanol; acetone, methyl ethyl ketone and methyl isobutyl ketone, etc. Examples include ketones; ethers such as tetrahydrofuran and dioxane; and hydroxyl group-containing ethers such as propylene glycol monomethyl ether.

  Further, a part of the component (a-1) (less than 50% by weight) may be replaced with another silane coupling agent. As other silane coupling agents, in addition to various known commercially available silane coupling agents, a silane coupling agent having a polyalkylene glycol structure that does not have a radical polymerizable functional group, a COOH group, or a COOR ′ group (R ′ is For example, a silane coupling agent having a substituent such as an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group, or a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms) , A silane coupling agent having an alicyclic structure, and a silane coupling agent obtained by a reaction between a bulky alcohol having a branched structure and an alkoxysilyl group having an NCO group, ) A silane coupling agent having an acryloyl group can be exemplified.

(A-4) Specific Method for Solvent-Free Component (A) The polyfunctional (meth) acrylate produced in the above (a-3) has 3 or more (meth) acryloyl groups in one molecule. The polyfunctional acrylate derivative (A) including the organic-inorganic composite bonded to the inorganic oxide fine particles by a covalent bond includes at least a component (Ai) and a solvent. When the solvent is removed before blending the component (A) and the component (B), the following method is desirable.

It is desirable to distill off the solvent under reduced pressure while blowing oxygen or air at a temperature of 50 ° C. or lower. In addition, although blowing of oxygen or air is desirable to be continuous, it may be intermittent. However, in this case, since the polymerization inhibition effect due to dissolved oxygen is weakened, it may be necessary to add 100 to 2000 ppm of a polymerization inhibitor (for example, p-methoxyphenol).
Basically, by such a method, the viscosity of the polyfunctional acrylate used as a raw material such as a polyfunctional (meth) acrylate having an OH group is substantially maintained, and a component (A) substantially free of a solvent is obtained. Can do.
In addition, about solvent distillation, after mix | blending component (A) and (B), you may carry out by the method similar to having described above. In this case, since the viscosity of the system can be kept low in advance, the efficiency of distilling off the solvent is good, and thickening, gelation, and insolubilization due to the polymerization reaction are unlikely to occur, and it is often preferable.

  Component (A) preferably has a viscosity at 25 ° C. of 50 mPa · s or more, more preferably 100 mPa, because it is easy to adjust the viscosity of the resulting active energy ray-curable resin composition to a certain range excellent in applicability. · S or more, preferably 10000 mPa · s or less, more preferably 7000 mPa · s or less. In the case of 50 mPa · s or more, since it has a relatively high molecular weight, it is preferable because the volatility is not too high or the substrate is not significantly affected, and if it is 10000 mPa · s or less, a reactive diluent is used. Since it can adjust to the preferable viscosity range excellent in applicability | paintability as an active energy ray curable resin composition, it is preferable.

  Component (A) is a modified colloidal silica in which a reaction product of pentaerythritol triacrylate and triethoxysilylpropyl isocyanate is bonded to colloidal silica, and dipentaerythritol pentaacrylate and triethoxysilylpropyl isocyanate as component (Ai). The reaction product contains a modified colloidal silica bonded to colloidal silica, a modified product of these modified colloidal silica with polyalkylene oxide, or a modified product of these modified colloidal silica with polycaprolactone. Is preferred.

  A modified product of polyalkylene oxide of a modified colloidal silica is a polyalkylene oxide whose one end is an OH group (the other end is an alkoxy, phenoxy, alkylphenoxy, acryloyl, methacryloyl group) instead of pentaerythritol triacrylate. Other than using, it can manufacture by the method similar to the colloidal silica modification which the reaction material of pentaerythritol triacrylate and triethoxysilylpropyl isocyanate couple | bonded with colloidal silica.

  In addition, polycaprolactone modified with polycaprolactone is pentaerythritol except that polycaprolactone with one end is OH group (the other end is alkoxy, phenoxy, alkylphenoxy, acryloyl, methacryloyl group) is used instead of pentaerythritol triacrylate. The reaction product of triacrylate and triethoxysilylpropyl isocyanate can be produced in the same manner as the modified colloidal silica in which colloidal silica is bonded.

(B) 1-4 functional (meth) acrylate and / or (meth) acrylamide The 1-4 functional (meth) acrylate and / or (meth) acrylamide as the component (B) in the present invention is contained in one molecule. Although it will not specifically limit if it contains 1-4 (meth) acryloyl groups, Since it is favorable in sclerosis | hardenability, it is more preferable if it contains 1-4 acryloyl groups in 1 molecule.

  Component (B) has a viscosity at 25 ° C. of preferably 1 mPa · s or more, more preferably 1.5 mPa, because it is easy to adjust the viscosity of the resulting active energy ray-curable resin composition to a certain range excellent in applicability. S or more, preferably 500 mPa · s or less, more preferably 200 mPa · s or less. When it is 1 mPa · s or more, it is preferable because the volatility is too high and does not attack the substrate, and when it is 500 mPa · s or less, an effect of lowering the viscosity of the resulting composition can be exhibited.

Specific examples of the component (B) include the following.
(1) Monofunctional (meth) acrylate or (meth) acrylamide Monofunctional (meth) acrylate or (meth) acrylamide is a liquid at 25 ° C. and has a viscosity of 1 to 500 mPa · s per molecule. Examples include (meth) acrylate or (meth) acrylamide having one (meth) acryloyl group. Specifically, for example, ethyl hexyl (meth) acrylate, lauryl (meth) acrylate, and its modified ethylene oxide, alkyl (meth) acrylate that is liquid at 25 ° C .; benzyl (meth) acrylate, phenylethyl (meth) acrylate Aralkyl (meth) acrylate, which is liquid at 25 ° C .; 25 ° C. having an alicyclic structure such as tricyclodecanyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and its ethylene oxide-modified product Liquid (meth) acrylates having a ring structure containing heteroatoms such as tetrahydrofurfuryl acrylate and its modified ethylene oxide (meth) acrylates having a liquid structure at 25 ° C .; Kurylamide derivatives; Epoxy acrylates such as acrylic acid adducts of phenylglycidyl ether and acrylic acid adducts of cyclohexene oxide; polyethylene acrylate monoacrylates terminated with OH groups, polyethylene glycol monoacrylates terminated with methoxy groups, and phenoxy groups terminated Polyethylene glycol monoacrylate, polyalkylene glycol monoacrylate such as polypropylene glycol monoacrylate having a phenoxy group at the end, and polyester acrylate such as polycaprolactone monoacrylate.

(2) Bifunctional (meth) acrylate or (meth) acrylamide The bifunctional (meth) acrylate or (meth) acrylamide is a liquid at 25 ° C. and has a viscosity of 2 in 1 molecule of 1 to 500 mPa · s. And (meth) acrylate or (meth) acrylamide having one (meth) acryloyl group. Specifically, for example, 25 such as butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, decanediol di (meth) acrylate, and their modified alkylene oxides. Polyalkylene glycol di (meth) acrylate liquid such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, etc. Acrylate; di (meth) acrylate having a cycloaliphatic structure such as tricyclodecane dimethanol di (meth) acrylate at 25 ° C .; dioxane glycol di (meth) acrylate (for example, manufactured by Nippon Kayaku Co., Ltd.) Di (meth) acrylates liquid at 25 ° C. having a ring structure containing heteroatoms such as Yalad R-604); liquids containing aromatic di- (meth) acrylates at 25 ° C. such as di (meth) acrylates of bisphenol A diethoxylate ) Acrylate; bis (meth) acrylamide of polyethylene glycol modified with amine at the end, bis (meth) acrylamide of polypropylene glycol modified with amine at the end, and the like.

(3) Trifunctional or tetrafunctional (meth) acrylate, or trifunctional or tetrafunctional (meth) acrylamide. As trifunctional or tetrafunctional (meth) acrylate or trifunctional or tetrafunctional (meth) acrylamide, 25 Examples thereof include (meth) acrylate or (meth) acrylamide which is liquid at ° C and has 3 or 4 (meth) acryloyl groups in one molecule having a viscosity of 1 to 500 mPa · s. Specifically, for example, trimethylolpropane triacrylate and its alkylene oxide modified product, alkylene oxide modified product of ditrimethylolpropane triacrylate, alkylene oxide modified product of pentaerythritol triacrylate, alkylene oxide modified product of pentaerythritol tetraacrylate, Examples include mono (meth) acrylamide di (meth) acrylates of ethylene oxide adducts of 3-amino-1,2-propanediol.

When particularly high curability is required, among the (meth) acrylate or (meth) acrylamide, a structure having an active hydrogen atom or the like that is susceptible to hydrogen abstraction, or a specific chemical structure having a structure having a nitrogen atom. It is preferable to use 1 to 4 functional (meth) acrylate or 1 to 4 functional (meth) acrylamide. Specific examples of such (meth) acrylate or (meth) acrylamide include the following (i) to (iii).
(I) is a (meth) acrylate having one (meth) acryloyl group in one molecule, directly or directly to an oxygen atom bonded to the (meth) acryloyl group, or an α-position carbon or β- It has a structure in which one selected from a (poly) cycloalkyl group, a (poly) cycloalkenyl group, a hydroxyalkyl group, a cyclic ether group, and a (poly) alkylene oxide group is bonded via a coordination carbon. (Meth) acrylates having these structures are preferred because of their good curability, and acrylates are more preferred.

  The (poly) cycloalkyl group, (poly) cycloalkenyl group, hydroxyalkyl group, cyclic ether group, and (poly) alkylene oxide group are directly bonded to an oxygen atom bonded to one (meth) acryloyl group of (i). Alternatively, they may be bonded via an α-position carbon or β-position carbon. Here, when there is one or more carbon atoms bonded to oxygen bonded to the (meth) acryloyl group, the first carbon atom bonded next to the oxygen atom is the α-position carbon, The second carbon atom is referred to as a β-position carbon, and bonding of each functional group to these carbon atoms is referred to as bonding via an α-position carbon or a β-position carbon.

  The (poly) cycloalkyl group or the (poly) cycloalkenyl group is not particularly limited as long as it is a cyclic alkyl group or an alkenyl group, and may have 3 or more carbon atoms, but is compatible with other components. It is preferable that it is 3-20 from a favorable thing. In addition, a ring is opened by a radical or a ring is excessively strained, and a 5-6 membered ring such as a cyclopentane ring and a cyclohexane ring, and a tricyclodecane ring, an adamantane ring, etc. A structure in which a 5- to 6-membered ring is condensed is particularly preferable.

When (i) has a (poly) cycloalkyl group or a (poly) cycloalkenyl group, a structure in which an oxygen atom is bonded directly or via an α-position carbon is preferable.
The hydroxyalkyl group is not particularly limited as long as it is an alkyl group having one or more hydroxyl groups and having 1 or more carbon atoms. However, since both the stability and curability of (meth) acrylate alone are good, It is preferred that there are 1 or 2 carbon atoms between the hydroxyalkyl groups, more preferably one.

As the hydroxyalkyl group, the alkyl group preferably has 1 or 2 carbon atoms. That is, it is preferably a hydroxymethyl group or a hydroxyethyl group.
In addition, when (i) has a hydroxyalkyl group, it is preferably bonded directly to an oxygen atom or via an α-position carbon.
Most preferred is a structure in which a hydroxyalkyl group having 2 carbon atoms is directly bonded to an oxygen atom.

  The cyclic ether group is not particularly limited as long as it is cyclic and includes an ether bond, but preferably has 2 or more carbon atoms, preferably 10 or less, more preferably 5 or less. Specific examples include an epoxy group having 2 carbon atoms, a trioxanyl group having 3 carbon atoms, a tetrahydrofuranyl group having 4 carbon atoms, a dioxanyl group, and a tetrahydropyranyl group having 5 carbon atoms. Of these, a trioxanyl group, a tetrahydrofuranyl group, a dioxanyl group, and a tetrahydropyranyl group are preferable.

Further, when (i) has a cyclic ether group, it is preferably bonded directly to an oxygen atom or via an α-position carbon.
The (poly) alkylene oxide group is not particularly limited as long as it is an alkyl group having an oxygen atom. However, since both the stability and curability of (meth) acrylate alone are good, the oxygen atom and the (poly) alkylene oxide are It is preferable that 1 to 3 carbon atoms exist between the oxygen atom in the group. In the present invention, the end of the carbon atom of the alkylene oxide group is bonded to the oxygen atom bonded to the (meth) acryloyl group, the α-position carbon, or the β-position carbon.

The alkyl group of the (poly) alkylene oxide group preferably has 1 to 6 carbon atoms, and more preferably has 2 or 3 carbon atoms. That is, (poly) ethylene oxide and (poly) propylene oxide groups are preferable.
In addition, when (i) has a (poly) alkylene oxide group, it is preferably bonded directly to an oxygen atom or via an α-position carbon.
Most preferably, the (poly) alkylene oxide group having 2 carbon atoms is directly bonded to the oxygen atom.

  The above (poly) cycloalkyl group, (poly) cycloalkenyl group, hydroxyalkyl group, cyclic ether group, and (poly) alkylene oxide group may all have a substituent. Although it does not specifically limit as a substituent, It is preferable that molecular weight is 15-350. The substituent may be chain-like or cyclic and may contain an oxygen atom, a nitrogen atom, or the like. Specific examples of the substituent include methyl group, ethyl group, propyl group, butyl group, methoxy group, ethoxy group, propoxy group, butoxy group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, cyclohexyl group. , Tricyclodecanyl group, phenyl group, benzyl group, dimethylaminoethyl group, dimethylaminopropyl group, tetrahydrofuranyl group, tetrahydropyranyl group, and the like. Particularly preferred are a methyl group, an ethyl group, a methoxy group, an ethoxy group, and a methoxyethyl group.

  (I) is not particularly limited as long as it has the structure as described above. Specifically, for example, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, tricyclo Decane mono (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic acid adduct of cyclohexene oxide, tricyclodecane methanol (meth) acrylate, adamantanemethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, tricyclodecane (Meth) acrylates having (poly) cycloalkyl groups such as ethanol mono (meth) acrylate and epoxycyclohexanemethyl acrylate; tricyclodecene mono (meth) acrylate, tricyclodece (Meth) acrylates having (poly) cycloalkenyl groups such as methanol (meth) acrylate and tricyclodecene ethanol mono (meth) acrylate; hydroxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, (Meth) acrylates having a hydroxyalkyl group such as 3-methoxy-2-hydroxypropyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate, tetrahydrofuranyl (meth) acrylate, solketal mono (meth) acrylate, 4- ( (Meth) acrylate having a cyclic ether group such as (meth) acryloxyethyltetrahydropyran; methoxymethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly Lopylene glycol mono (meth) acrylate, and terminal-methoxy compounds, terminal-phenoxy compounds thereof, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, tri (Meth) having (poly) alkylene oxide groups such as cyclodecane methanol ethoxylate mono (meth) acrylate, polyethylene glycol mono (meth) acrylate having a number average molecular weight of 150 to 500, alkyl at its ω-terminal, and phenyl-substituted products An acrylate etc. can be mentioned.

  Among these, cyclohexyl acrylate, tricyclodecene monoacrylate, tricyclodecane monoacrylate, 3-phenoxy-2-hydroxypropyl acrylate, polyethylene glycol monoacrylate, and terminal-methoxylated products thereof are preferable from the viewpoint of curability and availability. , End-phenoxylate, methoxyethyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofuranyl acrylate, particularly preferably tricyclodecane monoacrylate, polyethylene glycol monoacrylate and their end-methoxylate, end-phenoxylate, methoxyethyl Acrylate, tetrahydrofurfuryl acrylate.

  (Ii) is a (meth) acrylate having 2 to 4 (meth) acryloyl groups in one molecule, and directly or directly to an oxygen atom bonded to at least one (meth) acryloyl group One selected from a (poly) cycloalkylene group, a (poly) cycloalkenylene group, a hydroxyalkylene group, a cyclic ether group, and a (poly) alkylene oxide group is bonded via a -position carbon or a β-position carbon. It has a structure. A (meth) acrylate having such a structure is preferable because the curability is good, and an acrylate is more preferable.

  The (poly) cycloalkylene group, (poly) cycloalkenylene group, hydroxyalkylene group, cyclic ether group, and (poly) alkylene oxide group are at least one of 2 to 4 (meth) acryloyl groups possessed by (ii) It suffices if it is bonded to one oxygen atom directly or via an α-position carbon or β-position carbon, and it can be bonded to a plurality of oxygen atoms bonded to 2 to 4 (meth) acryloyl groups. , Directly or via an α-position carbon or β-position carbon.

The (poly) cycloalkylene group or (poly) cycloalkenylene group is not particularly limited as long as it is a cyclic alkylene group or an alkenylene group, and the number of carbons may be 3 or more, preferably 5 or more. Preferably it is 6 or more, preferably 20 or less, more preferably 15 or less. Specific examples include a cyclohexylene group, a tricyclodecanylene group, and a pentacyclopentadecanylene group.
When (ii) has a (poly) cycloalkyl group or a (poly) cycloalkenylene group, a structure bonded to an oxygen atom directly or via an α-position carbon is preferable.

The hydroxyalkylene group is not particularly limited as long as it is an alkylene group having one or more hydroxyl groups and having 1 or more carbon atoms. However, since both the stability and curability of (meth) acrylate alone are good, Preferably there are 1 or 2 carbon atoms between the hydroxyalkylene groups, more preferably one.
As the hydroxyalkylene group, the alkylene group preferably has 1 or 2 carbon atoms.

Further, when (ii) has a hydroxyalkylene group, it is preferably bonded directly to an oxygen atom or via an α-position carbon.
Most preferred is a structure in which a hydroxyalkylene group having 2 carbon atoms is directly bonded to an oxygen atom.
The cyclic ether group and the (poly) alkylene oxide group are the same as in the case of (i) above.

Any of the (poly) cycloalkylene group, (poly) cycloalkenylene group, hydroxyalkylene group, cyclic ether group, and (poly) alkylene oxide group may have a substituent. The substituent is the same as (i) when preferred.
(Ii) is not particularly limited as long as it has the structure as described above. Specifically, for example, tricyclodecane dimethanol di (meth) acrylate, tricyclodecane di (meth) acrylate, cyclohexane (Meth) acrylates having (poly) cycloalkylene groups such as dimethanol di (meth) acrylate and cyclohexanediethanol di (meth) acrylate; cyclohexenylene (meth) acrylate, tricyclodecenylene (meth) acrylate, tosilichrome (Meth) acrylates having a (poly) cycloalkenylene group such as decenedimethanol di (meth) acrylate; (meth) acrylates having a hydroxyalkylene group such as a (meth) acrylic acid adduct of 1,5-hexadiene diepoxide; Isosolver (Meth) acrylates having a cyclic ether group such as todi (meth) acrylate, 2,6-di (meth) acryloxymethyltetrahydropyran, 3,5-di (meth) acryloxyethyltetrahydropyran; polyethylene glycol di (meth) ) Acrylate, butanediol ethoxylate di (meth) acrylate, hexanediol ethoxylate di (meth) acrylate, tricyclodecane dimethanol ethoxylate di (meth) acrylate, 2,5-dimethoxy-1,6-hexanediol di ( (Meth) acrylate, (meth) acrylate having a (poly) alkylene oxide group such as polyethylene glycol di (meth) acrylate having a number average molecular weight of 150 to 500, triacrylate of ethylene oxide modified product of glycerin, , And the like triacrylate cyclohexene oxide modified product of glycerin.

  Of these, tricyclodecane dimethanol diacrylate, polyethylene glycol diacrylate, butanediol ethoxylate diacrylate, and hexanediol ethoxylate diacrylate are particularly preferred from the viewpoint of curability and availability, and tricyclodecane ethoxylate diacrylate is particularly preferred. It is a triacrylate of an ethylene oxide modified product of candimethanol diacrylate, polyethylene glycol diacrylate, hexanediol ethoxylate diacrylate, and glycerin.

(Iii) is (meth) acrylamide having 1 to 4 (meth) acryloyl groups in one molecule, wherein the amino group bonded to the (meth) acryloyl group is substituted with two alkyl groups. Have. However, two alkyl groups may be bonded directly or via a hetero atom. (Meth) acrylamide having these structures is preferable because of good curability, and acrylamide is more preferable.
The alkyl group in the amino group substituted with two alkyl groups is not particularly limited, but when the two alkyl groups are not bonded to each other, each of them is an alkyl group having 2 or less carbon atoms because of excellent curability. Preferably there is. More preferably, both are methyl groups.

When two alkyl groups are bonded to each other, the total number of carbon atoms of the two alkyl groups is preferably 2 or more, preferably 10 or less, more preferably 6 or less. Furthermore, examples of the hetero atom in the case of bonding through a hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom, and among them, an oxygen atom is preferable.
(Iii) is not particularly limited as long as it has the structure as described above. Specifically, for example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, methylenebis Examples thereof include N, N′-dimethyl form of (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidine, N- (meth) acryloylpiperidine, isocyanuric acid triacrylamide, and the like. Among these, N, N-dimethylacrylamide and N-acryloylmorpholine are preferable from the viewpoint of curability and availability.

  The active energy ray-curable resin composition of the present invention contains components (A) and (B) in a total amount of 100 parts by weight, of which (A) the polyfunctional (meth) acrylate derivative is 25 to 90 parts by weight. When it is 25 parts by weight or more, a cured film having high hardness and excellent scratch resistance is obtained, and when it is 90 parts by weight or less, the viscosity of the active energy ray-curable resin composition does not become excessively high and the coating property is excellent. Preferably it is 35 parts by weight or more, more preferably 50 parts by weight or more and 80 parts by weight or less.

On the other hand, (B) 1-4 functional (meth) acrylate and / or (meth) acrylamide is 10 to 75 parts by weight out of 100 parts by weight of the total amount of components (A) and (B). When the amount is 10 parts by weight or more, the resulting resin composition has a low viscosity, so that the coating property is excellent, and when it is 75 parts by weight or less, a cured film having good curability and high hardness is obtained. Preferably it is 15 parts by weight or more and 60 parts by weight or less.
Moreover, it is preferable that 1/3 or more of the total weight of a component (B) is the said (i)-(iii) from sclerosis | hardenability becoming favorable. More preferably, it is 35/100 or more, still more preferably 40/100 or more, and most preferably the total amount is (i) to (iii).

(C) Photopolymerization initiator As the photopolymerization initiator which is the component (C) in the present invention, known ones can be widely used. Alkylphenone type compounds such as aminoacetophenones and benzyl ketals; acylphosphine oxide type compounds; oxyphenyl acetates; benzoin ethers; aromatic ketones (benzophenones); oxime esters; ketone / amine compounds; And α-aminophenyl ketones, benzophenones, benzoylformic acid (esters), and oxime esters.

  Specifically, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin butyl ether, diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, 2,4,6-trimethylbenzoindiphenylphosphine oxide, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butan-1-one, Michler's ketone, isoamyl N, N-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, benzoylgi , Methyl benzoylformate, ethyl benzoylformate, CGI242 (manufactured by Ciba Specialty Chemicals Inc.), and OXE01 (manufactured by Ciba Specialist Li Tay Chemicals Inc.) preferred. Two or more of these photopolymerization initiators can be used in combination as appropriate.

  Among these, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)-are preferable because of improved curability. Α-aminophenyl ketones such as butan-1-one; benzophenones such as benzophenone, Michler's ketone, 2-chlorothioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone; methyl benzoylformate, benzoylformate, ethyl benzoylformate, Oxime esters such as CGI242 (manufactured by Ciba Specialty Chemicals) and OXE01 (manufactured by Ciba Specialty Chemicals) are preferred.

  Further, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzophenone, More preferably, methyl benzoylformate or the like is used, and 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butan-1-one and methyl benzoylformate are particularly preferred.

When these are used as the (C) component, it is more preferable that the above-mentioned (i) to (iii) are included as at least a part of the (B) component because the curability is more remarkably improved.
When the total weight of components (A) and (B) in the active energy ray-curable resin composition is 100 parts by weight, (C) the photopolymerization initiator is 2 to 5 parts by weight, preferably 2.5. It is at least 4.5 parts by weight. If it is less than 2 parts by weight, the curability is inferior, and if it is 5 parts by weight or more, the physical properties of the cured product are lowered.

From the viewpoint of curability, the component (C) preferably contains one or more selected from α-aminophenyl ketones, benzophenones, benzoylformic acid (esters), and oxime esters. The amount is preferably 1/3 or more of the total weight of the component (C), more preferably 1/2 or more, still more preferably 3/5 or more.
On the other hand, in the case of containing a photopolymerization initiator other than the α-aminophenyl ketones, benzophenones, benzoylformic acid (esters), and oxime esters, and α-hydroxyphenyl ketones, the curability is lowered and the coloring is reduced. Since it is difficult to cause a problem, when used, it is preferably used in a range not exceeding 1/2 of the total weight of the component (C).

(D-1) Active energy ray-curable compound containing one or more groups selected from polydimethylsiloxane group, perfluoroalkyl group and perfluoroalkylene group Component (D-1) active energy ray-curable compound in the present invention is , A polydimethylsiloxane group, a perfluoroalkyl group, and a perfluoroalkylene group are not particularly limited as long as they contain one or more groups selected from a perfluoroalkylene group. Including at least one group selected from a polydimethylsiloxane group of 10,000 or less, a perfluoroalkyl group having 4 or more carbon atoms, and a perfluoroalkylene group having 4 or more carbon atoms, and at least one in a side chain and / or a terminal (Meth) acryloyl group or an active energy ray-curable group such as an epoxy group preferable.

When the number average molecular weight of the polydimethylsiloxane group is 1000 or more, the antifouling performance is sufficiently exhibited, and when it is 10,000 or less, the transparency of the cured film becomes favorable. In addition, the perfluoroalkyl group and the perfluoroalkylene group have 4 or more carbon atoms, and the antifouling property is sufficiently exhibited.
Examples of those containing polydimethylsiloxane groups are Shin-Etsu Chemical Co., Ltd. polydimethylsiloxane containing methacryloyl groups at both ends, polydimethylsiloxane containing epoxy groups at both ends, polydimethylsiloxane containing epoxy groups at both ends and side chains. Siloxane, Tego-Rad (polydimethylsiloxane derivative having an acryloyl group at the side chain) manufactured by EVONIK (former Degussa), polydimethylsiloxane having an acryloyl group at both ends manufactured by Gelest, or main chain or side Examples thereof include a copolymer having polydimethylsiloxane in the chain and a side chain and / or a terminal having an acryloyl group and / or an epoxy group.

Examples of those containing a perfluoroalkyl group or alkylene group having 4 or more carbon atoms include perfluorobutylethyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, perfluorohexylethyl (meth) acrylate, or Examples thereof include a copolymer obtained by copolymerizing these and having a side chain and / or a terminal having an acryloyl group and / or an epoxy group.
Component (D-1) may contain two or more of these specific groups. Examples of such a compound include a copolymer having a polydimethylsiloxane group and a perfluorooctyl group and having an acryloyl group and / or an epoxy group at the side chain and / or terminal.

When the total weight of components (A) and (B) in the active energy ray-curable resin composition is 100 parts by weight, (D-1) the active energy ray-curable compound is 0.1 to 15 parts by weight. The amount is preferably 0.15 parts by weight or more and 9.5 parts by weight or less. If the amount is less than 0.1 parts by weight, it is difficult to impart sufficient stain resistance. On the other hand, if the amount exceeds 15 parts by weight, the surface hardness may decrease, the curability may decrease, and the transparency may decrease. Therefore, it is not preferable.
Since a structure obtained by reacting a carboxylic acid having a (meth) acryloyl group with an epoxy group (so-called epoxy (meth) acrylate structure) is considered to have a very high photocuring reactivity, the component (D-1) It is preferable to have such a structure.

  Component (D-1) is (D-2) a monomer containing a monomer containing one or more groups selected from a polydimethylsiloxane group, a perfluoroalkyl group, and a perfluoroalkylene group, and a (meth) acrylate having an epoxy group. Active energy ray-curing property having a structure corresponding to a structure obtained by reacting at least part of the epoxy group of the radical polymer of the mixture with carboxylic acid having one or more (meth) acryloyl groups in one molecule A polymer is preferable because the resulting active energy ray-curable resin composition has good curability. Among them, when the monomer containing one or more groups selected from the polydimethylsiloxane group, the perfluoroalkyl group, and the perfluoroalkylene group is dimercaptopolysiloxane, the viscosity of the resin composition and the other in the composition It is particularly preferable from the viewpoint of compatibility with the components and stain resistance of the resulting cured film.

  Regarding the production method of component (D-2) below, an example in which the monomer containing one or more groups selected from the polydimethylsiloxane group, perfluoroalkyl group, and perfluoroalkylene group is dimercaptopolysiloxane. An example of a preferable production method will be described. However, it can be produced in the same manner when the monomer containing one or more groups selected from the polydimethylsiloxane group, perfluoroalkyl group, and perfluoroalkylene group is other than dimercaptopolysiloxane.

Hereinafter, the amount (part by weight) of each component in 100 parts by weight of the monomer mixture as the raw material for producing the component (D-2) may be referred to as “use amount”.
In addition, a component (D-2) should just have the structure corresponded to the polymer obtained by the following method, and is not limited to what was obtained by the following manufacturing method.

<(D1) Dimercaptopolysiloxane>
The (d1) dimercaptopolysiloxane used for the production of the component (D-2) has a polysiloxane structure in which two or more repeating structural units of the following formula (3) are linked.

-(SiR ₁ R ₂ -O)-(3)
In formula (3), R ₁ and R ₂ each independently represents an alkyl group which may have a substituent or a phenyl group which may have a substituent, preferably a hydroxyl group or alkoxy An alkyl group which may be substituted with a group (preferably an alkoxy group and an alkyl group having 1 to 3 carbon atoms), and more preferably an alkyl group having 1 to 3 carbon atoms which has no substituent. And most preferably a methyl group.

  Examples of such compounds include α, ω-dimercaptopolydimethylsiloxane, α, ω-dimercaptopolydiethylsiloxane, α, ω-dimercaptopolymethylethylsiloxane, α, ω-dimercaptopolydihydroxymethylsiloxane. , Α, ω-dimercaptopolydimethoxymethylsiloxane, and the like, among which α, ω-dimercaptopolydimethylsiloxane is preferred, and this mercapto group may be directly linked to the polysiloxane group, or alkylene. It may be linked to a polysiloxane group via a group. More preferred is a polysiloxane (α, ω-dimercaptopropylpolydimethylsiloxane) in which a mercapto group is linked to a polysiloxane group via a propylene group. However, the present invention is not limited to these as long as the effects of the present invention can be obtained.

(D1) The dimercaptopolysiloxane preferably has a number average molecular weight of about 1000 to 5000 in order to achieve a good balance between stain resistance and hardness.
Such (d1) dimercaptopolysiloxane may be used alone or in combination of two or more.
The amount of (d1) dimercaptopolysiloxane used in the production of component (D-2) is preferably 0.01 parts by weight or more and 15 parts by weight or less. (D1) When the amount of dimercaptopolysiloxane used is 0.01 parts by weight or more, the stain resistance is sufficiently exerted, and the phase of component (D-2) obtained when it is 15 parts by weight or less and other components Since the solubility (the homogeneous compatibility of the system during the polymerization reaction and the compatibility between the component (D-2) and other components when used as a composition) is good and the hardness of the cured film obtained is high, preferable.

  More preferably, the amount of (d1) dimercaptopolysiloxane used is 1 part by weight or more. More preferably, the amount of (d1) dimercaptopolysiloxane used is 12 parts by weight or less.

<(D2) (Meth) acrylate having epoxy group>
(D2) Some typical specific examples of the (meth) acrylate having an epoxy group include (meth) acrylate having a glycidyl group such as glycidyl acrylate and glycidyl methacrylate; 3,4-epoxycyclohexyl acrylate, 3, Examples include (meth) acrylates in which an epoxy group is directly bonded to an alicyclic structure such as 4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. However, the present invention is not limited to these.

Among these, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate are easily available and easily modified with (meth) acrylic acid. 3,4-epoxycyclohexylmethyl methacrylate and the like are particularly preferable.
Such (d2) (meth) acrylates having an epoxy group may be used alone or in admixture of two or more.

  The amount of (d2) (meth) acrylate having an epoxy group in the production of component (D-2) is preferably 5 parts by weight or more and 60 parts by weight or less. (D2) When the amount of the (meth) acrylate having an epoxy group is 5 parts by weight or more, the curability is good due to the photoradical polymerization of the (meth) acryloyl group introduced by the carboxylic acid modification having the (meth) acryloyl group. The effect of improving surface curability such as increased hardness is sufficiently exerted, and when it is 60 parts by weight or less, the viscosity and liquid stability of the polymer solution containing the component (D-2) are improved, and it is cured by radical photopolymerization. It is preferable because the effect of increasing the hardness and increasing the hardness is obtained.

  More preferably, the amount of (a2) (meth) acrylate having an epoxy group is 15 parts by weight or more. More preferably, the amount of (a2) (meth) acrylate having an epoxy group is 55 parts by weight or less.

<(D3) Monofunctional mercaptan having a molecular weight of 100 to 300>
(D3) Monofunctional mercaptan having a molecular weight of 100 to 300 as a raw material for the production of component (D-2) for the purpose of expressing an excellent affinity with other components by controlling the molecular weight and an excellent defoaming property May be included. Further, as in the component (D-2), in the free radical polymerizable monomer having a functional group (for example, epoxy group, isocyanate group, alkoxysilyl group, etc.) that easily reacts with the mercapto group, The above reactive groups such as epoxy groups may cause side reactions and cause problems such as crosslinking / insolubilization / gelation. (D3) By using a monofunctional mercaptan having a molecular weight of 100 to 300, By controlling the reaction, crosslinking / insolubilization / gelation can be suppressed and a good component (D-2) can be produced.

  (D3) Examples of the monofunctional mercaptan having a molecular weight of 100 to 300 include alkyl mercaptans such as hexyl mercaptan, decyl mercaptan, dodecyl mercaptan, hexadecyl mercaptan, stearyl mercaptan; cycloalkyl mercaptan such as cyclohexyl mercaptan; thiophenol, chlorothio Aromatic mercaptans such as phenol and mercaptonaphthalene can be exemplified, but the invention is not limited thereto as long as the effects of the present invention can be obtained. Of these, alkyl mercaptans having 9 to 15 carbon atoms such as decyl mercaptan and dodecyl mercaptan are most preferable in consideration of reactivity, reaction selectivity, odor and the like.

When the molecular weight of the monofunctional mercaptan used in the active energy ray-curable resin composition of the present invention is 100 or more, the volatility is low, and the effect is easily exhibited without losing from the reaction system during the polymerization reaction. Moreover, it is preferable that the molecular weight of the monofunctional mercaptan is 300 or less because compatibility with other monomers is improved and phase separation is difficult to occur. A more preferable molecular weight of the monofunctional mercaptan is 150 or more and 250 or less.
Such (d3) monofunctional mercaptan may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In the production of component (D-2) (d3) when a monofunctional mercaptan having a molecular weight of 100 to 300 is used, the amount used is 0.01 parts by weight or more, particularly 0.1 parts by weight or more, and 5 parts by weight or less. In particular, the amount is preferably 4 parts by weight or less. (D3) When the amount of the monofunctional mercaptan used is 0.01 parts by weight or more, the concentration of (d3) monofunctional mercaptan becomes appropriate and the reactivity is sufficient, (d1) dimercaptopolysiloxane and (d2) epoxy Control can be performed so as not to cause a side reaction with the (meth) acrylate having a group. On the other hand, when the amount of (d3) monofunctional mercaptan used is 5 parts by weight or less, the reaction proceeds sufficiently so that unreacted monomers hardly remain, and the molecular weight of the resulting component (D-2) becomes appropriate, which is preferable. .

  When (d3) a monofunctional mercaptan having a molecular weight of 100 to 300 is used, (d1) a mercapto group of dimercaptopolysiloxane (hereinafter referred to as “M (d1)”) and (d3) a monofunctional having a molecular weight of 100 to 300. The molar ratio M (d1) / M (d3) of the mercaptan to the mercapto group (hereinafter referred to as “M (d3)”) is usually 0.01 or more, preferably 0.05 or more, more preferably 0.8. It is preferably used in an amount of 1 or more, 20 or less, preferably 15 or less, more preferably 10 or less. When M (d1) / M (d3) is 0.01 or more, (d1) crosslinking by reaction of a mercapto group of dimercaptopolysiloxane and (d2) an epoxy group of (meth) acrylate having an epoxy group, It can be controlled so that the increase in viscosity and the decrease in solubility due to branching do not occur substantially, and when it is 20 or less, the reaction proceeds sufficiently so that unreacted monomers hardly remain, and the resulting component (D-2) The molecular weight is suitable and preferable.

<(D4) Vinyl group-containing monomer>
In addition to the above (d1) to (d3), (d4) a vinyl group-containing monomer can be included as a raw material for producing the component (D-2). (D4) The vinyl group-containing monomer is not particularly limited as long as it has a vinyl group and the effects of the present invention can be obtained. Those that do not deteriorate the property, those that have a rigid skeleton and do not lower the hardness, and those that can further improve the stain resistance can be used.

Some specific examples of such (d4) vinyl group-containing monomers include styrene, its lower (1 to 4 carbon) alkyl group, alkenyl group-substituted derivatives, and C 1-20 alkyl (meta) Examples thereof include radical polymerizable monomers such as) acrylate, alkyl (meth) acrylamide, cycloalkyl (meth) acrylate having a (poly) cycloalkyl side chain having 5 to 20 carbon atoms, and (meth) acrylamides.
As these (d4) vinyl group-containing monomers, one kind may be used alone, or two or more kinds may be mixed and used.

  In the production of component (D-2), the amount of the (d4) vinyl group-containing monomer used is preferably 1 part by weight or more and 50 parts by weight or less. (D4) If the amount of the vinyl group-containing monomer used is 1 part by weight or more, the solubility and transparency are excellent. On the other hand, if it is 50 parts by weight or less, the scratch resistance and pencil hardness of the resulting cured film become good. ,preferable. More preferably, the amount of the (d4) vinyl group-containing monomer used is 5 parts by weight or more. More preferably, the amount of the (d4) vinyl group-containing monomer is 40 parts by weight or less.

<Solvent>
In radical polymerization of the monomer mixture containing the components (d1) to (d4) described above, a solvent may be added in order to improve uniformity.

Examples of such solvents include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether. Preferred examples include ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; aromatic hydrocarbon solvents such as toluene; and water.
These solvents may be used alone or in combination of two or more. When using 2 or more types, the solvent which does not become two layers but forms a uniform layer is preferable.

<Radical polymerization initiator>
A radical polymerization initiator is preferably used for radical polymerization of the monomer mixture containing the components (d1) to (d4) described above.
Although it does not specifically limit as this radical polymerization initiator, Usually, the well-known initiator generally used for radical polymerization can be used, Organic peroxides, such as a benzoyl peroxide and di-t-butyl peroxide, Azo compounds such as 2'-azobisbutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) are preferred. Take as an example.
One of these radical polymerization initiators may be used alone, or two or more thereof may be mixed and used.

<Radical polymerization method and conditions>
(D1) when radical polymerization is performed on the monomer mixture containing the components (d1) to (d2) described above, further using a component (d3), a component (d4), a solvent and a radical polymerization initiator as necessary. There are no particular restrictions on the method of mixing / dissolving each monomer component and solvent in (d4), but for example, after mixing the monomer component and solvent, the radical polymerization initiator is added within a certain time, preferably within 3 hours. It is preferred to add to initiate the polymerization.

The total concentration of the monomer components in the reaction solution subjected to radical polymerization is preferably 10% by weight or more and 60% by weight or less, and the radical polymerization initiator is preferably 0.1% by weight with respect to the total of the monomer components. % Or more, more preferably 0.2% by weight or more, preferably 10% by weight or less, more preferably 2% by weight or less.
Moreover, although preferable polymerization conditions change with radical polymerization initiators to be used, the polymerization temperature is usually 20 to 150 ° C., and the polymerization time is usually 1 to 72 hours.

<Carboxylic acid having (meth) acryloyl group>
In the production of component (D-2), a carboxylic acid having one or more (meth) acryloyl groups in one molecule, at least part of the epoxy group of the radical polymer usually obtained as described above, Preferably, a carboxylic acid having 1 to 5 (meth) acryloyl groups in one molecule is reacted (addition reaction).

  Examples of the carboxylic acid having a (meth) acryloyl group used here include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and terminal carboxylic acid. Polycaprolactone acrylate, pentaerythritol tri (meth) acrylate and acid anhydride adducts such as succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, dipentaerythritol penta (meth) acrylate and succinic anhydride, phthalic anhydride And adducts of acid anhydrides such as hexahydrophthalic anhydride. One of these may be used alone, or two or more thereof may be mixed and used.

<Addition reaction method and conditions>
In the example of the above addition reaction, the epoxy group of the radical polymer reacts with the carboxyl group of the carboxylic acid having a (meth) acryloyl group.
The radical polymer and the carboxylic acid having a (meth) acryloyl group are the ratio of the number of the epoxy group of the radical polymer to the carboxyl group of the carboxylic acid having a (meth) acryloyl group (hereinafter simply referred to as “epoxy group / carboxyl group”). Are preferably used at a ratio of 1 or more. The epoxy group / carboxyl group is preferably 10 or less, more preferably 5 or less, and still more preferably 2 or less.
When the epoxy group / carboxyl group is not less than the above lower limit value, it is possible to prevent a decrease in stability due to the carboxylic acid having a (meth) acryloyl group remaining unreacted, and when it is not more than the above upper limit value, the remaining epoxy group It is preferable because it can prevent a decrease in stability due to.

Moreover, it is preferable that 50 to 99% reacts with the carboxyl group of the carboxylic acid having a (meth) acryloyl group among the epoxy groups of the radical polymer.
This addition reaction is preferably carried out at 50 to 110 ° C. for 3 to 50 hours.
In this reaction, in order to accelerate the reaction, for example, triethylamine, tributylamine, triethylenediamine, N, N-dimethylbenzylamine, benzyltrimethylammonium chloride, triphenylphosphine and the like are used as one or more kinds as a catalyst. can do. When the catalyst is used, the amount used is preferably 0.01% by weight or more based on the reaction mixture (that is, the total of the radical polymer and the carboxylic acid having a (meth) acryloyl group), It is preferably 0.05% by weight or more. Moreover, it is preferable that it is 2 weight% or less, and it is more preferable that it is 1 weight% or less.

  Further, in this reaction, in order to prevent radical polymerization of a carboxylic acid having a (meth) acryloyl group due to the (meth) acryloyl group, for example, hydroquinone, hydroquinone monomethyl ether, catechol, pt-butylcatechol, phenothiazine, etc. It is preferable to use one or more polymerization inhibitors. The amount of the polymerization inhibitor used is preferably 0.01% by weight or more, more preferably 0.05% by weight or more based on the reaction mixture. Moreover, it is preferable that it is 1 weight% or less, and it is more preferable that it is 5 weight% or less.

The component (D-2) used for this invention can be obtained according to the above examples.
When the active energy ray-curable resin composition of the present invention contains a compound containing an epoxy group as the component (D-1), and further containing (E) a photocationic curing initiator, the surface curability is further improved, which is preferable. There is a case. Component (E) is not particularly limited as long as it is a cationically polymerizable photoinitiator and is a known photoacid generator, but is preferably a diaryliodonium salt type or a triarylsulfonium salt type as a counter ion. Can be exemplified by PF ₆ , SbF ₅ , AsF ₆ , BPh ₄ , CF ₃ OSO ₂ , and the like. In addition, when only this component has low curability, it may be preferable to use a combination of amines (such as triethanolamine), phosphines (such as tributylphosphine), and thioxanthones for sensitization. In addition, what can be used as (E) photocationic curing initiator is not restricted to what was shown above.

When the component (E) is included, the total weight of the components (A) and (B) is preferably 100 parts by weight, preferably 0.01 parts by weight or more and 2 parts by weight or less from the viewpoint of surface curability.
As long as the effects of the present invention are not impaired, the resin composition of the present invention contains at least one of an antistatic agent, a slipperiness imparting agent, an antifogging imparting agent, and a peelability imparting agent for the purpose of imparting various functionalities. This may be preferable.
Although not particularly limited, for example, as an antistatic agent, an antistatic agent as described in JP-A-2003-201444 is particularly preferable (a quaternary ammonium base-containing polymer or quaternary). Ammonium base-containing silane coupling agent, etc.).

Moreover, as a slipperiness | lubricity imparting agent, the polymer which has a polydimethylsiloxane group can be illustrated.
On the other hand, examples of the antifogging imparting agent include polymers and oligomers having hydrophilic groups such as hydrophilic group-modified colloidal silica, silicate-modified colloidal silica, and polyalkylene glycol groups in the side chain.
Furthermore, examples of the peelability-imparting agent include known silicone-based, fluorine-based, and long-chain acrylic oligomers to polymer types, and those containing a curable group.

As long as the effects of the present invention are not impaired in the resin composition of the present invention, the addition of UV absorbers and hindered amine light stabilizers for the purpose of imparting various other functionalities described above significantly improves the weather resistance. May be preferred.
Although it does not specifically limit as a ultraviolet absorber, A benzotriazole type, a benzophenone type, a salicylic acid type, a cyanoacrylate type, a triazine type ultraviolet absorber etc. can be mentioned as a preferable example.

The hindered amine light stabilizer is not particularly limited, and for example, an N-methyl compound such as Sanol LS765 (manufactured by Ciba Specialty Chemicals) is preferable, but ordinary NH such as LS-770 (manufactured by Ciba Specialty Chemicals) is preferred. The body can be used.
In the resin composition of the present invention, for the purpose of improving the cured film properties, an antioxidant (for example, hindered phenol-based, sulfur-based, phosphorus-based antioxidant, etc.), anti-blocking agent, slip agent, leveling agent, etc. Various additives generally blended in a composition that imparts this type of stain resistance may be blended. As a compounding quantity in this case, it is preferable to mix | blend 0.01 to 2weight% of the whole composition.

For the purpose of further improving the hardness of the cured film obtained in the present invention and imparting blocking resistance to the cured film, the inorganic fine particles may be blended untreated. As a compounding quantity in this case, it is preferable to mix | blend 0.01-20 weight% of the whole composition as solid content.
The active energy ray-curable resin composition of the present invention usually has a viscosity at 25 ° C. of 10 to 500 mPa · s. 10 mPa · s or more is preferable because it avoids the phenomenon of volatilization at the time of application or undesirable flow of the liquid and the film thickness does not become uniform, and if it is 500 mPa · s or less, the wettability is good. This is preferable because the solution spreads uniformly during coating and a uniform film thickness can be secured. Preferably it is 15 mPa * s or more, More preferably, it is 20 mPa * s or more, Preferably it is 450 mPa * s or less, More preferably, it is 400 mPa * s or less.

Moreover, the active energy ray-curable resin composition of the present invention does not contain an organic solvent in excess of 5% by weight of the composition, and can be handled as a substance that does not substantially contain an organic solvent. As a result, environmental pollution accompanying the escape of the organic solvent to the environment can be avoided, and the environmental load can be reduced. In addition, since the concentration of the liquid is constant, the liquid can be easily recycled. As a result, the environmental load is reduced and productivity is improved.
Specifically, the amount of the organic solvent is 5% by weight or less in the composition, and preferably 2% by weight of the organic solvent having a boiling point of 100 ° C. or less (for example, methanol, ethanol, isopropanol, acetone, methyl ethyl ketone). The following effects can be fully exhibited as it is below. In order to make the environmental load zero, more preferably, the composition does not contain any organic solvent.

Of the solvents other than organic solvents, water is preferably not contained in excess of 1% by weight in the composition. It is very difficult to manage water so that it does not contain at all. However, if it is 1% by weight or less, turbidity due to separation of liquid does not occur and curability is improved, which is preferable.
Since the active energy ray-curable resin composition of the present invention does not substantially contain an organic solvent, the composition is applied to form a coating film, and the process of drying the coating film is not performed. A cured film can be formed by irradiation with active energy rays.

[II] A laminate comprising a cured film comprising an active energy ray-curable resin composition and a hard coat layer comprising the cured film. Curing obtained by irradiating the active energy ray-curable resin composition of the present invention with active energy rays. A laminate having a film and a hard coat layer comprising the cured film is excellent in properties such as hardness and scratch resistance.

An article having a cured film formed by irradiating an active energy ray on the composition of the present invention for polymerization on the surface is excellent in properties such as hardness and scratch resistance. After the composition is applied to the surface of the article, the composition may be polymerized by irradiating active energy rays, or a film polymerized by irradiating active energy rays may be separately prepared and then laminated on the article.
The cured film of the present invention can be applied to various articles. For example, optical lenses, optical prisms, prism sheets, automobile window materials, building window materials, spectacle lenses, solar cell surface protection films, agricultural vinyl A transparent film of house, a transparent film for retroreflective sign surface protection, and the like can be mentioned.

The composition of the present invention is coated, dried and cured on various substrates to form a hard coat layer. Although the kind of base material is not specifically limited, The base material which consists of resin from the adhesiveness high etc. is preferable. The resin base material may be any of a plate shape, a sheet shape, and a film shape, and may be a molded product having an arbitrary shape. Moreover, a base material may be a part of laminated body, and another layer may be interposed between a base material and a cured film.
The resin substrate may be a thermoplastic resin or a cured resin cured by heat or active energy rays.

  Examples of the thermoplastic resin include polyethylene terephthalate (PET), polyester such as polybutylene terephthalate (PBT) and polyethylene naphthalate, polymethyl methacrylate (PMMA), and methyl methacrylate (MMA) -containing copolymer (methacrylic acid). Methyl-styrene copolymer resin (MS resin)), polycarbonate (PC), special polycarbonate (for example, Pure Ace manufactured by Teijin Limited), triacetyl cellulose, acrylonitrile-butadiene-styrene copolymer (ABS resin), modified polyolefin resin, hydrogen Polystyrene resins, cycloolefin resins (for example, Arton manufactured by JSR, Zeonex manufactured by Nippon Zeon, Zeonore, and Appel manufactured by Mitsui Chemicals, Inc.).

Examples of the curable resin include an epoxy resin, a urethane resin, a cured product of a thermosetting or photocurable acrylic resin, a cured product such as a thermosetting or photocurable organic-inorganic hybrid resin, and the like.
These base materials may be, for example, films formed by coating themselves, or may be molded products by various molding methods.
Since the cured film of the present invention is excellent in transparency, excellent in hardness and scratch resistance, it can be applied to optical materials that require high transparency. The optical material here refers to the optical properties of the material constituting it, such as transparency (and its wavelength dependence), absorption / emission / emission properties, refractive index difference from the outside world, small birefringence, and the above unique refraction. It refers to general molded articles used in applications that utilize various optical properties such as the balance between the rate and the Abbe number. Specific examples include an optical recording medium, an optical display, a lens, a lens array, an optical filter, a prism, and an optical fiber.

  At this time, when the base material needs to be transparent, the base material is preferably formed by any one of a coating method, a melt extrusion method, and a solvent cast method. Moreover, when a base material contains the functional group which can be hardened | cured with active energy ray light or a heat | fever, it may be more preferable when it hardens | cures by active energy ray irradiation or a heating. In addition, these substrates may be in the form of molded articles (articles), or other layers may be interposed between the substrate and the application surface of the composition of the present invention. The term “transparent” generally means that the transmittance of light having a target wavelength is 80% or more.

Preferred examples of the coating method include spin coating, dip coating, flow coating, spray coating, bar coating, gravure coating, roll coating, blade coating, and air knife coating.
A cured film is obtained by forming a coating film on the substrate by the coating method and then polymerizing by irradiating with active energy rays. The thickness of the cured film is not particularly defined, and may be, for example, 5 μm or more, or 2 μm or less. The active energy ray-curable resin composition of the present invention is extremely significant in that both thinning and thickening are possible. The thickness of the cured film to be applied is particularly preferably 0.01 to 50 μm, particularly preferably 2 to 20 μm when importance is attached to the hardness, and particularly preferably 0.04 to 2 μm when hardness is relatively unimportant. is there.

Examples of the irradiation method of active energy rays include, for example, ultraviolet rays emitted from a light source such as a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, and a tungsten lamp, or a particle accelerator of usually 20 to 2000 kV. Examples include a method of irradiating active energy rays such as extracted electron beam, α ray, β ray, γ ray, and the like.
A cured film cured with such active energy rays is particularly preferable because of its excellent balance between productivity and physical properties.

The cured film comprising the active energy ray-curable resin composition of the present invention can be particularly suitably used as a stain-resistant hard coat layer for optical recording media and optical displays.
A typical optical recording medium is an optical disk, but the type may be any of a phase change type, a dye type, a magneto-optical type, a read-only type, and the like. Of these, optical disks for high-density recording such as DVD, HD DVD, and Blu-Ray Disc are preferable. To increase the recording density, the recording mark and the beam diameter of the recording / reproducing laser beam are reduced, so that it is sensitive to dirt and scratches, and jitter is likely to increase and recording / reproducing errors are likely to increase. Is required.

  A preferred configuration is an optical recording medium having a multilayer film having at least a recording layer or a reflective layer on a substrate, and at least a hard coat comprising the cured film of the present invention on the outermost surface on the light incident side of the optical recording medium It is a laminated body having a structure having layers. If there is dirt or scratches on the outermost surface on the light incident side, the recording / reproducing beam is blocked and an error occurs. Therefore, it is preferable to provide the cured film of the present invention on the outermost surface on the light incident side as a stain-resistant hard coat layer. For example, (1) the light-incident surface is opposite to the substrate side with respect to the recording layer or reflective layer, such as Blu-Ray Disc, and (2) the substrate side is opposite to the recording layer or reflective layer, such as DVD. Some are light incident surfaces. In this case, the hard coat layer needs to be light transmissive. The light transmissive property generally refers to a state where the transmittance is 80% or more with respect to light having a wavelength of recording / reproducing light. The cured film of the present invention may be provided on the outermost surface opposite to the light incident side.

A preferred layer structure of the optical recording medium will be described below.
(1) Optical recording medium in which the multilayer film side surface is the recording / reproducing beam incident side surface The preferred layer structure of such an optical recording medium is a (reflection layer) recording layer, hard coat layer (cured film) on a substrate. ) In this order. More preferably, a light transmission layer is provided between the recording layer and the hard coat layer. Providing the light transmission layer is preferable because the distance between the light incident side outermost surface of the optical recording medium and the recording layer (reflection layer) is widened, and the recording / reproducing beam is less susceptible to contamination and scratches on the surface of the medium. The thickness of the light transmission layer is preferably 30 μm or more, and more preferably 70 μm or more. Further, the thickness of the light transmission layer is preferably 200 μm or less, and more preferably 150 μm or less.

Arbitrary layers may be provided between the respective layers according to the purpose. For example, an inorganic protective layer made of a dielectric or the like may be provided above and below the recording layer. Alternatively, in order to increase the recording capacity, a plurality of recording layers and reflection layers may be provided via a light transmission spacer layer. The light transmissive spacer layer is provided to prevent signals from being mixed between a plurality of recording layers, and the film thickness is preferably the same as that of the light transmissive layer.
Examples of particularly preferable layer configurations include a substrate / reflection layer / inorganic protective layer / recording layer / inorganic protective layer / light transmission layer / hard coat layer, substrate / reflection layer / light transmission layer / hard coat layer, and substrate / Reflective layer / inorganic protective layer / recording layer / inorganic protective layer / light transmissive spacer layer / reflective layer / inorganic protective layer / recording layer / inorganic protective layer / light transmissive layer / hard coat layer, substrate / inorganic protective layer / recording layer Preferred examples include / inorganic protective layer / light transmission layer / hard coat layer, but are not limited thereto.

The materials for the substrate, the recording layer, the reflective layer, and the inorganic protective layer are not particularly limited, and any known material for optical recording media can be used.
As the substrate, resins such as polycarbonate, polyacrylate, and polyolefin, or glass can be used. When recording / reproducing light is incident from the substrate side, the substrate needs to be transparent to the recording / reproducing light. The thickness of the substrate is usually 0.3 to 1.2 μm. In many cases, grooves (pits) or pits are formed on the substrate.

  The recording layer includes a phase change type, a dye type, and a magneto-optical type. The read-only type may not have a recording layer. For the phase change recording layer, a chalcogen-based alloy is often used, and examples thereof include a GeSbTe-based alloy, an InSbTe-based alloy, a GeSnTe-based alloy, and an AgInSbTe-based alloy. The thickness of the phase change recording layer is usually 3 nm to 50 nm. For the dye-type recording layer, azo dyes, cyanine dyes, phthalocyanine dyes, porphyrin dyes, and the like can be used, but are not limited thereto. The thickness of the dye-type recording layer is usually 50 nm to 10 μm.

The material of the inorganic protective layer is determined in consideration of the refractive index, thermal conductivity, chemical stability, mechanical strength, adhesion, and the like, and usually a dielectric is used. As the material for the inorganic protective layer, generally, a transparent or high melting point metal, semiconductor oxide, sulfide, oxysulfide, nitride, or fluoride such as Ca, Mg, or Li is used. The thickness of the inorganic protective layer is usually about 5 to 200 nm.
The reflective layer is preferably made of a material having high reflectance and thermal conductivity. Examples of the reflective layer material having a high reflectance and thermal conductivity include metals mainly composed of Ag, Au, Al, Cu and the like. Among them, Ag has a higher reflectance and thermal conductivity than Au, Al, and Cu. These include Cr, Mo, Mg, Zr, V, Ag, In, Ga, Zn, Sn, Si, Cu, Au, Al, Pd, Pt, Pb, Ta, Ni, Co, O, Se, V, Nb , Ti, O, N, etc. may be included up to about 5 atomic%. The thickness of the reflective layer is usually 30 to 200 nm. The reflective layer may be a so-called semi-reflective layer.

  The light-transmitting layer and the light-transmitting spacer layer need only be light-transmitting and have a predetermined thickness, and the material and formation method are not particularly limited, but a resin composition is usually used, and the following two methods are typically used. Formed with. The first method is a method in which a curable resin composition is applied by spin coating or the like and then cured by light or heat to form a film. If urethane acrylate is contained at this time, the hardness and scratch resistance of the surface can be increased while suppressing warpage due to curing shrinkage, which is preferable. In addition, it is also preferable to include inorganic oxide fine particles such as colloidal silica within the range not impairing the light transmittance in order to increase the surface hardness and scratch resistance. The second method is a method in which a film produced by solvent casting or melt extrusion molding is attached directly or via an adhesive. At this time, in order to further increase the hardness and scratch resistance of the surface, it is preferable to contain inorganic oxide fine particles such as colloidal silica as long as the light transmittance is not impaired. In some cases, grooves (pits) or pits are formed in the light transmitting spacer layer.

  A method for forming a hard coat layer comprising a cured film obtained from the composition of the present invention will be described. A general method is to apply a composition of the present invention on a layer as described above by spin coating or the like and then polymerize by irradiation with active energy rays to form a cured film. Alternatively, after coating on a peelable film and polymerizing and curing by irradiation with active energy rays to form a film, the film side is attached to the optical recording medium directly or via an adhesive, and the film is peeled off to form a hard coat layer A method is also preferred. Furthermore, after applying the composition of the present invention to a film produced by solvent casting or melt extrusion molding, it is polymerized by irradiation with active energy rays to form a cured film, directly or via an adhesive. A method of forming the light transmission layer and the hard coat layer at the same time is also preferable.

Examples of the optical recording medium having such a layer structure include a Blu-Ray Disc.
In both methods for forming the hard coat layer, in order to further enhance the surface hardness and scratch resistance, the inorganic oxide fine particles may be blended within a range that does not impair other properties such as transparency. it can.
In particular, when the composition is formed by spin coating, cured, and formed into a film, the use of a composition that increases the hardness of the film usually tends to cause warping due to curing shrinkage. In order to avoid this, it may be particularly preferable to include inorganic oxide fine particles and / or urethane acrylate.

(2) Optical recording medium whose surface on the substrate side is the recording / playback beam incident side surface A preferred layer structure of such an optical recording medium has a recording layer and a reflective layer in this order on the substrate, and the other side of the substrate A hard coat layer is provided on the surface. The recording / reproducing light is incident on the recording layer and the reflective layer through the hard coat layer and the substrate. A light transmission layer may be provided between the substrate and the hard coat layer.

Arbitrary layers may be provided between the respective layers according to the purpose. For example, an inorganic protective layer made of a dielectric or the like may be provided above and below the recording layer. In order to increase the recording capacity, a plurality of recording layers and reflection layers may be provided via a light transmission spacer layer.
Examples of particularly preferred layer structures include hard coat layer / substrate / inorganic protective layer / recording layer / inorganic protective layer / reflective layer, hard coat layer / substrate / reflective layer, and hard coat layer / substrate / inorganic protective layer. / Recording layer / Inorganic protective layer / Reflective layer / Light transmissive spacer layer / Inorganic protective layer / Recording layer / Inorganic protective layer / Reflective layer, Hard coat layer / Light transmissive layer / Substrate / Inorganic protective layer / Recording layer / Inorganic protective layer / Reflective layers and the like are preferred, but are not limited thereto.

The material and thickness of each layer are preferably the same as (1).
Examples of the optical recording medium having such a layer structure include various DVDs (including a DVD having a plurality of recording layers) such as DVD ± R, DVD ± RW, and DVD-RAM, and HD DVD. The formation method of the hard coat layer in this configuration is generally a method in which the composition of the present invention is applied on a substrate or the like by spin coating or the like, and then polymerized and cured by irradiation with active energy rays to form a film.
Among optical displays, a representative is a touch panel optical display, but this has a different layer structure depending on the type of the touch panel. For example, in the case of the resistance film type, a transparent film with a transparent conductive layer (usually a polyester film is used, but an alicyclic olefin skeleton-containing polymer film, an optical polycarbonate film, an optical acrylic film, a triacetyl cellulose film, etc. Other transparent optical films can also be used on the outermost surface of the display, and scratch / stain resistance (particularly fingerprint resistance) is essential. This format is widely used in mobile phones, game machines, portable music players, information terminals, car navigation systems, digital cameras, and the like.

  Also, in the case of the electrostatic capacity method, it has been widely used in automatic teller machines (ATMs), ticket vending machines, and some touch panel-operable personal computers, but from the viewpoint of protecting the transparent conductive film. Therefore, it is necessary to provide a thin optical film that imparts antifouling and antireflection properties in the outermost layer. Furthermore, when forming a touch panel with a new capacitance method that has recently been rapidly spreading in mobile phones and the like, the outermost surface is often an acrylic protective plate, and the surface also has scratch resistance and antifouling properties. It is essential to have. In the future, such capacitive touch panels are expected to greatly expand applications such as car navigation, digital cameras, game machines, notebook computers, and digital signage.

The hard coat layer made of the cured film of the present invention is particularly preferably used on the surface where a pen or a finger touches in such an optical display.
As a general coating method for forming the hard coat layer comprising the cured film of the present invention, the above-mentioned method can be mentioned as an example, but in the case of an optical recording medium, spin coating is preferred. When the coating composition is formed by spin coating the resin composition of the present invention, the coating solution can be applied uniformly in a short time as long as the coating object is rotated at a high speed, and a volatile organic solvent can be applied. Even if a small amount of water remains, the drying process can be omitted because most of it is volatilized during application. Therefore, spin coating is the most suitable coating method for optical recording medium applications from various aspects such as production efficiency, quality stability, and reduction of production equipment costs.

  On the other hand, especially in the case of a resistive film type optical display, usually, a hard coat layer is formed on the opposite side of the conductive film of the wide film or sheet, or the opposite side of the film or sheet with the conductive film. A hard coat film (or sheet) with a conductive film prepared by laminating a film with a hard coat layer is used. Therefore, as a coating method for forming the hard coat layer, general coating methods (roll coater, gravure coater, knife coater, blade coater, curtain coater, etc.) can be widely used.

Also, in the case of a capacitive optical display, usually, a film with a hard coat layer is usually stuck on the surface, and the coating method for forming a hard coat layer with such a film is the same as above. Even when the IML method or IMD method is used with a new capacitance type, it is necessary to form a (hard) coat film on the film before decorating and transferring, and the coating method is the same as above.
In the case of a small amount evaluation, a method such as bar coater, dip coating, spin coating or the like may be used.

The thickness of the cured film is not particularly defined, but in the case of an optical recording medium, it is preferably 0.01 to 20 μm, and particularly when hardness is important, it is preferably 2 to 10 μm. When the hardness is not relatively important, it is particularly preferably 0.01 to 2 μm. In the case of an optical display, it is preferably 0.1 to 20 microns, more preferably 2 to 10 microns.
The cured film made of the active energy ray-curable resin composition of the present invention and the hard coat layer made of the cured film preferably satisfy the following physical properties.

1) Pencil hardness On a polycarbonate film having a thickness of 1 mm, a coating film made of the composition of the present invention having a thickness of 3 μm is formed. using a high pressure mercury lamp is ^two, the pencil hardness of the surface of the cured film obtained by irradiating such ultraviolet rays the integrated quantity of light 1000 mJ / cm ² to is usually HB or more. Preferably it is F or more. In addition, the irradiance in this case is measured using an illuminometer that is JIS-compliant (JIS-C 1609-1 2006) and has a sensor for wavelength 254 nm.

Here, the pencil hardness is 6B, 5B,..., B, HB, F, H, 2H, 3H,.
According to the composition of the present invention, since the curability is good, the surface of the cured film to be obtained has a high pencil hardness even under the mild ultraviolet irradiation conditions as described above. Therefore, it can be particularly suitably used for applications such as optical recording media that are required to be cured under relatively mild ultraviolet irradiation conditions.

2) Contact angle A coating film made of the composition of the present invention having a thickness of 3 μm is formed on a polycarbonate film having a thickness of 1 mm, and the irradiance at a wavelength of 254 nm is 400 mW / cm ² under the condition of an oxygen concentration of 20%. The contact angle of water on the surface of the cured film obtained by irradiating ultraviolet rays with an integrated light quantity of 1000 mJ / cm ² using a high pressure mercury lamp is 80 degrees or more, and the contact angle with hexadecane is 25 degrees or more. It is preferable.
In the cured film of this invention, since the contact angle with respect to water and hexadecane is high, the outstanding stain resistance is shown.

3) ESCA (XPS)
A coating film made of the composition of the present invention having a thickness of 3 μm is formed on an easily adhesive polyethylene terephthalate (PET) film having a thickness of 100 μm, and the irradiance at a wavelength of 254 nm is 400 mW / weight under the condition of an oxygen concentration of 20%. using a high pressure mercury lamp cm ^2, and when irradiated with ultraviolet light so that the integrated light quantity of 500 mJ / cm ^2, the content of the anti-fouling property imparting group at the position of thickness 3nm from the film surface of the cured film, The average content of the stain resistance imparting group in the entire cured film is preferably at least 3 times, and more preferably 3.2 to 100 times. That is, according to the composition of the present invention, it is preferable that the stain resistance-imparting group is specifically present at a high concentration on the surface of the cured film. It is one of the characteristics of the composition of the present invention that the cured film can have such a structure. As a result, the content of the stain resistance-imparting group in the composition is, for example, 1% by weight of the entire composition. Even if it is low, the amount of the stain resistance-imparting group on the surface of the coating film increases, and as a result, the stain resistance of the cured film becomes excellent.

In the present specification, the stain resistance imparting group refers to a group capable of imparting stain resistance such as a polydimethylsiloxane group, a perfluoroalkyl group, a perfluoroalkylene group, and the like.
The content of the stain resistance-imparting group can be determined, for example, by measurement with an X-ray photoelectron spectrometer (hereinafter referred to as ESCA or XPS). That is, using ESCA (XPS), the atomic ratio in the range of 3 nm from the surface can be determined and compared with the average composition ratio of the composition. Here, for example, when a fluorine-based stain resistance imparting group is used, the F / C ratio can be compared by obtaining an Si / C ratio when a silicone stain resistance imparting group is used. .

4) Abrasion resistance A film made of the composition of the present invention having a thickness of 3 μm was formed on an easily adhesive polyethylene terephthalate (PET) film having a thickness of 100 μm. When a high-pressure mercury lamp having an irradiance of 400 mW / cm ² is used and ultraviolet rays are irradiated so as to have an integrated light quantity of 500 mJ / cm ² , the resulting cured film preferably has an abrasion resistance of 25.0 or less. . In addition, this abrasion resistance measuring method is described in the item of the below-mentioned Example. The irradiance at this time is measured using an illuminometer that is JIS-compliant (JIS-C 1609-1 2006) and has a sensor for wavelength 254 nm.

5) Fingerprint resistance When the active energy ray-curable resin composition of the present invention is used, a fingerprint or an artificial fingerprint liquid is attached to the surface of a cured film or a hard coat layer and wiped off with a tissue paper at a load of 200 g. 3 reciprocating within the wiping operation, and more preferably in operation within two reciprocating, fully as fingerprints can be removed, it is possible to obtain a fingerprint wiping property good surface properties are extremely. The artificial fingerprint liquid is a mixture of triolein / 1-11 kinds of powder for JIS test (Kanto Loam, manufactured by Japan Powder Industrial Technology Association) /methoxypropanol=1/0.4/10 (weight ratio),
It is a liquid used for fingerprint resistance evaluation of next-generation optical discs.

  Many anti-fouling agents that have been developed as anti-fingerprint agents for DVDs and next-generation optical discs and as anti-fingerprint agents for laminates for optical displays can be wiped off, even if the amount of attachment or diameter is small. At times, the slipperiness (slip property) is too high or the hardness is insufficient, so that it is easy to spread on the surface, and many wipes have three or more reciprocations, but the cured film and the hard coat layer of the present invention are Since it has a high hardness after curing and does not have excessive slipperiness, it can be wiped off with a small number of wipes.

Further, even if fingerprints or artificial fingerprint liquid are attached, wiped 3 times with tissue paper at a load of 200 g, and wiping operation repeated 20 times, the fingerprint removal property does not deteriorate.
Even if a stain-resistant imparting agent that can be wiped off with a small number of wipes is used, the conventional one has insufficient hardness or the stain-resistant imparting agent itself is not fixed to the surface of the cured film. Repeating the operation will result in fine scratches on the surface several times to a few dozen times, and fingerprints (or artificial fingerprint liquid) may enter the gaps, or the stain-proofing agent itself may be lost from the surface, removing the fingerprints. However, the cured film and the hard coat layer of the present invention have high hardness after curing, and a compound having a stain resistance-imparting group is fixed on the film surface. Preferably, even if the operation is repeated 40 times or more, the wiping property of the fingerprint (or artificial fingerprint liquid) does not deteriorate, and it has a very high performance durability.

6) Curability On a polycarbonate film having a thickness of 1 mm, a coating film made of the resin composition for hard coat of the present invention having a thickness of 3 μm is formed, and the irradiance at a wavelength of 254 nm under the condition of an oxygen concentration of 20%. When a high-pressure mercury lamp having a power of 400 mW / cm ² is used to irradiate ultraviolet rays so as to have an integrated light quantity of 500 mJ / cm ² , it is preferable to obtain a cured film that has been cured until completely tack-free. In addition, the irradiance in this case is measured using an illuminometer that is JIS-compliant (JIS-C 1609-1 2006) and has a sensor for wavelength 254 nm.

The present invention will be described more specifically with reference to the following examples. The following materials, amounts used, ratios, processing details, processing procedures, and the like can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
In the examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively. Further, “substantially solvent-free” in the examples means that an organic solvent is not contained in excess of 5% by weight in the composition.
The physical properties of the active energy ray-curable resin composition obtained in the following examples and the like and the cured film made of the composition were evaluated by the following methods.

(1) Viscosity The active energy ray-curable resin composition was measured at 25 ° C. and 30 to 60 rpm (unit: mPa · s) using a Brookfield viscometer (Brookfield DV-I type).
(2) Appearance The appearance of the active energy ray-curable resin composition was visually evaluated as follows.
◯: No foreign matter can be visually confirmed and uniform.
X: Foreign matter can be confirmed visually, and is non-uniform.

(3) Curability On a polycarbonate film having a thickness of 1 mm, a coating film made of an active energy ray-curable resin composition having a thickness of 3 μm is formed by spin coating, and at a wavelength of 254 nm under the condition of an oxygen concentration of 20%. Using a high-pressure mercury lamp having an irradiance of 400 mW / cm ² , the curability when irradiated with ultraviolet rays was evaluated as follows. In addition, the irradiance in this case is based on JIS (JIS-C 1609-1 2006) and using an illuminometer Eye UV tester UV-PFA1 light receiving unit PD-254 (Iwasaki Electric Co., Ltd.) having a sensor for wavelength 254 nm. It was measured.

A: Accumulated light quantity ≦ 300 mJ / cm ² , the cured film surface becomes tack-free.
○: 300 mJ / cm ² <integrated light quantity ≦ 500 mJ / cm ² , and the cured film surface becomes tack-free.
Δ: 500 mJ / cm ² <integrated light quantity ≦ 1000 mJ / cm ² , and the cured film surface becomes tack-free.
X: Integrated light quantity = 1000 mJ / cm ² , and the cured film surface does not become tack-free.

(4) -1 Transparency (haze value)
As described later, the haze value of the laminate obtained by forming the cured film on the polycarbonate film was measured and evaluated based on the conditions of JIS K-7105.
(4) -2 Transparency (visual)
The cured film was visually evaluated as follows.
○: The coating film is completely cloudy, cloudy, and whitened.
Δ: The coating film is uniformly and slightly cloudy.
X: The coating film is clouded unevenly, or partially or entirely cloudy, or whitening is observed.

(5) Pencil hardness About the cured film, it measured based on the conditions of JIS K-5400 using a JIS compliant pencil hardness meter (manufactured by Dazai Equipment Co., Ltd.) and evaluated with the hardest pencil count without scratches.
(6) Scratch resistance The cured film was rubbed with steel wool # 0000 with a load of 200 g and evaluated as follows.
A: After 10 reciprocations, no scratches can be visually confirmed.
◯: No flaws can be visually confirmed after 5 reciprocations, and flaws can be visually confirmed after 10 reciprocations.
X: Remarkable flaws can be confirmed visually by 5 reciprocations.

(7) Contact angle of water 0.002 ml of pure water was dropped on the cured film, and the contact angle after 1 minute was measured. The contact angle was measured using a contact angle meter (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.) (unit: degree).
(8) Contact angle of hexadecane 0.002 ml of hexadecane was dropped onto the cured film, and the contact angle after 1 minute was measured. The contact angle was measured using a contact angle meter (DropMaster 500, manufactured by Kyowa Interface Science Co., Ltd.) (unit: degree).

(9) Fingerprint adherence An artificial fingerprint solution is spin-coated at 3000 rpm on a polycarbonate substrate with a thickness of 1.1 mm that is injection-molded into an optical disc shape, and dried at 60 ° C. for 3 minutes to produce an artificial fingerprint liquid master. did. The artificial fingerprint liquid is a mixture of triolein / 1-11 kinds of powder for JIS test (Kanto Loam, manufactured by Japan Powder Industrial Technology Association) /methoxypropanol=1/0.4/10 (weight ratio), It is a liquid used for fingerprint resistance evaluation of next-generation optical discs.

On this master, no. 1. Prepare a transfer material with the smaller end face of silicone rubber uniformly roughened with # 240 abrasive paper, press the roughened end face with a constant load of 4.9 N for 10 seconds, and then evaluate the curing The end face is pressed against the film surface with a constant load of 4.9 N (operation L1).
Further, the operation of pressing the roughened end face on the master disk with a constant load of 4.9 N for 10 seconds was repeated n times continuously to increase the adhesion amount of the artificial fingerprint liquid, and then the cured film surface to be evaluated The end face is pressed with a constant load of 4.9 N (operation Ln).

By visually observing the adhesion diameter of the artificial fingerprint liquid by this operation with a microscope with a scale of 100 times, the operation Ln in which n is maximum within the range where the maximum adhesion diameter is kept to 20 μm or less is defined as the artificial fingerprint liquid adhesion. did.
Ln that maximizes n is preferably L3 or L4, and more preferably L4.

(10) Fingerprint wiping property The nasal oil was used as a substitute for sebum, the nasal oil was placed on the thumb, and the thumb was pressed against the cured film for 3 seconds to attach a fingerprint to the cured film. The surface of the fingerprint was lightly wiped with tissue paper (manufactured by Crecia), and the number of reciprocations until it became visually invisible with a distance of 15 cm was evaluated as the fingerprint wiping property.
(11) Durability for wiping off fingerprints The nasal oil was used as a substitute for sebum. The operation of wiping the fingerprint with a tissue paper (made by Crecia Co., Ltd.) wound around a 200 g weight was performed three times. This operation was repeated up to the 20th time. After the 20th operation, when the fingerprint was not visible with a distance of 15 cm, it was evaluated as ◯, and when it was visually visible, it was evaluated as x.

(12) Magic-resistant adhesion A line was drawn with an oil-based magic marker (Mckey Care ultra-fine (black) thin made by Zebra), and evaluated as ◯ if the line was repelled after 30 seconds, and x if not repelled.
(13) draw a line in the magic wipe of oil-based magic marker (fine of Zebra Co., Ltd. McKee care ultra-fine (black)), after 30 seconds, wipe the surface with a tissue paper (CRECIA Co., Ltd.), it is wiped with 3 round trip within If it was not wiped off, it was rated as x.

<Synthesis Example 1> Synthesis of a polyfunctional acrylate derivative (A-1) containing an organic-inorganic composite in which a polyfunctional acrylate having three or more acryloyl groups in one molecule is bonded to inorganic oxide fine particles through covalent bonds 1 kg of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Kayarad DPHA, Nippon Kayaku Co., Ltd.), 50 g of γ-triethoxysilylpropyl isocyanate (KBE9007, Shin-Etsu Silicone Co., Ltd.), dibutyltin dilaurate 0.2 g, hydroquinone monomethyl After stirring and mixing 0.5 g of ether, the temperature was raised to 90 ° C. under an air stream and maintained for 1 hour. Infrared spectroscopic analysis (hereinafter sometimes abbreviated as IR) confirmed that the absorption corresponding to the NCO group had completely disappeared, and then returned to room temperature, and the product was taken out (silane coupling agent 1, Hereinafter referred to as SC1). This reaction was quantitative.

Next, 400 g of methyl ethyl ketone (MEK) -dispersed organosilica sol (MEK-ST, 30% MEK dispersion, manufactured by Nissan Chemical Co., Ltd.), 400 g of SC1 above, 0.4 g of hydroquinone monomethyl ether, 4 g of acetylacetone aluminum were mixed thoroughly, 8 g of water was added and stirring was continued for 3 hours or more at room temperature. Thereafter, the temperature is increased to 50 to 70 ° C. in an air atmosphere, and stirring is continued at that temperature for 2 hours or more. A dispersion was obtained.
MEK was distilled off while continuously supplying air from this solution to obtain substantially solvent-free (A-1). The viscosity at 25 ° C. was 6000 mPa · s.

<Synthesis Example 2> Synthesis of a polyfunctional acrylate derivative (A-2) including an organic-inorganic composite in which a polyfunctional acrylate having three or more acryloyl groups in one molecule is bonded to inorganic oxide fine particles by a covalent bond In Synthesis Example 1, instead of 1 kg of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Kayarad DPHA, manufactured by Nippon Kayaku Co., Ltd.), a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Kayarad DPHA, Japan Silane coupling in the same manner as in Synthesis Example 1 except that 0.5 kg of Kayaku Co., Ltd.) and 0.5 kg of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Biscoat # 300, Osaka Organic Chemical Co., Ltd.) were used. Agent 2 (below , Indicated as SC2. This reaction was quantitative.

  Subsequently, in Synthesis Example 1, a substantially solvent-free colloidal silica modification product (A-2) was obtained in the same manner as in Synthesis Example 1 except that SC2 was used instead of SC1. The viscosity at 25 ° C. was 3000 mPa · s.

<Synthesis Example 3> Synthesis of a polyfunctional acrylate derivative (A-3) containing an organic-inorganic composite in which a polyfunctional acrylate having three or more acryloyl groups in one molecule is bonded to inorganic oxide fine particles through a covalent bond In Synthesis Example 1, instead of 1 kg of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Kayarad DPHA, Nippon Kayaku Co., Ltd.), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Biscoat # 300, Osaka Organic Silane coupling agent 3 (hereinafter referred to as SC3) was obtained in the same manner as in Synthesis Example 1 except that 1.0 kg was used. This reaction was quantitative.

  Subsequently, in Synthesis Example 1, a substantially solvent-free modified colloidal silica (A-3) was obtained in the same manner as in Synthesis Example 1 except that SC3 was used instead of SC1. The viscosity at 25 ° C. was 800 mPa · s.

<Synthesis Example 4> Synthesis of active energy ray-curable compound (d-1) In a 1000 ml separable round bottom flask, 50 g of perfluorooctylethyl methacrylate, 10 g of lauryl methacrylate, α, ω-dimercaptopropylpolydimethylsiloxane (number average molecular weight) 1600) 10 g, glycidyl methacrylate 30 g, dodecyl mercaptan 2 g (number of SH groups of dodecyl mercaptan / α, number of SH groups of ω-dimercaptopropylpolydimethylsiloxane = 1.78, total number of SH groups / number of epoxy groups = 0.106) and 200 g of 1-methoxy-1-propanol (PGM) were added, and the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, 2,2′-azobis (2,4-dimethylvaleronitrile) (V65) was divided into 2 portions, a total of 1.5 g was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The number average molecular weight was 15000 and the solid content concentration was 34%.

Next, after heating to 90 ° C. in an air atmosphere, 0.1 g of p-methoxyphenol and 0.5 g of triphenylphosphine were added. After 5 minutes, 15.3 g of acrylic acid was dissolved in 50 g of PGM and added dropwise over 30 minutes. During this time, the liquid temperature was kept at 90 to 105 ° C. Thereafter, the liquid temperature was raised to 110 ° C. and held for 8 hours, and then returned to room temperature to obtain an active energy ray-curable compound (d-1). The number average molecular weight was 15000 and the solid content concentration was 33%.
The number average molecular weight was measured by gel permeation chromatography (GPC) method using THF as a solvent. The molecular weight is a molecular weight in terms of polystyrene. The solid content concentration is the amount of residual solids (average value of 3 points) after taking 1 g of liquid in an aluminum cup and vacuum drying at 80 ° C.

<Synthesis Example 5> Synthesis of active energy ray-curable compound (d-2) In a 1000 ml separable round bottom flask, 35 g of methyl methacrylate, 15 g of α, ω-dimercaptopropylpolydimethylsiloxane (number average molecular weight 1600), 50 g of glycidyl methacrylate 2 g of dodecyl mercaptan (number of SH groups of dodecyl mercaptan / α, number of SH groups of ω-dimercaptopropylpolydimethylsiloxane = 0.52, total number of SH groups / number of epoxy groups = 0.081), 200 g of PGM In addition, the internal temperature was raised to about 60 ° C. under a nitrogen stream. Thereafter, V65 was divided into two portions, 1.5 g in total was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The number average molecular weight was 16000, and the solid content concentration was 34%.
Next, the same operation as in Synthesis Example 4 was performed except that acrylic acid was changed to 25.5 g to obtain an active energy ray-curable compound (d-2). The number average molecular weight was 16000, and the solid content concentration was 35%.

Synthesis Example 6 Synthesis of Active Energy Ray Curing Compound (d-3) In a 1000 ml separable round bottom flask, 75 g of methyl methacrylate, 5 g of hydroxyethyl methacrylate, α, ω-dimercaptopropylpolydimethylsiloxane (X-22-167B) (Manufactured by Shin-Etsu Chemical Co., Ltd.); 20 g of number average molecular weight 1600) and 200 g of methyl ethyl ketone were added, and the internal temperature was raised to about 60 ° C. under a nitrogen stream. Next, V65 was divided into two portions, a total of 1.5 g was added, and stirring was continued at 65 ° C. for 6 hours. Thereafter, the internal temperature was raised to 80 ° C., V65 was completely deactivated, and then returned to room temperature. The number average molecular weight was 15000 and the solid content concentration was 34%.

  Thereafter, 5.4 g of 2-isocyanate ethyl acrylate (Karenz AOI (manufactured by Showa Denko KK)), 0.05 g of dioctyltin dilaurate and 0.05 g of p-methoxyphenol were added and reacted at 70 ° C. for 4 hours in an air atmosphere. After introducing an acrylic group into the side chain, the temperature was returned to room temperature to obtain an active energy ray-curable compound (d-3). The number average molecular weight was 16000, and the solid content concentration was 35%.

<Examples 1 to 14>
In the composition shown in Table 1, the components (A), (B), (C), and (D-1) are blended, and the active energy ray-curable resin composition that is a transparent liquid and substantially solvent-free is used. Obtained. When (d-1) and (d-2) were used as the component (D-1), the remaining solvent was removed under reduced pressure to less than 5% by weight while blowing air after blending. The physical properties of the composition are as shown in Table 1. In any case, the viscosity at 25 ° C. was in a preferable range, and the coating property was excellent.

Next, a coating film made of an active energy ray-curable resin composition having a thickness of 3 μm is formed on a polycarbonate film having a thickness of 1 mm by spin coating, and the irradiance at a wavelength of 254 nm under the condition of an oxygen concentration of 20%. Table 2 shows the physical properties of the cured film obtained by using a high-pressure mercury lamp having a current density of 400 mW / cm ² and irradiating ultraviolet rays so as to obtain an integrated light quantity of 1000 mJ / cm 2. In addition, the irradiance in this case is based on JIS (JIS-C 1609-1 2006) and using an illuminometer Eye UV tester UV-PFA1 light receiving unit PD-254 (Iwasaki Electric Co., Ltd.) having a sensor for wavelength 254 nm. It was measured. In any case, the pencil hardness was HB or higher, and other physical properties such as transparency and scratch resistance were also excellent.

  Table 3 shows the results of evaluation of contact angles of water and hexadecane of the cured film and various stain resistances. In all cases, the contact angle of water on the surface was 80 degrees or more, the contact angle of hexadecane was 25 degrees or more, and the contamination resistance was excellent.

<Comparative Examples 1-5>
In the composition shown in Table 4, the components (A), (B), (C) and (D-1) are blended, and the active energy ray-curable resin composition which is a transparent liquid and substantially solvent-free is used. Obtained. The physical properties of the composition are as shown in Table 4. Comparative Examples 1 to 5 have a large proportion of component (A), and all have viscosities at 25 ° C. exceeding 500 mPa · s. Therefore, the coating properties are inferior, and coating with no coating defects or uniform film thickness is difficult. Met.

<Comparative Examples 6-8>
In the composition shown in Table 4, each component is blended as components (A), (B), (C), and (D-1), is a transparent liquid, and is a substantially solvent-free active energy ray-curable resin. A composition was obtained. The physical properties of the composition are as shown in Table 4. In any case, the viscosity at 25 ° C. was in a preferable range, and the coating property was excellent.
Next, Table 5 shows the physical properties of cured films obtained in the same manner as in Examples 1 to 14 using the active energy ray-curable resin composition having the composition shown in Table 4. In all cases, the pencil hardness was 2B or less, and tackiness remained insufficient under mild active energy ray irradiation conditions. Further, physical properties such as scratch resistance were inferior, which was not preferable.

<Comparative Examples 9-11>
In the composition shown in Table 4, each component is blended as components (A), (B), (C), and (D-1), is a transparent liquid, and is a substantially solvent-free active energy ray-curable resin. A composition was obtained. The physical properties of the composition are as shown in Table 4. In any case, the viscosity at 25 ° C. was in a preferable range, and the coating property was excellent.
Next, Table 5 shows the physical properties of cured films obtained in the same manner as in Examples 1 to 14 using the active energy ray-curable resin composition having the composition shown in Table 4. In any case, since the amount of component (C) is small, the pencil hardness is 2B or less, and tackiness remains insufficient under mild active energy ray irradiation conditions. Further, physical properties such as scratch resistance were inferior, which was not preferable.

<Comparative Examples 12 and 13>
In the composition shown in Table 4, each component is blended as components (A), (B), (C), and (D-1), is a transparent liquid, and is a substantially solvent-free active energy ray-curable resin. A composition was obtained. The physical properties of the composition were as shown in Table 4. The viscosity at 25 ° C. was in the preferred range and the coating property was excellent.
Next, Table 5 shows the physical properties of cured films obtained in the same manner as in Examples 1 to 14 using the active energy ray-curable resin composition having the composition shown in Table 4. The pencil hardness was 3B, and tack remained and the curability was insufficient under the mild irradiation conditions of active energy rays. Further, physical properties such as scratch resistance were inferior, which was not preferable.

<Production Example 1>
A reflective layer, a second dielectric layer, a recording layer, a first layer are formed on the surface of a disk-shaped support substrate (made of polycarbonate, thickness 1.1 mm, diameter 120 mm) on which grooves are formed for information recording. An optical recording medium for Blu-ray Disc (intermediate product) on which one dielectric layer was formed was prepared.

After applying a radical polymerizable active energy ray-curable material having the following composition to the surface of the first dielectric layer by a spin coating method, an integrated light quantity of 1000 mJ / cm ² is obtained using a high-pressure mercury lamp with an output density of 60 W / cm. The film was irradiated with ultraviolet light to form a light-transmitting protective layer having a thickness of 97 μm after curing. The pencil hardness of this surface was 4B.

(Composition of radical polymerizable active energy ray curable material for light transmission protective layer)
60 parts by weight of urethane acrylate oligomer (urethane acrylate produced by reacting an isocyanate-terminated oligomer obtained by adding isophorone diisocyanate to polytetramethylene glycol having an average molecular weight of 800 to hydroxyethyl acrylate)
20 parts by weight of isocyanuric acid ethylene oxide-modified triacrylate (Toagosei Co., Ltd., Aronix M313)
Tetrahydrofurfuryl acrylate 20 parts by weight Irgacure 184 3 parts by weight

<Examples 15 to 17>
An active energy ray-curable resin composition having the composition shown in Table 6 was obtained in the same manner as in Examples 1-14.
This composition was applied onto the transparent protective layer formed in Production Example 1 by a spin coating method to form a coating film. Using a high pressure mercury lamp with an irradiance of 400 mW / cm ² at a wavelength of 254 nm under the condition of an oxygen concentration of 20%, this coating film was irradiated with ultraviolet rays so as to have an integrated light quantity of 1000 mJ / cm 2, and after curing A hard coat layer having a thickness of 3 μm was prepared. In addition, the irradiance in this case is based on JIS (JIS-C 1609-1 2006) and using an illuminometer Eye UV tester UV-PFA1 light receiving unit PD-254 (Iwasaki Electric Co., Ltd.) having a sensor for wavelength 254 nm. It was measured.
About the surface physical properties of the hard coat layer, transparency (visual evaluation), pencil hardness, contact angle (water, hexadecane), stain resistance (artificial fingerprint liquid adhesion, artificial fingerprint liquid wiping property, artificial fingerprint liquid wiping durability) ) Was evaluated. The results are shown in Table 8 for contamination resistance and Table 7 for other physical properties.

The hard coat layer prepared from the active energy ray-curable resin composition (Examples 15 to 17) of the present invention has a high contact angle and is particularly excellent in adhesion among stain resistances. As a result, wiping property and wiping durability are obtained. It was also excellent in properties, and a preferable Blu-ray Disc could be obtained.
In addition, Examples 15 to 17 in which a cured film having a film thickness of 3 μm is formed on a PC substrate via a light transmission protective layer correspond to Blu-ray Disc applications.

For reference, pencil hardness, contact angle, and stain resistance of an optical recording medium (next-generation optical disc (Blu-ray Disc)) that has a hard coat layer coated and cured on the surface for commercial use. Evaluated. The results are shown in Table 9.
Although commercially available products A, B, and C have excellent adhesion of artificial fingerprint liquid, the wiping property exceeds 3 reciprocations and the wiping durability is low. From the cured film of the active energy ray-curable resin composition of the present invention, It was clearly inferior to the hard coat layer.

<Examples 18 to 20>
Active energy ray-curable resin compositions having the compositions shown in Table 6 were obtained in the same manner as in Examples 15-17.
This composition was applied to a biaxially stretched PET film (Mitsubishi Resin Co., Ltd., Diafoil T600E100) having a thickness of 100 μm and having an easy-adhesion treatment layer on the surface thereof to form a coating film. Using a high pressure mercury lamp with an irradiance of 400 mW / cm ² at a wavelength of 254 nm under the condition of an oxygen concentration of 20%, this coating film was irradiated with ultraviolet rays so as to have an integrated light quantity of 1000 mJ / cm 2, and after curing A hard coat layer having a thickness of 5 μm was prepared. In addition, the irradiance in this case is based on JIS (JIS-C 1609-1 2006) and using an illuminometer Eye UV tester UV-PFA1 light receiving unit PD-254 (Iwasaki Electric Co., Ltd.) having a sensor for wavelength 254 nm. It was measured.
About the surface physical properties of the hard coat layer, transparency (visual evaluation), pencil hardness, contact angle (water, hexadecane), stain resistance (artificial fingerprint liquid adhesion, artificial fingerprint liquid wiping property, artificial fingerprint liquid wiping durability) ) Was evaluated. The results are shown in Table 11 for contamination resistance and Table 10 for other physical properties.

The hard coat layer prepared from the active energy ray-curable resin composition of the present invention has a high contact angle, particularly excellent adhesion among stain resistance, and as a result, excellent wiping property and wiping durability. In particular, it was possible to obtain a preferable one for a surface protective coating for a touch panel display.
In addition, Examples 18-20 which formed the cured film with a film thickness of 5 micrometers on a PET film base material respond | correspond to a touchscreen display use.

Claims (10)

When the following (A), (B), (C) and (D-2) are included, and the content of (A) and (B) is 100 parts by weight of the total amount of (A) and (B) (A) is 35 to 90 parts by weight, and the content of (C) is 2 to 5 parts by weight with respect to 100 parts by weight of the total amount of (A) and (B). ) Is 0.1 to 15 parts by weight with respect to 100 parts by weight of the total amount of (A) and (B), and the active energy ray-curable resin composition has a viscosity at 25 ° C. of 10 to 500 mPa · s. An active energy ray-curable resin composition, which is a product and does not contain more than 5% by weight of an organic solvent in the composition.
(A) Multifunctional (meth) acrylate derivative containing an organic-inorganic composite in which a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in one molecule is bonded to inorganic oxide fine particles by covalent bonds body (B) 1-4 (meth) acryloyl groups and / or in one molecule containing (meth) acrylamide group, a 1-4-functional (meth) acrylate and / or (meth) acrylamide <br / > (C) Photopolymerization initiator (D-2) A monomer containing one or more groups selected from a polydimethylsiloxane group, a perfluoroalkyl group, and a perfluoroalkylene group, and a monomer containing a (meth) acrylate having an epoxy group And a carboxylic acid having one or more (meth) acryloyl groups in one molecule is reacted with at least a part of the epoxy groups of the radical polymer in the mixture. The active energy ray-curable polymer having a structure corresponding to the The active energy ray-curable resin composition according to claim 1, wherein the (B) includes at least one of the following (i) to (iii).
(I) a (meth) acrylate having one (meth) acryloyl group in one molecule, directly or directly to an oxygen atom bonded to the (meth) acryloyl group, an α-position carbon or a β-position A (meth) acrylate (ii) to which one selected from (poly) cycloalkyl group, (poly) cycloalkenyl group, hydroxyalkyl group, cyclic ether group, and (poly) alkylene oxide group is bonded via carbon. ) A (meth) acrylate having 2 to 4 (meth) acryloyl groups in one molecule, directly or directly to the oxygen atom bonded to at least one (meth) acryloyl group or the α-position carbon Alternatively, via a β-position carbon, (poly) cycloalkylene group, (poly) cycloalkenylene group, hydroxyalkylene group, cyclic ether group, and (Meth) acrylate (iii) to which one selected from alkylene oxide groups is bonded (meth) acrylamide having 1 to 4 (meth) acryloyl groups in one molecule, the (meth) acryloyl group (Meth) acrylamide in which the amino group bonded to is substituted with two alkyl groups (however, the two alkyl groups may be bonded directly or through a hetero atom)   The active energy ray-curable resin composition according to claim 2, wherein 1/3 or more of the total weight of the (B) is the (i) to (iii). Wherein (B) is one containing 1 to 4 acryloyl groups in one molecule, the active energy ray curable resin composition according to any one of claims 1 to 3. (A) is a modified colloidal silica in which a reaction product of pentaerythritol triacrylate and triethoxysilylpropyl isocyanate is bonded to colloidal silica, or a reaction product of dipentaerythritol pentaacrylate and triethoxysilylpropyl isocyanate is converted into colloidal silica. colloidal silica modifications bound, modified product with a polyalkylene oxide of colloidal silica modifications, or modified products by polycaprolactone these colloidal silica modifications, including any of, or any of the preceding claims 1 the active energy ray curable resin composition according to item. Wherein (C) is α- aminophenyl ketones, benzophenones, benzoylformate (esters), and one or more selected from an oxime esters, active energy according to any one of claims 1 to 5 A linear curable resin composition. The active energy ray curable resin composition according to any one of claims 1 to 6, which is used for optical materials. The active energy ray curable resin composition according to any one of claims 1-7, cured film formed by irradiating an active energy ray.   The laminated body which has the hard-coat layer which consists of a cured film of Claim 8 on the surface.   The active energy ray-curable resin composition according to any one of claims 1 to 7 is applied to form a coating film, and the active energy ray is irradiated and cured without passing through the step of drying the coating film. The manufacturing method of the cured film which forms a film | membrane.