JP2019142164A - Layered body including cyclic olefin-based resin base material, and method for producing layered body including cyclic olefin-based resin base material - Google Patents

Abstract

To provide a layered body obtained by successively layering a cured coating layer of a curable resin composition and an inorganic substance layer on a cyclic olefin resin base material, the layered body having excellent interlaminar adhesiveness and exhibiting characteristics such as transparency, scratch resistance, hardness, and curl resistance.SOLUTION: In the layered body obtained by successively layering a cured coating layer (II) with an active energy ray curable composition and an inorganic substance layer (III) on a cyclic olefin-based resin base material (I), the active energy ray curable composition includes silica fine particles (A) having an average primary particle diameter within a range of 1 to 100 nm, a polymerizable unsaturated compound (B), and a photopolymerization initiator (C), and the content of the silica fine particles (A) is 30 to 85 mass% based on all the cured coating formation components of the active energy ray curable composition.SELECTED DRAWING: None

Description

  The present invention relates to a laminate comprising a cyclic olefin resin substrate, and more specifically, has excellent adhesion to the cyclic olefin resin substrate and is resistant to the substrate. The present invention relates to a laminate obtained by sequentially laminating a cured coating layer of an active energy ray-curable composition capable of imparting characteristics such as scratch resistance and an inorganic material layer, and a method for producing the same.

  In recent years, cyclic olefin-based resin films have been increasingly used as optical members for mobile phones, smartphones, liquid crystal displays and the like due to their high transparency and low hygroscopic functionality. Since the cyclic olefin resin film has a relatively low surface hardness, it is easily damaged. Therefore, a hard coat layer is provided on the film surface. However, the adhesion between the cyclic olefin resin film and the hard coat layer is not always sufficient. Therefore, before forming the hard coat layer, an easy adhesion treatment step such as applying a corona discharge treatment, a plasma treatment or an ozone treatment, an easy adhesion primer composition to the cyclic olefin resin film surface in advance was necessary ( Patent Document 1).

  Further, in Patent Document 2, a specific molecular weight range polyether diol, a polyisocyanate having no aromatic group and a hydroxyl group-containing (meth) acrylate reaction product of a specific molecular weight range urethane (meth) acrylate, a specific molecular weight range A composition for an active energy ray-curable optical material comprising a di (meth) acrylate, a compound having two phenyl skeletons and one (meth) acryloyl group, and a compound having one methacryloyl group has been proposed. However, the hard coat layer obtained from the composition sometimes has insufficient coating film hardness, scratch resistance, and adhesion to the cyclic olefin resin film.

  Furthermore, Patent Document 3 proposes a laminate comprising a layer made of a cyclic olefin resin and a layer made of a curable composition containing a diphenyl sulfide compound, a benzophenone compound, and a compound having a (meth) acryloyl group. However, the coating film hardness, scratch resistance, and interlayer adhesion may not be sufficient.

  On the other hand, an inorganic material layer is formed on a plastic substrate to impart mechanical, electrical, optical, or chemical functions. In this case, the plastic substrate and the inorganic material are provided. In order to ensure sufficient interlayer adhesion with a layer, it has been proposed to have a laminated structure in which a cured resin layer of a curable resin composition is interposed. For example, Patent Document 4 describes a surface-modified plastic plate for windows in which a cured film of an active energy ray-curable primer composition is formed on a plastic plate and an inorganic material layer is formed thereon. Yes. However, when the substrate is a cyclic olefin-based resin, the interlayer adhesion between the substrate and the cured resin layer and / or the interlayer adhesion between the resin cured layer and the inorganic material layer may not be sufficient. In some cases, the obtained laminate characteristics such as friction resistance and transparency are still not sufficient.

Special table 2008-518280 gazette JP 2008-249972 A JP2015-127102A JP-A-4-202240

  The present invention has been made in view of the above circumstances, and an object of the present invention is a laminate in which a cured coating layer and an inorganic material layer of a curable resin composition are sequentially laminated on a cyclic olefin resin substrate. And providing a laminate excellent in interlayer adhesion between the cyclic olefin resin substrate and the cured coating layer of the resin composition, and further, an interlayer between the cured coating layer of the resin composition and the inorganic substance layer. It is providing the laminated body which is excellent also in adhesiveness. A further object of the present invention is to provide a laminate that can exhibit excellent properties in terms of transparency, scratch resistance, hardness, curl resistance, and the like. The present invention further relates to a method for producing such a laminate.

  Under such circumstances, the present inventors have intensively studied, and as a result, an active energy ray-curable composition having a specific composition as a curable resin composition for forming a cured film on a cyclic olefin-based resin substrate. It has been found that the above problems can be solved by using a product.

The present invention includes the embodiments shown in the following sections:
Item 1
On the cyclic olefin-based resin substrate (I), a laminate comprising a cured coating layer (II) made of an active energy ray-curable composition and an inorganic substance layer (III) sequentially laminated,
The active energy ray-curable composition includes silica fine particles (A) having an average primary particle diameter in the range of 1 to 100 nm, a polymerizable unsaturated compound (B), and a photopolymerization initiator (C), The laminated body whose content of a silica fine particle (A) is 30-85 mass% on the basis of the total cured film formation component of the said active energy ray hardening-type composition.
Item 2
The laminate according to claim 1, wherein the silica fine particles (A) contain organic-modified silica fine particles having an unsaturated group.
Item 3
The laminate according to claim 1 or 2, wherein the polymerizable unsaturated compound (B) contains a polymerizable unsaturated compound (b1) having a urethane bond.
Item 4
The laminate according to any one of claims 1 to 3, wherein the film thickness of the cured coating layer (II) of the active energy ray-curable composition is in the range of 0.5 to 8 µm.
Item 5
The laminate according to any one of claims 1 to 4, wherein the cyclic olefin-based resin substrate (I) is not subjected to easy adhesion treatment.
Item 6
A method for producing a laminate,
Coating the active energy ray-curable composition on the cyclic olefin-based resin substrate (I) that has not been subjected to easy adhesion treatment, and forming a coating layer with the active energy ray-curable composition;
Irradiating the active energy ray curable composition with an active energy ray to form a cured coating layer (II) with the active energy ray curable composition;
Forming at least one inorganic substance layer (III) on the cured coating layer (II) by a dry film-forming method;
The active energy ray-curable composition comprises silica fine particles (A) having an average primary particle size in the range of 1 to 100 nm, a polymerizable unsaturated compound (B), and a photopolymerization initiator (C). A method for producing a laminate, wherein the content of the silica fine particles (A) is 30 to 85% by mass based on the total cured film forming component of the active energy ray-curable composition.

  According to the present invention, a laminate in which a cured film layer and an inorganic material layer of a resin composition are sequentially laminated on a cyclic olefin resin substrate, having sufficient interlayer adhesion, and further transparent In addition, it is possible to provide a laminate that can exhibit excellent properties in terms of scratch resistance, hardness, curl resistance, and the like.

  The laminate of the present invention has a structure in which a cured coating layer of a specific active energy ray-curable composition is formed on a cyclic olefin resin substrate, and an inorganic material layer is further laminated thereon.

<Cyclic olefin resin substrate (I)>
The laminate according to the present invention is based on a cyclic olefin resin. Although various cyclic olefin resin molded products can be used as the substrate, a cyclic olefin resin film is particularly preferable.

  The cyclic olefin resin film may be a homopolymer or a copolymer as long as it is a polymer of cyclic olefin, and can be used without any particular limitation. Examples of commercially available cyclic olefin resin films include “ZEONOR” manufactured by Zeon Corporation; “ARTON” manufactured by JSR Corporation; “TOPAS” manufactured by Polyplastics Corporation; “Appel” manufactured by Mitsui Chemicals, Inc. ”,“ F film ”manufactured by Gunze Co., Ltd., and the like.

In addition, the surface of the cyclic olefin resin film is usually subjected to surface roughening treatment by a sandblasting method, a solvent treatment method, etc. in order to improve the adhesion with the cured film of the active energy ray-curable composition, an electrical treatment (corona It is common to perform easy adhesion treatment such as discharge treatment, atmospheric pressure plasma treatment), chromic acid treatment, ozone / ultraviolet ray / electron beam irradiation treatment, oxidation treatment, and coating treatment with a primer composition. The energy ray curable composition has high adhesion to the cyclic olefin resin film without performing such easy adhesion treatment.
The thickness of the cyclic olefin resin film is preferably in the range of 50 to 200 μm, more preferably in the range of 80 to 150 μm, and still more preferably in the range of 90 to 130 μm. By setting the thickness of the film substrate within the above range, curling can be easily suppressed even when a hard coat layer made of the active energy ray-curable composition of the present invention is provided on one side of the cyclic olefin resin film.

<Hardened coating layer (II)>
The laminate according to the present invention comprises a cured coating layer (II) made of an active energy ray-curable composition having a specific composition on a cyclic olefin-based resin substrate (I). By adopting a laminated structure in which the cured coating layer (II) is disposed between the cyclic olefin-based resin substrate (I) and the inorganic substance layer (III), the cyclic olefin resin substrate (I) and the cured coating layer ( II) Adhesiveness between the cured coating layer (II) and the inorganic material layer (III) as well as interlayer adhesion with II), and also excellent in terms of friction resistance and transparency It is possible to provide a laminate that can exhibit the above characteristics. Hereinafter, the active energy ray-curable composition for forming the cured coating layer (II) will be described.

<< Active energy ray-curable composition >>
The active energy ray-curable composition used in the present invention comprises silica fine particles (A) having an average primary particle diameter in the range of 1 to 100 nm, a polymerizable unsaturated compound (B), and a photopolymerization initiator (C). including.

Silica particles (A)
The silica particles (A) used in the present invention have an average primary particle diameter in the range of 1 to 100 nm, and specifically include dry silica, wet silica, silica gel, calcium ion exchanged silica fine particles, colloidal silica, and the like. Can do.
The average primary particle diameter of the silica particles (A) is 1 to 100 nm, and from the viewpoint of the scratch resistance of the cured film, it is advantageous to use those having a relatively large average primary particle diameter. From the viewpoint of compatibility between the transparency and the transparency of the cured film, the range of 5 nm to 100 nm is preferable.
When the average primary particle size is less than 1 nm, when the silica particles (A) are mixed with other organic materials, the effect of improving the scratch resistance of the coating and the adhesion to the substrate may be reduced. is there. If the average primary particle diameter exceeds 100 nm, the transparency of the material may be impaired.

  The average primary particle diameter of the silica particles can be measured by particles observed with an electron microscope such as a transmission electron microscope (TEM). Or you may use the commercial item by which the specific particle diameter was displayed. In the present invention, the average primary particle diameter of the silica particles is taken with a transmission electron microscope, 20 particles on a straight line drawn at random are observed as primary particles, and the number average diameter of the maximum diameter is determined by image analysis. As a value obtained by calculating a measured value. At this time, when the silica particles were not circular, a diameter corresponding to a circle having the same area was obtained and used as the diameter of the silica particles.

  The silica particles (A) may be those whose surfaces are not modified with organic substances, but those containing organic substance-modified silica particles whose particle surfaces are modified with organic substances from the viewpoint of a balance between transparency and scratch resistance. What contains the organic substance modified silica which has a saturated group is preferable. The organic modification of the surface here means to be in the form of a complex in which an organic compound or an organic group is physically or chemically (preferably chemically) introduced to the surface of the silica particles. Examples of the organic compound or organic group to be introduced include those known in the art, and while maintaining the transparency of the coating obtained by active energy ray curing, the silica particle content is improved and the scratch resistance is excellent. It is preferable that it has an unsaturated group from the point which can obtain a film.

The unsaturated group means an unsaturated group capable of radical polymerization, and can react with the polymerizable unsaturated compound (B) described later. The unsaturated group capable of radical polymerization is a functional group having a carbon-carbon double bond (also called a polymerizable double bond), for example, vinyl group, (meth) acryloyl group, (meth) acrylamide group, A vinyl ether group, an allyl group, etc. can be mentioned, In this invention, a (meth) acryloyl group is especially preferable.
In the present specification, “(meth) acrylate” means acrylate or methacrylate, “(meth) acryloyl” means acryloyl or methacryloyl, and “(meth) acrylamide” means “acrylamide or methacrylamide”. means.

  The silica particles (A) may be dispersed in a dispersion medium. Examples of the dispersion medium include water; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, isobutanol, and n-butanol; ethylene Examples thereof include polyhydric alcohol solvents such as glycol; polyhydric alcohol derivatives such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diacetone alcohol. As the dispersion medium, water and / or a lower alcohol solvent having 3 or less carbon atoms are preferable.

  Commercially available colloidal silica includes methanol silica sol (average particle size 10-15 nm), MA-ST-M (average particle size 20-25 nm), IPA-ST (average particle size 10-15 nm), IPA-ST-L. (Average particle size 40-50 nm), IPA-ST-ZL (average particle size 70-100 nm), MEK-ST-40 (average particle size 10-15 nm), MEK-ST-L (average particle size 40-50 nm) MEK-ST-ZL (average particle size 70-100 nm), DMAC-ST (average particle size 10-15 nm), NPC-ST-30 (average particle size 10-15 nm), PGM-ST (average particle size 10-10 nm) 15 nm), EAC-ST (average particle size 10-15 nm), IPA-ST-UP (average particle size 9-15 nm), ST-UP (average particle size 40-100) m), ST-OUP (average particle size 40 to 100 nm), ST-20L (average particle size 40 to 50 nm), ST-30 (average particle size 10 to 15 nm), MEK-ST-40 (average particle size 10 to 10 nm) 15 nm), ST-O-40 (average particle size 20-25 nm), ST-N-40 (average particle size 20-25 nm), ST-C (average particle size 10-15 nm), ST-NS (average particle size) 8-11 nm), ST-O (average particle size 10-15 nm), ST-50 (average particle size 20-25 nm), ST-OL (average particle size 40-50 nm), MEK-AC-2140Z (average particle size) 10-15 nm), PGM-AC-2140Y (average particle size 10-15 nm), MEK-AC-4130Y (average particle size 40-50 nm), MEK-AC-5140Z (average particle size 70) 100nm) (all trade names, and the like is manufactured by Nissan Chemical Industries, Ltd.), and the like.

  The total content of the silica particles (A) is 30% by mass or more based on the total cured film forming component in the active energy ray-curable composition from the viewpoint of scratch resistance, curl resistance and adhesion. 40 mass% or more is preferable, 50 mass% or more is more preferable, and 55 mass% or more is particularly preferable. Moreover, from a transparency point, it is 85 mass% or less, 80 mass% or less is preferable and 70 mass% or less is more preferable. The film obtained from the active energy ray-curable composition used in the present invention is very excellent in transparency even when the content of the silica particles (A) is high, and has good adhesion to the substrate and scratch resistance. Also excellent.

Polymerizable unsaturated compound (B)
The polymerizable unsaturated compound (B) is a compound having one or more polymerizable unsaturated groups in the molecule. The polymerizable unsaturated group is an unsaturated group capable of radical polymerization, and specifically includes, for example, an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a maleimide group, and a vinyl ether group. Can be mentioned. Of these polymerizable unsaturated groups, an acryloyl group and a methacryloyl group are preferable, and an acryloyl group is particularly preferable from the viewpoint of excellent reactivity.

  The polymerizable unsaturated compound (B) may have an ester bond, a urethane bond, a urea bond, a thiourethane bond, or the like in the molecule, particularly from the viewpoint of scratch resistance and curling property. A polymerizable unsaturated compound (b1) having a urethane bond can be suitably used, and examples of the polymerizable unsaturated compound (b1) having a urethane bond include a urethane (meth) acrylate compound.

  The urethane (meth) acrylate compound particularly preferably used in the active energy ray-curable composition of the present invention has an unsaturated group equivalent of 110 or more and less than 600 and a weight average molecular weight of 600 to 6,000. Preferably there is. The urethane (meth) acrylate is a compound having at least one urethane bond and at least one (meth) acryloyl group in one molecule. From the viewpoint of excellent reactivity among the (meth) acryloyl groups. An acryloyl group is particularly preferred.

  In this specification, when the molecular weight of the compound having an unsaturated group is M and the number of unsaturated groups contained per molecular weight is σ, the unsaturated group equivalent is a value represented by M / σ.

The weight average molecular weight of the urethane (meth) acrylate is preferably in the range of 600 to 6,000, preferably in the range of 1,000 to 5,800, from the viewpoint of coating appearance, coating hardness, and flexibility. It is particularly preferred.
In this specification, the weight average molecular weight is the retention time (retention capacity) of a standard polystyrene having a known molecular weight measured under the same conditions as the retention time (retention capacity) measured using a gel permeation chromatograph (GPC). Is a value obtained by converting to a molecular weight of polystyrene. Specifically, “HLC-8120GPC” (trade name, manufactured by Tosoh Corporation) is used as a gel permeation chromatograph apparatus, and “TSKgel G4000HXL”, “TSKgel G3000HXL”, “TSKgel G2500HXL” and “TSKgel” are used as columns. G2000HXL "(trade name, all manufactured by Tosoh Corporation), using a differential refractometer as the detector, mobile phase: tetrahydrofuran, measurement temperature: 40 ° C, flow rate: 1 mL / min Can be measured below.

As the urethane (meth) acrylate, for example,
(1) reacting a polyisocyanate compound with a compound having a hydroxyl group and a (meth) acryloyl group;
(2) reacting an isocyanate group-containing (meth) acrylate monomer with a polyurethane polyol obtained by reacting a polyisocyanate compound and a polyol;
The reaction product manufactured by methods, such as these, are mentioned.

  Examples of the polyisocyanate compound used for the production of urethane (meth) acrylate include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, lysine diisocyanate, and isophorone diisocyanate. Arocyclic diisocyanate compounds such as 4,4′-methylenebis (cyclohexyl isocyanate), aromatics such as tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate Diisocyanate compounds, dimers or trimers of these diisocyanates (Biu Tsu DOO adducts or isocyanurate ring type adducts and the like) and the like.

  Examples of the compound having a hydroxyl group and a (meth) acryloyl group used for the production of urethane (meth) acrylate include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and 2-hydroxyethyl (meth). Acrylate, glycerol di (meth) acrylate, and alkylene oxide modified or lactone modified compounds obtained by adding ethylene oxide, propylene oxide, ε-caprolactone, γ-butyrolactone, etc. to these, and polyisocyanates to these compounds And the like can be mentioned.

  Examples of polyols used in the production of urethane (meth) acrylate include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, polycaprolactone diol, and polyester. Examples include polyols and polyether polyols.

  Examples of the isocyanate group-containing (meth) acrylate monomer include polyisocyanates such as hexamethylene diisocyanate and active hydrogen-containing polymerizable monomers such as isocyanate ethyl (meth) acrylate, isocyanate propyl (meth) acrylate, and hydroxyethyl (meth) acrylate. Examples include unsaturated compounds obtained by adding compounds.

Moreover, a commercial item can also be used as urethane (meth) acrylate. For example, the purple light series UV-1700B, UV-6300B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-7650B of Nippon Synthetic Chemical Industry Co., Ltd. Art resin series UN-3320HA, UN-3320HC, UN-3320HS, UN-904, UN-906S, UN-901T, UN-905, UN-952, EBECRYL series EBECRYL 4666, manufactured by Daicel Ornex Co., Ltd. EBECRYL4680, EBECRYL8210, EBECRYL1290, EBECRYL8254, KRM series KRM8528, KRM8200, KRM8200AE, KRM8904 can be mentioned.
Urethane (meth) acrylates can be used alone or in combination of two or more.

  As the polymerizable unsaturated compound (b2) other than the polymerizable unsaturated compound (b1) having a urethane bond, which is used as the polymerizable unsaturated compound (B) in the present invention, the polymerizable unsaturated compound (B2) is included in its chemical structure. It is a compound having at least one heavy bond, and the type thereof is not particularly limited as long as it does not inhibit the adhesion which is the subject of the present application, and examples thereof include monofunctional polymerizable unsaturated compounds and polyfunctional polymerizable unsaturated compounds.

  Examples of the monofunctional polymerizable unsaturated compound include esterified products of monohydric alcohol and (meth) acrylic acid. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, N-acryloyloxyethylhexahydro Examples include phthalimide. Moreover, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, etc. Carboxyl group-containing (meth) acrylate; Glycidyl group-containing polymerizable unsaturated compounds such as glycidyl (meth) acrylate and allyl glycidyl ether; Vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene; N , N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, nitrogen-containing alkyl (meth) acrylates such as Nt-butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N- Me Chill (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Polymerizable amide compounds such as N, N-dimethylaminopropyl (meth) acrylamide and N, N-dimethylaminoethyl (meth) acrylamide; N- (2-methacryloyloxyethyl) ethyleneurea, hydroxyethylethyleneurea (meth) acrylate And alkoxylated urea (meth) acrylates.

  Examples of the polyfunctional polymerizable unsaturated compound include esterified products of polyhydric alcohol and (meth) acrylic acid (polymerizable unsaturated compound having at least two ester bonds in the molecule; polyester (meth) acrylate). In some cases). Specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, tricycloden Di (meth) acrylates such as candimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, hydrogenated hexafluorobisphenol A di (meth) acrylate, etc. Compound: glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, ε-caprolactone modified tris (acrylic) Roxyethyl) isocyanurate and other tri (meth) acrylate compounds; pentaerythritol tetra (meth) acrylate and other tetra (meth) acrylate compounds; dipentaerythritol hexa (meth) acrylate; thiol compounds and isocyanato (meth) acrylates And (poly) thiourethane (meth) acrylate compounds and the like that have been used. These polymerizable unsaturated compounds can be used alone or in combination of two or more.

When the active energy ray-curable composition used in the present invention contains a polymerizable unsaturated compound (b1) having a urethane bond as the polymerizable unsaturated compound (B), the content is curl resistance and adhesion. When considering properties, scratch resistance, transparency, weather resistance, etc., the content is preferably 15% by mass or more based on the total cured film forming component in the active energy ray-curable composition.
When the active energy ray-curable composition used in the present invention contains a polymerizable unsaturated compound (b2) other than the polymerizable unsaturated compound (b1) having a urethane bond, its content takes into consideration curl resistance. When it does, it is preferable that it is less than 40 mass% with respect to all the cured film formation components in an active energy ray hardening-type composition.
That is, the polymerizable unsaturated compound (b1) having a urethane bond and the other polymerizable unsaturated compound (b2) are 100/0 to 0/100, in terms of curl resistance, 15/85 to 70/30. It can adjust suitably within the range.
Most preferably, the silica particle (A), the polymerizable unsaturated compound (b1) having a urethane bond, and a photopolymerization initiator are used for all the cured film forming components contained in the active energy ray-curable composition used in the present invention. The total mass of (C) is preferably 80% by mass or more.
Here, in this specification, the total cured film forming component in the active energy ray-curable composition used in the present invention is a residue (solid content) obtained by removing a solvent such as water or an organic solvent from the composition. It means the total mass.

Photopolymerization initiator (C)
The photopolymerization initiator (C) is a compound that absorbs active energy rays and generates free radicals (even in the form of an intermediate), and may be a mixture of two or more compounds. Photoinitiators (C) include photochemically activatable compounds (for example, benzoin), combinations of chromophores and coinitiators (for example, benzophenone and tertiary amines), mixtures thereof, sensitizers, Redox systems such as combinations of coinitiators (eg thioxanthone and tertiary amine) or chromophores (eg thioxanthone and aminoketone), combinations of H ₂ O ₂ and iron (II) salts, dyes and boron Examples thereof include electron transport pairs such as acid salts and / or amines.

  Specific examples of the photopolymerization initiator (C) include α-diketone compounds such as benzyl and diacetyl; acyloin compounds such as benzoin; acyloin ether compounds such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Thioxanthone compounds such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone, thioxanthone-4-sulfonic acid; benzophenone, o-methylbenzoylbenzoate, 4-methylbenzophenone, 4-phenylbenzophenone, 4,4′-bis (dimethyl) Benzophenone compounds such as amino) benzophenone and 4,4′-bis (diethylamino) benzophenone; Michler's ketone compound; acetophenone, 2- (4-toluenesulfonyloxy) 2-phenylacetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2 -Morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, α-isohydroxyisobutylphenone, α, α'-dichloro-4-phenoxyacetophenone Acetophenone compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (acyl) phosphine oxide; anthraquinone, 1 Quinones 4- naphthoquinone; phenacyl chloride, trihalomethyl phenyl sulfone, tris (trihalomethyl) -s-halogen compounds such as triazine; can be exemplified peroxides such as di -t- butyl peroxide.

Examples of commercially available photopolymerization initiators (C) include IRGACURE-127, IRGACURE-184, IRGACURE-261, IRGACURE-369, IRGACURE-500, IRGACURE-651, IRGACURE-754, IRGACURE-819, Irgacure-907, Irgacure-CGI-1700, Irgacure-2959, Irgacure-TPO, Darocur-1173 (above, trade name, manufactured by BASF); Kayacure-MBP, Kayacure-DETX-S, Kayacure- DMBI, Kayacure-EPA, Kayacure-OA (above, Nippon Kayaku Co., Ltd., trade name); Vicure-10, Vicure-55 (above, STAUFER Co Trigonal P1 (manufactured by Akzo Co., Ltd., trade name); Sandray 1000 (SANDORZ Co., LTD.) , Product name); Deep (DEAP) (manufactured by APJOHN Co., LTD., Product name); CantaCure-PDO, CantaCure-ITX, CantaCure-EPD (above, Ward Brekinsop (WARD) BLEKINSSOP Co., LTD., Trade name), ESACURE KIP 150, ESACURE ONE (LABMERTI, trade name), and the like.
The said photoinitiator (C) can be used individually or in combination of 2 types or more, respectively.

  Among these photopolymerization initiators (C), particularly preferred are benzophenone-based initiators and / or thioxanthone-based initiators (c1), benzoin-based, α-hydroxyacetophenone-based and acylphosphinesides. There may be mentioned at least one selected from (c2). In addition, initiators (c1) and (c2) can be suitably used even when combined, and when both are combined, it is preferable to use them in the range of 100/0 to 99/1 at a mass ratio of c1 / c2. The range of 99/1 to 70/30 is more preferable. By containing these initiators, the coating film obtained from the active energy ray-curable composition is particularly excellent in terms of adhesion to the cyclic olefin-based resin substrate and scratch resistance.

Suitable benzophenone initiators include, for example, benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, acrylated Benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 4, 4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone and the like can be mentioned.
Suitable examples of the thioxanthone initiator include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone.

Suitable benzoin initiators include benzoin, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzoin methyl ether (2-methoxy-2-phenylacetophenone), benzoin ethyl ether (2-ethoxy- Examples thereof include benzoin derivatives such as 2-phenylacetophenone), benzoin isopropyl ether (2-isopropoxy-2-phenylacetophenone), and benzoin isobutyl ether (2-isobutoxy-2-phenylacetophenone).
Preferred α-hydroxyacetophenone initiators are 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methylpropiophenone, and preferred acylphosphine oxide initiators are 2,4,6-trimethyl. Examples thereof include benzoyl-diphenyl-phosphine oxide and SpeedCure XKm (trade name: manufactured by Lambson).

In addition, the solid content of the photopolymerization initiator (C) in the active energy ray-curable composition used in the present invention is the silica particles (A) from the viewpoint of ensuring curability, coating hardness, and adhesion to the substrate. And it is in the range of 0.01-30 mass parts with respect to 100 mass parts of total solid content of the polymerizable unsaturated compound (B), More preferably, it exists in the range of 1-15 mass parts.
When the integrated irradiation amount of the active energy ray is 200 mJ / cm ² or less, the solid content of the photopolymerization initiator (C) is the sum of the silica particles (A) and the polymerizable unsaturated compound (B). The inside of the range of 10-30 mass parts is preferable with respect to 100 mass parts of solid content.

Other Components The active energy ray-curable composition used in the present invention may further contain various additives as necessary, and may be diluted with a solvent as required. Additives include, for example, ultraviolet absorbers, light stabilizers, antioxidants, rheology control agents, surface conditioners (silicon-based surface conditioners, acrylic-based surface conditioners, fluorine-based surface conditioners, vinyl-based surface conditioners. Etc.), surfactants, resin particles, lubricants, defoamers, mold release agents, silane coupling agents, antistatic agents, antifogging agents, colorants, and the like. The active energy ray-curable composition of the present invention may further contain an ultraviolet absorber and / or a light stabilizer for applications requiring light resistance.

Ultraviolet absorber As the above-mentioned ultraviolet absorber, conventionally known organic ultraviolet absorbers and inorganic ultraviolet absorbers can be used. For example, benzotriazole absorbers, triazine absorbers, salicylic acid derivative absorbers, benzophenone Examples include absorbents and other compounds (hydroxyphenyltriazine, oxalic anilide, cyanoacrylate, etc.). Examples of the inorganic ultraviolet absorber include fine particle titanium oxide, fine particle zinc oxide, and fine particle iron oxide. Moreover, the said ultraviolet absorber may have a polymerizable unsaturated group. When it contains the said ultraviolet absorber, content of this ultraviolet absorber is 0.01-10 mass% with respect to all the cured film formation components, Preferably it exists in the range of 0.05-9 mass%. Is preferred.

Light Stabilizer The light stabilizer is not particularly limited, and conventionally known light stabilizers can be widely used, and a hindered piperidine compound is preferable. A hindered piperidine compound is a compound having at least one hindered piperidine group in one molecule.
Examples of the hindered piperidine compound include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4- Benzoyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4 Monomer type such as -hydroxyphenyl] methyl} butylmalonate; poly {[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] Oligomeric tie such as [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) iminol]} Ones; 4-hydroxy-2,2,6,6-tetramethyl-1, but things like the polyester bond type such as a polyester product of piperidine ethanol and succinic acid, not limited thereto. A known polymerizable light stabilizer can also be used as the light stabilizer.

Commercially available products of the light stabilizer include, for example, TINUVIN 123, TINUVIN 152, TINUVIN 292 (trade name, manufactured by BASF), HOSTAVIN 3050, HOSTAVIN 3052, HOSTAVIN 3058 (trade name, manufactured by Clariant), Adeka Stab LA-82 (trade name, stock) The company ADEKA).
These can be used alone or in combination of two or more.
Moreover, when it contains the said light stabilizer, the content is 0.01-10 mass% with respect to all the cured film formation components, Preferably it is in the range of 0.05-9 mass%. It is.

  It is preferable to select the solvent as appropriate because it can adjust the solution viscosity of the active energy ray-curable composition of the present invention as appropriate, and can adjust the film thickness particularly when performing thin film coating. The organic solvent that can be used here is not particularly limited as long as it can dissolve or disperse the active energy ray-curable composition of the present invention. For example, aromatic hydrocarbons such as toluene and xylene; methanol and ethanol And alcohols such as isopropanol and t-butanol; esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. These solvents can be used alone or in combination of two or more.

Method for preparing active energy ray-curable composition The active energy ray-curable composition used in the present invention comprises the silica particles (A), polymerizable unsaturated compound (B), and photopolymerization initiator (C) described above. As an essential component, and additional components used as necessary can be mixed in a solvent and dissolved or dispersed.

<Inorganic substance layer (III)>
The inorganic substance layer (III) in the present invention is not particularly limited as long as it is formed by a dry film forming method, and can be selected according to the characteristics to be imparted to the laminate, for example, At least one or more kinds of various metals or metal oxides, nitrides and sulfides having elements such as Si, Ti, Zn, Al, Ga, In, Ce, Bi, Sb, B, Zr, Sn, and Ta. A layer having a main component can be mentioned. In addition, for example, a diamond-like carbon (hereinafter referred to as DLC) film layer having high hardness and excellent insulating properties may be used. The DLC film is a carbon film with an amorphous structure mainly composed of carbon-to-carbon SP3 bonds. It is a diamond-like carbon film that is extremely hard, has a low coefficient of friction, wear resistance, corrosion resistance, and gas barrier properties, and is excellent in insulation. is there.

  The inorganic material layer (III) in the present invention may be at least one or more layers. When the inorganic material layer (III) is a multilayer, the stacking order thereof and the type of the inorganic material layer (III) are not particularly limited. Further, the inorganic material layer (III) may be various functional layers such as an ultraviolet absorbing layer and a functional layer.

  Among these, the outermost inorganic substance layer (III) is a metal from the viewpoint of obtaining a surface layer having high hardness, interlayer adhesion with a cured coating layer, transparency of a laminated film, and excellent chemical stability. A layer made of an oxide, particularly a silicon oxide compound, is particularly preferable.

  When one layer of the inorganic material layer (III) is a DLC layer, it is preferable that the above metal oxide layer is laminated and then laminated as the outermost layer from the viewpoint of having the above performance.

  The method for laminating the inorganic material layer (III) in the present invention is not particularly limited as long as it is a dry film forming method. For example, resistance heating evaporation, electron beam evaporation, molecular beam epitaxy, ion beam deposition, ion plating, Physical vapor deposition methods such as sputtering (hereinafter also referred to as “PVD”) and chemical vapor deposition methods such as thermal CVD, plasma CVD, photo CVD, epitaxial CVD, atomic layer CVD, and catCVD (hereinafter also referred to as “CVD”). Among them, plasma CVD (Chemical Vapor Deposition) is particularly preferable from the viewpoint of film forming temperature and film forming speed. Here, the dry film-forming method is generally called a dry process by treating the material surface using a gas phase or a molten state.

  As the inorganic material layer (III), when a silicon oxide layer is formed by plasma CVD, an organic silicon compound can be suitably used as a raw material. Specific examples include tetraethoxysilane, hexamethyldisiloxane, trimethoxysilane, methyltriethoxysilane, 1,1,3,3-tetramethyldisiloxane, tetramethoxysilane, methoxytrimethylsilane, tetramethylsilane, Examples include hexamethyltrisiloxane, tetrachlorosilane, trichloromethylsilane, trimethylchlorosilane, dimethyldichlorosilane, and dimethylchlorosilane.

Further, when the DLC layer is formed by plasma CVD, a hydrocarbon compound is used as a raw material. Specific examples include toluene, acetylene, methane, hexane and the like.
When the inorganic material layer (III) is formed by the plasma CVD method, in addition to the raw material organic silicon compound and hydrocarbon compound, as a decomposition gas, hydrogen gas, methane gas, ozone gas, oxygen gas, carbon monoxide gas, carbon dioxide Carbon gas, nitrogen gas, nitrogen dioxide gas, dinitrogen monoxide gas, or the like is used. Among these, any one of oxygen gas, ozone gas, nitrogen dioxide gas, dinitrogen monoxide gas, dioxide gas, monoxide gas, or a combination of two or more thereof can be suitably used.

  Thus, various inorganic material layers (III) can be formed by appropriately selecting a raw material containing various metal raw materials and a decomposition gas, and raw materials for forming the inorganic material layer (III). May be used alone or in combination of two or more.

  In addition, the thickness of the inorganic material layer (III) is preferably 10 nm or more from the viewpoint of scratch resistance, and more preferably 20 nm or more for maintaining sufficient wear resistance. The upper limit of the thickness per layer of the inorganic material layer (III) is not particularly limited, but is preferably 5 μm or less, particularly preferably 2 μm or less. If the thickness of the inorganic material layer (III) is less than 10 nm, sufficient scratch resistance may not be exhibited. In order to adjust the thickness of the inorganic material layer (III), for example, the processing time or the like may be adjusted under the setting conditions of an apparatus such as plasma CVD. The inorganic material layer may be a plurality of layers.

The laminate according to the present invention has an excellent appearance, weather resistance, scratch resistance, and other properties not found in organic coatings, since the inorganic material layer laminated as described above is an inorganic substance, and also has an active energy. It can be excellent in interlayer adhesion with the cured coating layer (II) by the wire curable composition, and extremely excellent in weather resistance, water resistance and scratch resistance.
<Method for producing laminate>
The laminate according to the present invention comprises a step of coating an active energy ray-curable composition on the cyclic olefin-based resin substrate (I) to form a coating layer of the active energy ray-curable composition, and the active energy. A step of irradiating a coating layer made of a linear curable composition with active energy rays to form a cured coating layer (II) made of the active energy ray curable composition, and a dry film formation on the cured coating layer (II) And a step of forming at least one inorganic substance layer (III) by a construction method. Here, the active energy ray-curable composition includes silica fine particles (A) having an average primary particle diameter in the range of 1 to 100 nm, a polymerizable unsaturated compound (B), and a photopolymerization initiator (C). Content of the said silica fine particle (A) is 30-85 mass% on the basis of the total cured film formation component of the said active energy ray hardening-type composition.
According to the active energy ray-curable composition used in the present invention, although the silica fine particles are contained at a high concentration and the silica fine particles are densely packed in the layer, problems such as a decrease in transparency and cracking are caused. A cured film having excellent adhesion to both the inorganic material layer (III) and the cyclic olefin resin-based substrate (I) without causing any problems, and is not subjected to easy adhesion treatment. Even when an olefin-based resin base material is used, a laminated structure having excellent interlayer adhesion can be formed.

Coating process The method for coating the active energy ray-curable composition of the present invention is not particularly limited. For example, spray, rotary atomizer, dip coating, die coating, micro gravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, transfer coating, dip coating, spinner coating, wheeler coating, brush It can be applied by painting, solid coating by silk screen, wire bar coating, flow coating or the like. Electrostatic application may be performed during coating.

Coating thickness The coating thickness is usually 0.5 to 100 µm, preferably 0.5 to 8 µm, more preferably 1 to 7.8 µm in terms of cured thickness. The active energy ray-curable composition of the present invention can form a cured film excellent in sufficient adhesion with a substrate, transparency and scratch resistance, particularly in a thin film of 10 μm or less.

  In forming the cured coating layer (II) in the present invention, the active energy ray-curable composition is applied onto the substrate, and after setting and / or preheating, the active energy ray is irradiated. Also good. This step of setting and / or preheating is performed in order to reduce or remove volatile components in the coating immediately after coating, and can be performed by an air blow, an IR furnace, or the like. The setting can be usually performed by leaving the coated article to stand in a dust-free atmosphere for 30 seconds to 600 seconds at room temperature. Preheating (preheating) can be usually performed by heating the coated article in a drying furnace at a temperature of 40 to 110 ° C., preferably 50 to 100 ° C. for 30 seconds to 30 minutes. Moreover, when performing an air blow, it can carry out by spraying the air heated to normal temperature or the temperature of 25 to 80 degreeC normally to the coating surface of a to-be-coated article. The preheating time can be preferably 30 seconds to 600 seconds. Moreover, when performing heating and active energy ray irradiation mentioned later together, it is good also considering the heat (for example, the heat | fever which a lamp | ramp emits) from the irradiation source of a light ray as a heat source. Further, when light irradiation is performed after heating, the light irradiation may be performed in a state where the object to be coated is heated (a state having residual heat).

Active energy ray irradiation The coating applied to the substrate can be polymerized by irradiation with active energy rays to form a cured coating. A well-known thing can be used as an active energy ray irradiated. Specific examples include ultraviolet light, visible light, laser light (near infrared laser, visible light laser, ultraviolet laser, etc.), microwave, electron beam, electromagnetic wave, and the like. Of these active energy rays, ultraviolet rays can be suitably used from the viewpoint of economy.

A well-known thing can be used as an irradiation source of an active energy ray. Specifically, for example, ultra high pressure, high pressure, medium pressure, low pressure mercury lamp, electrodeless lamp, chemical lamp, carbon arc lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, LED (Light Emitting Diode), light emitting diode ), Sunlight, etc. can be used. In addition, a pulsed emission type active energy ray irradiation apparatus can also be used.
In addition, the irradiation with active energy rays may be performed on the entire region and / or part of the region through, for example, a mask or a laser beam. It is also possible to cure the coating only in a specific area by the means.
The irradiation amount of the active energy ray varies depending on the irradiation source, but may be within a range where the active energy ray-curable composition can be polymerized. For example, when a high-pressure mercury lamp is used, the integrated irradiation amount is 100 to 500 mJ. / Cm ² , particularly preferably in the range of 200 to 500 mJ / cm ² .
Formation of Inorganic Material Layer (III) The inorganic material layer (III) can be formed by a dry film forming method as described in <Inorganic material layer (III)>.

  Since the laminate according to the present invention has a laminated structure in which a cured coating layer and an inorganic material layer of a specific active energy ray-curable composition are sequentially laminated on a cyclic olefin resin substrate, sufficient interlayer adhesion is achieved. And can exhibit excellent properties in terms of friction resistance and transparency. In addition, the laminated inorganic material layer can impart various properties such as excellent appearance, weather resistance, and scratch resistance that are not found in organic coatings.

  Hereinafter, the present invention will be described in more detail with reference to production examples and examples. However, the present invention is not limited to these. In each example, “parts” and “%” indicate “parts by mass” and “mass%” unless otherwise specified.

(Production Example 1) Active energy ray-curable composition No. 1
Silica fine particles No. 1 (* 1) 150 parts (solid content 60 parts), polymerizable unsaturated compound No. 1 40 parts (solid content 40 parts) (* 5), DETX (* 10) 6.0 parts as photopolymerization initiator, DAROCURE 1173 (* 14) 0.8 parts in solids, BYK-354 ( * 15) (trade name, acrylic surface conditioning agent) 0.10 parts by solid content, TINUVIN 1130 (* 16) as solid UV absorber 0.20 parts by solid content, and HOSTAVIN 3052 as light stabilizer (* 17) is mixed with 0.20 part of solid content, diluted with ethyl acetate to a solid content of 40% and stirred. 1 was produced. Table 1-1 shows the blending amount of each component in terms of solid content mass ratio. The silica particle content in the table is mass% based on the total cured film forming component of the active energy ray-curable composition.

(Production Examples 2-28) Active energy ray-curable composition No. 2-28
In Production Example 1, active energy ray curing with a solid content of 40% in Production Examples 2 to 28 is the same as Production Example 1 except that the composition of each component is shown in Tables 1-1 to 1-3. Mold composition No. 2 to 28 were obtained. The composition of each composition shown in Tables 1-1 to 1-3 is the solid content mass ratio of each component.

(* 1) to (* 17) in Table 1-1 to Table 1-3 mean the following.
(* 1) Silica fine particles No. 1: MEK-ST-40, trade name, manufactured by Nissan Chemical Co., Ltd., MEK-ST40, trade name, manufactured by Nissan Chemical Industries, colloidal silica, average primary particle size 13 nm, methyl ethyl ketone dispersion, solid content 40% by mass
(* 2) Silica fine particles No. 2: Organic matter-modified silica fine particle dispersion having an unsaturated group obtained by the following production method, average primary particle size 23 nm, solid content 40% by mass; Production method 2> Colloidal silica (Snowtex ST-O-40; trade name, dispersion medium; water, silica concentration; 40% by mass, average primary particle diameter) in a separable flask equipped with a reflux condenser, a thermometer and a stirrer 23 parts, manufactured by Nissan Chemical Industries, Ltd.) 250 parts (silica fine particle amount is 100 parts), 3-methacryloyloxypropyltrimethoxysilane 10 parts, p-methoxyphenol 0.2 parts and isopropanol 143 parts The temperature was increased while stirring. When the reflux of volatile components began, propylene glycol monomethyl ether was added and azeotropically distilled to replace the solvent in the reaction system. Subsequently, the reaction was carried out with stirring at 95 ° C. for 2 hours, then the temperature was lowered to 60 ° C., 0.03 part of a quaternary ammonium salt was added, and the reaction was further carried out with stirring for 1 hour. After completion of the reaction, volatile components were distilled off under reduced pressure, and propylene glycol monomethyl ether was further added for azeotropic distillation. The operation of adding propylene glycol monomethyl ether and performing azeotropic distillation several times was performed to replace the solvent. 2 was obtained. The obtained silica fine particles No. 2 has an average primary particle size of 23 nm, The solid content of the dispersion liquid 2 was 40% by mass.

(* 3) Silica fine particles No. 3: MEK-ST-ZL, trade name, manufactured by Nissan Chemical Industries, colloidal silica, average primary particle size 85 nm, methyl ethyl ketone dispersion, solid content 30 quality,
(* 4) Silica fine particles No. 4: <Silica fine particle No. 2), except that the colloidal silica is Snowtex MP-2040 (trade name, dispersion medium: water, silica concentration: 40 mass%, average primary particle size: 200 nm, manufactured by Nissan Chemical Industries, Ltd.). An organic-modified silica fine particle dispersion having an unsaturated group, an average primary particle size of 200 nm, and a solid content of 40% by mass were obtained.
(* 5) Polymerizable unsaturated compound No. 1: KARAYAD-DPHA, trade name, manufactured by Nippon Kayaku Co., Ltd., average polymerizable unsaturated group number 6, molecular weight 524, dipentaerythritol hexaacrylate,
(* 6) Polymerizable unsaturated compound No. 2: EBECRYL 884, trade name, Daicel Ornex Co., Ltd., average polymerizable unsaturated group number 3, weight average molecular weight 1,250, esterified product of polyhydric alcohol and acrylic acid (polyester acrylate),
(* 7) Polymerizable unsaturated compound No. 3: Aronix M-325, trade name, manufactured by Toagosei Co., Ltd., 3 average polymerizable unsaturated groups, weight average molecular weight 538, ε-caprolactone-modified tris (acryloxyethyl isocyanurate, urethane acrylate (* 8) non-polymerizable Saturated compound No. 4: urethane acrylate, average number of polymerizable unsaturated groups of 9, weight average molecular weight of 3,700,
(* 9) Polymerizable unsaturated compound No. 5: Urethane acrylate, average number of polymerizable unsaturated groups of 10, weight average molecular weight 4,900,
(* 10) DETX: photopolymerization initiator (a1), 2,4-diethylthioxanthen-9-one, thioxanthone-based initiator,

(* 11) IRGACURE 651: Photopolymerization initiator (a2), trade name, manufactured by BASF, benzoin-based initiator, 2,2-dimethoxy-1,2-diphenylethane-1-one (* 12) IRGACURE TPO: Photopolymerization initiator (a2), trade name, manufactured by BASF, acylphosphine oxide-based initiator, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
(* 13) IRGACURE 184: Photopolymerization initiator (a2), trade name, manufactured by BASF, α-hydroxyacetophenone-based initiator, 1-hydroxycyclohexyl phenyl ketone,
(* 14) DAROCURE 1173: Photopolymerization initiator (a2), trade name, manufactured by BASF, α-hydroxyacetophenone initiator, 2-hydroxy-2-methylpropiophenone,
(* 15) BYK-354: BYK-354: trade name, manufactured by Big Chemie Japan, acrylic surface conditioner, solid content 51% by mass
(* 16) TINUVINE 1130: trade name, manufactured by BASF, ultraviolet absorber, benzotriazole, solid content 88% by mass,
(* 17) HOSTAVINE 3052: trade name, manufactured by Clariant Japan, a hindered piperidine light stabilizer.

<Method for producing laminate>
(Examples and Comparative Examples)
In the base material 1 (cyclic olefin resin base material: COP base material (I), indicated as COP in the table), the active energy ray-curable composition No. 1 was coated with a bar coater under the condition that the film thickness was 4 μm, preheated at 100 ° C. for 30 seconds to remove the solvent, and then irradiated with ultraviolet rays (peak top wavelength 365 nm) with an irradiance of 150 mW / cm with an ultraviolet irradiation device. ² was applied under the condition that the cumulative irradiation amount was 500 mJ / cm ^2, and the coating was cured to produce a cured coating layer (II). Next, an inorganic material layer (III) shown in Table 2-1 was laminated thereon using a plasma CVD apparatus so as to have a film thickness of 1.5 μm (Example 1). Similarly, the test laminated bodies of Examples 2-31 and Comparative Examples 1-4 shown in Table 2-1 to Table 2-3 and Table 3 were obtained. About each obtained test laminated body, it used for the following evaluation test. The evaluation results are shown in Tables 2-1 to 2-3 and Table 3.

The substrate 1 used the following.
Base material 1: A4 size 100 μm thick cyclic olefin resin base material (“ZEONOR FILM, ZF16-100”, trade name, manufactured by Nippon Zeon Co., Ltd., haze value less than 0.1%, total light transmittance 92% Above, pencil hardness HB].
Further, instead of the base material 1, a base material 2 (polyethylene terephthalate resin base material: PET base material, expressed as PET in the table) and coated on a non-easy-adhesion treated surface is referred to as Reference Example 1 and is easy to adhere. Laminated bodies were respectively prepared as Reference Example 2 by coating the treated surface. Each obtained laminate was used as a test plate for various tests as in Example 1.
The base material 2 used the following.
Base material 2: A4 size polyethylene terephthalate film having a thickness of 100 μm (“Cosmo Shine A4100” trade name, manufactured by Toyobo Co., Ltd., haze value 0.9%, total light transmittance 92.0%).

Test item 1. Transparency Based on JIS K7361-1 (1997), the total light transmittance of each obtained laminate was measured from the inorganic layer (III) side. Moreover, based on JISK7136 (2000), the haze value of the laminated body was similarly measured from the inorganic layer (III) side. Evaluation was performed according to the following criteria. If the total light transmittance is 91.0% or more and the haze value is 5% or less, the transparency is good.
<Total light transmittance>
3: 91% or more,
2: 90% or more and less than 91% 1: less than 90%,
<Haze value>
3: Less than 0.5% 2: More than 0.5% and less than 5% 1: More than 5%

Test item 2. Adhesiveness Make 100 1mm x 1mm goby meshes according to JIS K 5600-5-6 (1990) on the inorganic layer (III) surface of each test plate until it reaches the substrate, and attach adhesive tape to the surface Then, the remaining state and peeling interface of the goby eye coating after abrupt peeling were examined, and the adhesion was evaluated according to the following criteria.
5: Remaining number / total number = 100/100, no missing edges,
4: Remaining number / total number = 95 to 100/100, and there is a lack of edges,
3: Remaining number / total number = 90 to less than 95/100, with missing edges,
2: Remaining number / total number = 80 to less than 90/100 with missing edges,
1: Remaining number / total number = 79 or less / 100 missing edges.

Test item 3. Pencil hardness In accordance with JIS K 5600-5-4, the surface of the inorganic layer (III) of each laminate was gradually increased in hardness at a 45 degree angle and a load of 750 g with respect to the surface. The hardness of the hardest pencil that did not occur is evaluated as the pencil hardness. A pencil hardness F or higher is considered good.

Test item 4. Scratch resistance Steel wool method: Commercial steel wool (# 0000) was rubbed 50 times with a load of 1000 g on the inorganic layer (III) surface of each test plate, and the surface of the laminate was visually observed and evaluated according to the following criteria. Since scratch resistance is good, the number of scratches was evaluated.
5: No crack, no peeling, or no scratch,
4: There is no crack, no peeling, or the number of scratches is less than 5.
3: No cracking or peeling, or 5 or more and less than 10 scratches are recognized, but no problem in practical use 2: No cracking, peeling, or 10 or more but less than 20 scratches are recognized,
1: Cracking, peeling, or significant scratches are observed.

Test item 5. Curl resistance The center part of each laminate was cut into 10 cm squares to prepare test samples. In the evaluation, the warpage of the four corners was measured with a ruler, and the total of the four points was taken as the curl value in the test sample.
4: less than 5 mm,
3: 5 mm or more and less than 20 mm,
2: 20 mm or more and less than 50 mm,
1: 50 mm or more.

Claims (6)

On the cyclic olefin-based resin substrate (I), a laminate comprising a cured coating layer (II) made of an active energy ray-curable composition and an inorganic substance layer (III) sequentially laminated,
The active energy ray-curable composition includes silica fine particles (A) having an average primary particle diameter in the range of 1 to 100 nm, a polymerizable unsaturated compound (B), and a photopolymerization initiator (C), The laminated body whose content of a silica fine particle (A) is 30-85 mass% on the basis of the total cured film formation component of the said active energy ray hardening-type composition.   The laminate according to claim 1, wherein the silica fine particles (A) contain organic-modified silica fine particles having an unsaturated group.   The laminate according to claim 1 or 2, wherein the polymerizable unsaturated compound (B) contains a polymerizable unsaturated compound (b1) having a urethane bond.   The laminate according to any one of claims 1 to 3, wherein the film thickness of the cured coating layer (II) of the active energy ray-curable composition is in the range of 0.5 to 8 µm.   The laminate according to any one of claims 1 to 4, wherein the cyclic olefin-based resin substrate (I) is not subjected to easy adhesion treatment. A method for producing a laminate,
Coating the active energy ray-curable composition on the cyclic olefin-based resin substrate (I) that has not been subjected to easy adhesion treatment, and forming a coating layer with the active energy ray-curable composition;
Irradiating the active energy ray curable composition with an active energy ray to form a cured coating layer (II) with the active energy ray curable composition;
Forming at least one inorganic substance layer (III) on the cured coating layer (II) by a dry film-forming method;
Including
The active energy ray-curable composition includes silica fine particles (A) having an average primary particle diameter in the range of 1 to 100 nm, a polymerizable unsaturated compound (B), and a photopolymerization initiator (C), The content of the silica fine particles (A) is 30 to 85% by mass based on the total cured film forming component of the active energy ray-curable composition,
A manufacturing method of a layered product.