KR102030996B1 - Uv-curable resin composition, and laminate using same - Google Patents

Abstract

An object of the present invention is to provide an ultraviolet curable resin composition excellent in a blue light cut function. The ultraviolet curable resin composition of this invention is (A): polyfunctional (meth) acrylate, (B): photoinitiator, (C): compound which has naphthalimide frame | skeleton, and / or compound which has perylene frame | skeleton It is the ultraviolet curable resin composition containing the blue light absorbent containing and whose quantity of the said (C) component is 0.7-2.0 mass% of a non volatile component.

Description

UV curable resin composition and laminated body using the same {UV-CURABLE RESIN COMPOSITION, AND LAMINATE USING SAME}

The present invention relates to an ultraviolet curable resin composition and a laminate using the same.

In recent years, artificial light sources such as LEDs of liquid crystal displays and the like that have been widely used emit light having a wavelength of around 385 to 495 nm, so-called blue light. Blue light may cause symptoms in a person, such as stable fatigue or dry eyes; Hypofunction of the retina; It has been pointed out that the body's clock has been adversely affected because it suppresses the secretion of melatonin which promotes sleep.

Moreover, the near-infrared absorption film which has a near-infrared absorption layer is provided in the surface of an electronic image display apparatus. Since the infrared absorbing dye contained in the near-infrared absorbing layer is generally decomposed by ultraviolet rays contained in sunlight, a benzotriazole-based ultraviolet absorber is used to suppress this (for example, Patent Document 1).

Patent Document 1: Japanese Unexamined Patent Publication No. 2009-6513

However, the present inventors have found that ultraviolet absorbers such as the conventional benzotriazole-based have low blue light cut function.

Then, an object of this invention is to provide the ultraviolet curable resin composition excellent in a blue light cut function.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching that the said subject should be solved, the ultraviolet curable resin composition containing the compound which has a naphthalimide frame | skeleton and / or the compound which has a perylene frame | skeleton as a blue light absorber is blue-light cut. It found the outstanding thing in the function, and completed this invention.

That is, this invention is as follows.

1. The ultraviolet curable resin composition containing following (A)-(C) component, and the quantity of the said (C) component is 0.7-2.0 mass% of a non volatile component.

(A): polyfunctional (meth) acrylate

(B): photoinitiator

(C): A blue light absorbent containing at least one of a compound having a naphthalimide skeleton and a compound having a perylene skeleton

2. The ultraviolet curable resin composition according to the above 1, wherein the (C) component further contains a compound having a benzotriazole skeleton.

3. 자외선 The ultraviolet curable resin composition according to the above 1 or 2, wherein the component (C) contains at least a compound having a perylene skeleton.

4. The quantity of at least any one of the compound which has the said naphthalimide skeleton, and the compound which has the said benzotriazole skeleton with respect to 1.0 mass part of compounds which have the said perylene skeleton in said 3 is 0.0-50.0 mass Mrs. UV curable resin composition.

5. The ultraviolet curable resin composition according to the above 1, wherein the (C) component is only a compound having a naphthalimide skeleton.

6. The ultraviolet curable resin composition in any one of said 1, 2, 5 containing (D): silica further.

7. The ultraviolet curable resin composition in any one of said 1, 2, 5 containing a solvent further.

8. The ultraviolet curable resin composition as described in any one of said 1, 2, 5 which does not contain an infrared absorber.

9. Laminated body which has a film and the cured film obtained using the ultraviolet curable resin composition of said 1 on the said film.

10. The laminated body of said 9 obtained through the process of coating the ultraviolet curable resin composition in any one of said 1, 2, 5 on a film, drying, and irradiating an ultraviolet-ray.

11. The laminate according to 9, which is used for an electronic image display device.

The ultraviolet curable resin composition of this invention is excellent in a blue light cut function.

The laminated body of this invention is excellent in a blue light cut function.

1: is sectional drawing which shows an example of the laminated body of this invention typically.
2 is a graph showing the UV-visible light absorption spectrum of the laminate.

The present invention will be described in detail below.

The ultraviolet curable resin composition (composition of the present invention) of the present invention,

It is an ultraviolet curable resin composition containing following (A)-(C) component and the quantity of the said (C) component is 0.7-2.0 mass% of a non volatile component.

(A): polyfunctional (meth) acrylate

(B): photoinitiator

(C): Blue light absorbent containing a compound having a naphthalimide skeleton and / or a compound having a perylene skeleton

The composition of this invention has the characteristic which absorbs the light of 385 (+/- 5)-495 (+/- 5) nm area | region, so-called blue light, by containing (C) component. A compound having a naphthalimide skeleton and a compound having a perylene skeleton can absorb blue light and emit light as light in another region.

Moreover, the composition of this invention is high in the hardness of the hardened film obtained by containing (A) component, and is excellent in adhesiveness with respect to a base material.

In addition, in this invention, (A) component may only be called (A). The same applies to the component (B), the component (C) and the component (D).

(A): A polyfunctional (meth) acrylate is demonstrated below.

(A) contained in the composition of this invention will not be restrict | limited especially if it is a compound which has 2 or more of (meth) acryloyloxy groups.

Here, as referring to "(meth) acryloyloxy group with an acrylic" refers to acrylic acryloyloxy group (CH ₂ = CHCOO-) acryloyloxy group or a methacryloyloxy (CH ₂ = C (CH ₃₎ COO-), and "( Methacrylate "means acrylate or methacrylate.

The (meth) acryloyloxy group can be bonded to an organic group. As an organic group, the hydrocarbon group which may have a hetero atom, such as an oxygen atom, a nitrogen atom, and a sulfur atom, is mentioned, for example. As a hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, these combinations are mentioned, for example. The hydrocarbon group may include a straight chain or branched phase and may have an unsaturated bond.

It is preferable that (A) has 4-12 (meth) acryloyloxy groups from a viewpoint that the hardness of a cured film is high and is excellent in adhesiveness with respect to a base material.

As a polyfunctional (meth) acrylate, the (meth) acrylic acid ester of a polyhydric alcohol and urethane (meth) acrylate are mentioned, for example.

As a (meth) acrylic acid ester of polyhydric alcohol, For example, trifunctional systems, such as a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, and dipentaerythritol tri (meth) acrylate; Tetrafunctional systems such as pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and tripentaerythritol tetra (meth) acrylate; Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, And 5-functional or higher functional systems such as tripentaerythritol octa (meth) acrylate.

As a urethane (meth) acrylate, the (meth) acrylic acid ester of a polyhydric alcohol (for example, the thing which has at least 1 hydroxyl group as a (meth) acrylic acid ester of a polyhydric alcohol is mentioned in this case, for example). And a reactant with a polyisocyanate compound.

As a (meth) acrylic acid ester of the polyhydric alcohol used when manufacturing urethane (meth) acrylate, the same thing as the above is mentioned, for example.

As a polyisocyanate compound used when manufacturing a urethane (meth) acrylate, For example, tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylene diisocyanate, Aromatic polyisocyanates such as tetramethylxylene diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; Hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis (isocyanatemethyl) cyclohexane, dicyclohexylmethane di Aliphatic polyisocyanates such as isocyanates (including chain and / or alicyclic systems); These isocyanurate bodies, biuret bodies, and adduct bodies; And urethane prepolymers.

Polyisocyanate compounds for forming the urethane prepolymer are as described above. The polyol for forming the urethane prepolymer is not particularly limited. For example, polyoxyalkylene polyols, such as a polypropylene polyol, etc. are mentioned.

(A) A component is (meth) acryl in one molecule like dipentaerythritol hexa (meth) acrylate and pentaerythritol tri (meth) acrylate from a viewpoint that hardness is high and excellent in adhesiveness and an optical characteristic especially, The compound which has 3-6 loyloxy groups is preferable.

(A) component can be used individually or in combination of 2 types or more, respectively.

When (meth) acrylic acid ester of polyhydric alcohol and urethane (meth) acrylate are used together as (A) component, from a viewpoint that hardness is high, and it is excellent in adhesiveness and an optical characteristic, it is the (meth) acrylic acid ester of polyhydric alcohol, It is preferable that urethane (meth) acrylate is 1-200 mass parts, and, as for the quantity ratio of urethane (meth) acrylate, with respect to 100 mass parts of (meth) acrylic acid esters of a polyhydric alcohol, it is more preferable that it is 10-100 mass parts. Do.

The component (A) is not particularly limited with respect to its preparation. For example, a conventionally well-known thing is mentioned.

(B): A photoinitiator is demonstrated below. (B) contained in the composition of this invention will not be specifically limited if it can superpose | polymerize (A) by light. As a photoinitiator (B), an acetophenone type compound, a benzoin ether type compound, a benzophenone type compound, a sulfur compound, an azo compound, a peroxide compound, a phosphine oxide type compound, etc. are mentioned, for example. Specifically, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, Diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl Carbonyl compounds such as -1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one and 1-hydroxycyclohexylphenyl ketone; Sulfur compounds such as tetramethyl thiuram monosulfide and tetramethyl thiuram disulfide; Azo compounds such as azobisisobutyronitrile and azobis-2,4-dimethylvalero; Peroxide compounds, such as a benzoyl peroxide and di-t- butyl peroxide, etc. are mentioned.

Among them, 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1- from the viewpoints of light stability, high efficiency of light cleavage, surface hardenability, compatibility, low volatility and low odor. Phenyl-propan-1-one and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one are preferred.

(B) can be used individually or in combination of 2 types or more, respectively.

It is preferable that it is 0.5-12 mass parts with respect to 100 mass parts of (A), and, as for the quantity of (B), it is more preferable that it is 3-9 mass parts.

(C) component is demonstrated below. The component (C) contained in the composition of the present invention is a blue light absorbent containing a compound having a naphthalimide skeleton and / or a compound having a perylene skeleton.

The compound having a naphthalimide skeleton is not particularly limited. The naphthalimide skeleton may have a substituent. The naphthalimide skeleton is represented by the following formula.

The nitrogen atom in the said formula is a hydrogen atom, for example; It can combine with the hydrocarbon group which may have a hetero atom, such as an oxygen atom, a nitrogen atom, and a sulfur atom. The hydrocarbon group is as above.

As a commercial item of the compound which has a naphthalimide frame | skeleton, Lumogen F Violet 570 (made by BASF Corporation) is mentioned, for example.

Since the compound which has a naphthalimide frame | skeleton can absorb the low wavelength side area | region (385-420 nm) among blue light, and is excellent in transparency, it is preferable.

When (C) is only a compound which has a naphthalimide frame | skeleton, it is preferable because it is excellent in a blue light cut function, and since the color of a cured film does not have a yellowish color, it is excellent in transparency.

The compound having a perylene skeleton is not particularly limited. The perylene skeleton may have a substituent. The perylene skeleton is represented by the following formula.

As a commercial item of the compound which has a perylene skeleton, Lumogen F Yellow 083 (made by BASF Corporation) is mentioned, for example.

The compound having a perylene skeleton can absorb a region (420 to 495 nm) on the longer wavelength side than the compound having a naphthalimide skeleton among the blue light.

The component (C) may further contain a compound having a benzotriazole skeleton. The compound having a benzotriazole skeleton is not particularly limited. The benzotriazole skeleton may have a substituent. The benzotriazole skeleton is represented by the following formula.

The nitrogen atom of the 2nd position in the said formula is a hydrogen atom, for example; It can combine with the hydrocarbon group which may have a hetero atom, such as an oxygen atom, a nitrogen atom, and a sulfur atom. The hydrocarbon group is as above.

As a commercial item of the compound which has a benzotriazole skeleton, Tinuvin Carbo protect (made by BASF Corporation) is mentioned, for example.

The compound having a benzotriazole skeleton can absorb light having a wavelength of 220 to 430 nm.

It is preferable that (C) contains at least the compound which has a perylene skeleton from a viewpoint of being excellent in a blue light cut function. In this case, it is 0.0-50.0 mass parts for the quantity of the compound which has a naphthalimide skeleton, and / or the compound which has a benzotriazole skeleton with respect to 1.0 mass part of compounds which have a perylene skeleton from the same reason as above. It is preferable and it is more preferable that it is 1.0-45.0 mass parts.

Here, "the amount of the compound which has a naphthalimide skeleton and / or the compound which has a benzotriazole skeleton" means either the compound which has a naphthalimide skeleton as a (C) component, and the compound which has a benzotriazole skeleton In the case of using a compound of the above, the content of the compound is used, and in the case of using both a compound having a naphthalimide skeleton and a compound having a benzotriazole skeleton as the component (C), the total amount of these compounds is meant. .

In this invention, the quantity of (C) component is 0.7-2.0 mass% of the quantity of the non volatile component contained in the composition of this invention from a viewpoint of being excellent in a blue light cut function, and being excellent in transparency and solubility.

Here, a "non-volatile component" means the component which does not volatilize when heated at 105 degreeC for 1 hour under normal pressure, and it is the thing of (A), (B), and (C) which are contained in the composition of this invention. When it contains non-volatile components and additives, such as (D) silica and filler which are optional components mentioned later, the component which also contains these non-volatile components is said.

In this case, it is preferable that the quantity of (A) component is 60-98 mass% of the quantity of the said non volatile component from a viewpoint that it is excellent in a blue light cut function, the hardness of a cured film is high, and is excellent in adhesiveness, It is more preferable that it is 80-95 mass%.

It is preferable that it is 0.5-12 mass% of the quantity of the said non volatile component from a viewpoint that the quantity of (B) component is more excellent in a blue light cut function, the hardness of a cured film is high, and is excellent in curability, and it is 2-8 It is more preferable that it is mass%.

It is preferable that the quantity of (C) component is 1.0-2.0 mass% of the quantity of the said nonvolatile component from a viewpoint that it is excellent in a blue light cut function, excellent in transparency and solubility, and does not impair adhesiveness.

When the composition of this invention contains (D) silica further mentioned later, the quantity of (A) component is more excellent in a blue light cut function, the hardness of a hardened film is high, and it is the said non-fluorescence from a viewpoint that it is excellent in adhesiveness. It is preferable that it is 60-98 mass% of the quantity of a foot component, and it is more preferable that it is 75-90 mass%.

It is preferable that it is 0.5-12 mass% of the quantity of the said non volatile component from a viewpoint that the quantity of (B) component is more excellent in a blue light cut function, the hardness of a cured film is high, and is excellent in curability, and it is 2-8 It is more preferable that it is mass%.

It is preferable that the quantity of (C) component is 1.0-2.0 mass% of the quantity of the said nonvolatile component from a viewpoint that it is excellent in a blue light cut function, excellent in transparency and solubility, and does not impair adhesiveness.

The amount of component (D) is from 1 to 20% by mass of the amount of the nonvolatile component, from the viewpoint of being excellent in anti-blocking properties, recoat properties, and adhesion workability in the next step. It is preferable that it is and it is more preferable that it is 5-15 mass%.

It is preferable that the composition of this invention contains (D): silica further from a viewpoint of being excellent in the anti-blocking property, recoat property, and adhesive workability of the following process of a coating film. Silica is not particularly limited. For example, wet silica, dry silica, fumed silica, diatomaceous earth, etc. are mentioned. Silica can be used individually or in combination of 2 types or more, respectively.

(D) It is preferable that a silica contains fumed silica from a viewpoint of being excellent in transparency.

(D) Silica is preferably 20 to 400 m ² / g of an adsorption specific surface area measured by the BET (nitrogen) method because of its excellent anti-blocking properties, recoat properties, and adhesion workability in the following steps. It is more preferable that it is 40-300 m <^2> / g.

Moreover, 5-100 nm is preferable from a viewpoint that the primary particle diameter of a silica (D) can express transparency of a coating film, while being excellent in the anti-blocking property, recoat property, and adhesive workability of the next process, and 10-10- 70 nm is more preferable.

As (D) silica, what disperse | distributed (D) silica to one part or all part of polyfunctional (meth) acrylate (A) can be used. According to this method, the silica (D) which is easy to associate with microparticles | fine-particles disperse | distributes in a matrix more favorably, and the transparency of the coating film obtained becomes favorable. Specifically, for example, after obtaining a master batch in which (D) silica is dispersed in part or all of the polyfunctional (meth) acrylate (A) in advance, a method of mixing and using the master batch and the remaining components is desirable.

The amount of (D) silica is 1 to 20 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of being excellent in anti-blocking properties, recoating properties, and adhesive workability in the next step, and expressing transparency of the coating film. It is preferable that it is a mass part, and it is more preferable that it is 8-18 mass parts.

It is preferable that the composition of this invention contains a solvent further from a viewpoint of making (C) easy to melt | dissolve in a composition, and being excellent also in coatability.

The solvent is not particularly limited as long as it can dissolve (C). For example, ketones, such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; Alcohols such as propylene glycol monomethyl ether (PGME) and isopropyl alcohol (IPA); Cycloalkanes such as cyclohexane; Aromatic hydrocarbon compounds, such as toluene, xylene, and benzyl alcohol, are mentioned. Especially, cyclohexanone and MIBK are preferable from a viewpoint of being excellent in solubility, drying property, and paintability.

A solvent can be used individually or in combination of 2 or more types, respectively.

It is preferable that the quantity of a solvent is 60-300 mass parts with respect to 1 mass part of (C) from a viewpoint of making it easy to melt | dissolve (C) in a composition and being excellent in coatability.

The quantity of a solvent can be 85-5 mass% in composition whole quantity.

The composition of this invention can be made to contain no infrared absorber (in this case, the quantity of an infrared absorber is 0 mass% in a composition). When the composition of this invention contains an infrared absorber, the quantity can be 0.1-10 mass% or less of the whole composition. The infrared absorber is not particularly limited as long as it can absorb infrared rays (near infrared rays, mid infrared rays, far infrared rays). For example, a conventionally well-known thing is mentioned.

The composition of this invention is an ethylenic compound other than (A), a blue light absorbent other than (C), a ultraviolet absorber, fillers other than (D), and an antioxidant, in the range which does not impair the objective of this invention. And additives such as antistatic agents, flame retardants, tackifiers, dispersants, antioxidants, antifoams, leveling agents, gloss removers, light stabilizers, dyes, and pigments.

As a leveling agent, a silicone type leveling agent, an acryl type leveling agent, a vinyl leveling agent, a fluorine-type leveling agent, etc. are mentioned, for example.

The composition of the present invention is not particularly limited with respect to its preparation. For example, it can manufacture by mixing uniformly (A), (B), (C), (D) which can be used as needed, and a solvent. You may dissolve (C) in a solvent beforehand and use it.

The composition of the present invention can be used, for example, as a composition for forming a film having a blue light cut function, a plastic surface protective agent, a hard coat paint, a hard coat agent, an ultraviolet curable paint, a primer composition, and the like.

The material of the base material to which the composition of the present invention can be applied is not particularly limited. For example, plastic, rubber, glass, a metal, a ceramic etc. are mentioned. The form of a base material can be made into a film, for example.

The plastic which can apply the composition of this invention may be any of a thermosetting resin and a thermoplastic resin. Examples of the plastic include polyethylene terephthalate (PET), cycloolefin-based polymers (monopolymers, copolymers, and hydrogenated products. For example, COP or COC), polymethyl methacrylate resin (PMMA resin). And hard-adhesive resins such as polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, and polyamide resin.

COC is a copolymer (cycloolefin copolymer) of tetracyclo dodecene and olefins, such as ethylene. In addition, COP is a polymer (cycloolefin polymer) obtained by ring-opening-polymerizing norbornene and hydrogenating. Examples of the structures of COC and COP are shown below.

The base material may be subjected to a surface treatment such as, for example, a corona treatment.

The method (application method) of applying the composition of this invention to a base material is not specifically limited, For example, well-known coating methods, such as brush coating, shedding coating, immersion coating, spray coating, and spin coat, can be employ | adopted. .

As a hardening method of the composition of this invention, the hardening method by an ultraviolet-ray is mentioned. When hardening the composition of this invention by ultraviolet irradiation, as irradiation amount (accumulated light quantity) of the ultraviolet-ray used when hardening the composition of this invention, 200-3,000mJ / cm <^2> is preferable from a viewpoint of quick hardening property and workability. . The apparatus used for irradiating an ultraviolet-ray is not specifically limited. For example, a conventionally well-known thing is mentioned. You may use heating together in hardening.

The composition of this invention is excellent in a blue light cut function, the hardness of the hardened film obtained is high, and is excellent in adhesiveness and optical characteristics (transparency).

When the composition of the present invention is cured to a film thickness of 10 μm on a PET film, the average absorbance of light in the 385-495 nm region is preferably 7% or more, and preferably 15% or more.

It is preferable that pencil hardness at the time of hardening the composition of this invention to the film thickness of 10 micrometers on PET film is more than HB, and it is preferable that it is F or more.

Transparency when the composition of the present invention is cured to a film thickness of 10 μm on a PET film or COP film is preferably 85% or more in total light transmittance and less than 10% in haze value, and 90% or more in total light transmittance and 5% in haze value. It is preferable that it is less than.

The laminated body of this invention is demonstrated below.

The laminated body of this invention is a laminated body (film with a hardened film) which has a film and the cured film obtained using the ultraviolet curable resin composition of this invention on the said film.

The film and ultraviolet curable resin composition used for the laminated body of this invention are the same as the above.

The laminate of the present invention is not particularly limited with respect to its manufacture. For example, it can obtain by apply | coating and hardening the composition of this invention to a film.

The laminated body of this invention is demonstrated using an accompanying drawing below. The present invention is not limited to the accompanying drawings. 1: is sectional drawing which shows an example of the laminated body of this invention typically. In FIG. 1, the laminate 100 has a film 102 and a cured coating 104. The thickness of the film and the cured film is not particularly limited. The thickness of a film can be 50-300 micrometers. The thickness of a cured film can be 0.1-100 micrometers.

The laminated body of this invention is excellent in a blue light cut function, has high hardness, and has a cured film excellent in adhesiveness and optical characteristics.

As a manufacturing method of the laminated body of this invention, the method of coating the ultraviolet curable resin composition of this invention on a film, drying, and irradiating an ultraviolet-ray is mentioned, for example.

When coating an ultraviolet curable resin composition on a film, the method of coating is not specifically limited. For example, the application method similar to the above is mentioned.

After coating, the temperature at the time of drying a composition can be 20-110 degreeC.

When irradiating an ultraviolet-ray after drying, the method and conditions which irradiate an ultraviolet-ray to a composition are not specifically limited. For example, the hardening method similar to the above is mentioned.

The laminated body of this invention can be used for an electronic image display apparatus and an eyeglass lens, for example.

As an electronic image display apparatus, it is a personal computer, a television, for example; Display application electronic device components, such as a touch panel, are mentioned.

The laminate of the present invention can be embedded in an electronic image display device or the like or later attached (for example, affixed from the outside). When the laminated body of this invention is incorporated in an electronic image display apparatus etc., it can apply to parts other than a reflecting plate, for example. Specifically, it can be applied to a lens sheet, a diffusion sheet, and a light guide plate.

The cured film can be formed by directly applying the composition of the present invention to an electronic image display device.

Example

An Example is shown to the following and this invention is concretely demonstrated to it. However, this invention is not limited to these.

<Production of Composition>

The composition shown in the following 1st table | surface was mixed using the quantity (mass part) shown to the same table, and the composition was manufactured.

<Production of laminated body>

First, the composition (paint) obtained as described above was subjected to a polyethylene terephthalate film (PET dough: trade name U46, manufactured by Toray Industries, Inc., thickness of 125 μm) or a cycloolefin film (COP dough: subjected to corona treatment): ZF16-100, manufactured by ZEON CORPORATION, 100 μm thick, was coated using a bar coater with a clearance setting of 10 μm at the film thickness after drying, and dried for 1 minute under conditions of 80 ° C. After irradiating this, it irradiates ultraviolet-rays (UV) using GS UV SYSTEM made from KAWAGUCHI SPRING MFG. Co., Ltd. (UV irradiation conditions: illumination intensity: 300mW / cm <^2> , accumulated light quantity 300 mJ / cm <^2> , UV irradiation apparatus), hardened a composition, and obtained the laminated body.

<Evaluation>

The following evaluation was performed using the composition or laminated body manufactured as mentioned above. The results are shown in the first table.

(Average cut rate of blue light of the hardening film)

The laminated body manufactured as mentioned above was irradiated with the light of the wavelength of 385 nm-495 nm region using the Hitachi spectrophotometer 3900H as an apparatus, and the average transmittance | permeability (%) was measured. The average transmittance of the PET film dough (alone) and COP dough (alone) was also measured (the results were 12.0% and 10.3%, respectively), and these were applied to the following equation to average the cut ratio of blue light of the laminate. Was calculated.

Average cut rate (%) of blue light of the cured film = (average transmittance of the laminate)-(average transmittance of the PET film or COP dough alone)

The average cut ratio of the blue light of the cured coating was?

Only the base material (PET film) and the absorption spectrum of Comparative Example 3, Example 1, 3, 6, 7 are shown in the graph of FIG.

(Pencil hardness)

In accordance with JIS K5600-5-4: 1999 using the obtained laminated body (condition: angle of inclination of 45 degree of laminated body, the force of 9.8N, tip diameter 1.8mm, tip length 3.0mm), pencil hardness of a coating film Was measured.

(Adhesiveness)

On the cured film of the laminate obtained as described above, 100 sheets of 2 mm checkerboard eyes (10 × 10) were made, the cellophane adhesive tape was completely attached to the checkerboard, and immediately one end of the tape was kept perpendicular to the laminate. Instantly peeled off and checked the number of tiles left without peeling off completely. In the table, the result was described using the remaining number of checkerboard as the numerator and the total number of checkerboard (100) as the denominator.

(Light transmittance, haze)

The total light transmittance and the haze of the laminate were measured using a haze meter (HM-150, manufactured by Murakami Shikisai Kijutsu Kenkyujo Co., Ltd.). The result is shown as an average value of the sample number n = 3.

Total light transmittance can be 85% or more, and haze can be made into less than 10% by a haze value. The evaluation criteria are slightly good when the total light transmittance is 85% or more and less than 90%, and the haze value is 5% or more and less than 10%, and when the total light transmittance is 90% or more and 5% or less in the haze value. The case where the total light transmittance is 90% or more and the haze value is 1.3% or less is shown as good "◎" as "good".

(Soluble)

After mixing all the components, the appearance of the composition after 2 hours at room temperature was observed, and the case where (C) was not dissolved in the composition was defined as × and (C) was not dissolved.

The detail of each component shown by the 1st table | surface is as follows.

A1: dipentaerythritol hexaacrylate (DPHA), trade name Miramer M600, manufactured by Toyo Chemicals Co., Ltd.

A2: Reactant which reacted hydroxy (meth) acrylate and hexamethylene diisocyanate which contain urethane acrylate, brand name NX103-161, dipentaerythritol hexaacrylate (DPHA) as a main component in 81/19 (mass ratio), Made by Asia Industry Co., Ltd., (a pure urethane acrylate content * is 79.4% by mass of solids)

B1: 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, trade name Irgacure 2959, manufactured by BASF Corporation

D1: Fumed silica (corresponding to component (D), powder, adsorption specific surface area of 130 m ² / g by BET (nitrogen) method, average primary particle diameter of 16 nm, trade name Aerosil R972 (manufactured by Nippon Aerosol Co., Ltd.)) And a DPHA ((A) component. Tradename Miramer M600, manufactured by Toyo Chemical Co., Ltd.), obtained by mixing fumed silica / DPHA = 20/80 (mass ratio) (master batch).

Leveling agent: Nonionic fluorine-based surfactant, trade name FTX-218 dispersion, manufactured by Neos Corporation

C1: Blue light absorbent, a compound having a naphthalimide skeleton, Lumogen F Violet 570, manufactured by BASF Corporation

C2: blue light absorbent, compound having a perylene skeleton, Lumogen F Yellow 083, manufactured by BASF Corporation

C3: Blue light absorbent, compound having benzotriazole skeleton, Tinuvin Carbo protect, manufactured by BASF Corporation

Solvent 1: methyl isobutyl ketone (MIBK)

Solvent 2: Cyclohexanone

As is clear from the results shown in Table 1, Comparative Example 3 and Comparative Example 5, which did not include a compound having a naphthalimide skeleton and / or a compound having a perylene skeleton, did not have a blue light cut function. The comparative example 1 which does not contain the compound which has a naphthalimide skeleton, and / or the compound which has a perylene skeleton, and instead contains the compound which has a benzotriazole skeleton had the low blue light cut function. The comparative example 2 whose quantity of (C) component is less than 0.7 mass% of the non volatile component of a composition had low blue light cut function. In Comparative Example 4 in which the amount of the component (C) exceeded 2.0% by mass of the nonvolatile components of the composition, sedimentation was observed in the solution, and a sufficient coating material was not obtained.

On the other hand, Examples 1-9 are excellent in a blue light cut function. In particular, when (C) component is only a compound which has a naphthalimide frame | skeleton (Examples 1, 2 and 9), as is clear also from the evaluation result of transparency (total light transmittance / haze), there is no coloring of a cured film, and transparency Outstanding on Moreover, when (C) component contains the compound which has a naphthalimide frame | skeleton, and the compound which has a perylene skeleton (Example 3, 5, 6, 7), it is excellent in a blue light cut function.

2 is a graph showing the UV-visible light absorption spectrum of the laminate. In FIG. 2, "only a base material" means the polyethylene terephthalate film alone used for manufacture of a laminated body in an Example. As is clear from the results shown in FIG. 2, Examples 1, 3, 6, and 7 absorb blue light as well as the substrate and Comparative Example 3. FIG. In addition, Example 1 has no absorption in the longer wavelength region of blue light and is excellent in transparency than Example 3, 6, and 7. Embodiments 3, 6 and 7 can absorb blue light in a wide range within the blue light region.

100: laminate
102: film
104: hardened film

Claims (11)

The ultraviolet curable resin composition containing following (A)-(C) component, and the quantity of the said (C) component is 0.7-2.0 mass% of a non volatile component.
(A): polyfunctional (meth) acrylate
(B): photoinitiator
(C): A blue light absorbent containing at least one of a compound having a naphthalimide skeleton and a compound having a perylene skeleton. The method of claim 1,
The ultraviolet curable resin composition in which the said (C) component contains the compound which has a benzotriazole skeleton further. The method according to claim 1 or 2,
The ultraviolet curable resin composition in which the said (C) component contains the compound which has a perylene skeleton at least. The method of claim 3,
The ultraviolet curable resin composition whose quantity of the compound which has the said naphthalimide skeleton and the compound which has the said benzotriazole skeleton with respect to 1.0 mass part of compounds which have the said perylene skeleton is 0.0-50.0 mass parts. The method of claim 1,
The ultraviolet curable resin composition whose said (C) component is only a compound which has a naphthalimide skeleton. The method according to any one of claims 1, 2, and 5,
(D): UV cure resin composition containing silica further. The method according to any one of claims 1, 2, and 5,
Ultraviolet curable resin composition containing a solvent further. The method according to any one of claims 1, 2, and 5,
The ultraviolet curable resin composition which does not contain an infrared absorber. The laminated body which has a film and a cured film obtained using the ultraviolet curable resin composition of Claim 1 on the said film. The method of claim 9,
The laminated body obtained through the process of coating the ultraviolet curable resin composition of any one of Claims 1, 2, and 5 on a film, drying, and irradiating an ultraviolet-ray. The method of claim 9,
The laminated body used for an electronic image display apparatus.

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