TW201446899A - Ultraviolet-curable resin composition and layered product using the same - Google Patents

Abstract

The purpose of the present invention is to provide an UV-curable resin composition that exhibits superior blue-light blocking properties. The UV-curable resin composition according to the present invention includes (A) a polyfunctional (meth)acrylate, (B) a photopolymerization initiator, and (C) a blue-light absorbing agent that includes a compound having a naphthalimide skeleton and/or a compound having a perylene skeleton, with the content of constituent (C) being 0.7-2.0 mass% relative to the non-volatile constituents.

Description

UV curable resin composition and laminate using the same

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

In recent years, liquid crystal displays and the like have become popular, and artificial light sources such as LEDs emit light having a wavelength of about 385 to 495 nm, which is called blue light. It has been pointed out that the negative effects of blue light on the human body include symptoms such as eye fatigue and dryness; retinal function decline; inhibition of melatonin secretion that promotes sleep, leading to physiological clock disorder.

Further, a surface of the electronic image display device is provided with a near-infrared absorbing film having a near-infrared absorbing layer. The infrared absorbing pigment contained in the near-infrared ray absorbing layer is generally decomposed by ultraviolet rays contained in sunlight, and in order to suppress this, a benzotriazole-based ultraviolet absorbing agent is used (for example, Patent Document 1).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-6513

However, the inventors have found that the conventional benzotriazole-based ultraviolet absorber has poor anti-blue light function.

Accordingly, an object of the present invention is to provide an ultraviolet curable resin composition excellent in anti-blue light function.

In order to solve the above problems, the present inventors have found that an ultraviolet curable resin composition containing a compound having a naphthoquinone imine skeleton and/or a compound having an anthracene skeleton as a blue light absorber has excellent anti-blue light function. Thus, the present invention has been completed.

That is, the present invention is as follows.

An ultraviolet curable resin composition comprising the following components (A) to (C), wherein the component (C) is 0.7 to 2.0% by mass of the nonvolatile component.

(A): Polyfunctional (meth) acrylate

(B): Photopolymerization initiator

(C): a blue light absorber containing a compound having a naphthoquinone imine skeleton and/or a compound having an anthracene skeleton

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

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

4. The ultraviolet curable resin composition according to the above 3, wherein the compound having the naphthylquinone imine skeleton and/or the compound having the benzotriazole skeleton is 1.0 part by mass based on the compound having the anthracene skeleton It is 0.0 to 50.0 parts by mass.

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

6. The ultraviolet curable resin composition according to any one of the above 1 to 5, further comprising (D): cerium oxide.

7. The ultraviolet curable resin composition according to any one of the above 1 to 6, which further contains a solvent.

8. The ultraviolet curable resin composition according to any one of the above 1 to 7, which does not contain an infrared ray absorbing agent.

A laminate comprising a film and a cured film obtained by using the ultraviolet curable resin composition according to any one of the above 1 to 8 on the film.

10. The laminate according to the above 9, which is obtained by applying the ultraviolet curable resin composition according to any one of the above 1 to 8 to a film, drying it, and irradiating the ultraviolet ray.

11. The laminate of 9 or 10 above, which is used in an electronic image display device.

The ultraviolet curable resin composition of the present invention is excellent in the anti-blue light function.

The laminate of the present invention is excellent in anti-blue light function.

100‧‧‧Layer

102‧‧‧film

104‧‧‧ hardened film

Fig. 1 is a cross-sectional view schematically showing an example of a laminate of the present invention.

Fig. 2 is a graph showing a UV-visible absorption spectrum of a laminate.

The invention is described in detail below.

The ultraviolet curable resin composition of the present invention (the composition of the present invention) contains the following components (A) to (C), and the amount of the component (C) is from 0.7 to 2.0% by mass of the nonvolatile component. Resin composition.

(A): Polyfunctional (meth) acrylate

(B): Photopolymerization initiator

(C): a blue light absorber containing a compound having a naphthoquinone imine skeleton and/or a compound having an anthracene skeleton

The composition of the present invention has a characteristic of absorbing a light having a region of 385 (±5) to 495 (±5) nm, that is, a so-called blue light, by containing the component (C). A compound having a naphthoquinone imine skeleton and a compound having an anthracene skeleton can absorb blue light and emit light in other regions.

Further, the composition of the present invention contains (A) component because The hardened film obtained by this has high hardness and is excellent in adhesion to a substrate.

Further, in the present invention, the component (A) may be simply referred to as (A). The components (B), (C) and (D) are also the same.

The following description (A): polyfunctional (meth) acrylate.

The (A) contained in the composition of the present invention is not particularly limited as long as it is a compound having two or more (meth) acryloxy groups.

Here, "(meth)acryloxy" means propylene methoxy (CH ₂ =CHCOO-) or methacryloxy (CH ₂ =C(CH ₃ )COO-), "(methyl) "Acrylate" means acrylate or methacrylate.

The (meth)acryloxy group can be bonded to an organic group. The organic group may, for example, be a hydrocarbon group which may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and combinations thereof. The hydrocarbon group may contain a linear chain, a branched chain, or may have an unsaturated bond.

From the viewpoint of having high hardness of the cured film and excellent adhesion to the substrate, (A) preferably has 4 to 12 (meth)acryloxy groups.

Examples of the polyfunctional (meth) acrylate include (meth) acrylates of polyhydric alcohols and urethane (meth) acrylates.

Examples of the (meth) acrylate of the polyhydric alcohol include a trifunctional group such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, or dipentaerythritol tri(meth)acrylate; a tetrafunctional system such as pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate; and dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(methyl) Acrylate, three quarters Five or more functional groups such as tetraol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and tripentaerythritol octa (meth) acrylate.

Examples of the urethane (meth) acrylate include a (meth) acrylate of a polyhydric alcohol (in this case, as a (meth) acrylate of a polyhydric alcohol, for example, at least one hydroxyl group is mentioned) A reactant of a polyisocyanate compound.

Examples of the (meth) acrylate of the polyol used in the production of the urethane (meth) acrylate include the same as described above.

Examples of the polyisocyanate compound used in the production of the urethane (meth) acrylate include toluene diisocyanate, diphenylmethane diisocyanate, phenyl diisocyanate, and polymethylene polyphenylene polyisocyanate. , an aromatic polyisocyanate such as benzodimethyl diisocyanate, tetramethyl dimethyl diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate or triphenylmethane triisocyanate; hexamethylene di Isocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, trans cyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis (isocyanate methyl) An aliphatic polyisocyanate such as cyclohexane or dicyclohexylmethane diisocyanate (including chain and/or alicyclic); such isocyanurate, biuret, adduct; and amine group Formate prepolymer.

The polyisocyanate compound used to form the urethane prepolymer is synonymous with the above. The polyol used to form the urethane prepolymer is not particularly limited. For example, polyoxyalkylene polyols such as polypropylene polyols can be cited. Alcohol, etc.

In view of the fact that the (A) component is preferably dipentaerythritol hexa(meth) acrylate and pentaerythritol tri(meth) acrylate, it has 3 points in one molecule, such as high hardness and excellent adhesion and optical properties. ~6 (meth) propylene oxime compounds.

The component (A) may be used alone or in combination of two or more.

When the (meth) acrylate and the urethane (meth) acrylate of the polyol are used in combination as the component (A), the viewpoint of high hardness, excellent adhesion, and optical properties is considered. The ratio of the amount of the (meth) acrylate to the urethane (meth) acrylate is, compared with 100 parts by mass of the (meth) acrylate of the polyol, the urethane (meth) acrylate is Preferably, it is 1 to 200 parts by mass, more preferably 10 to 100 parts by mass.

The manufacture of the component (A) is not particularly limited. For example, those well known in the past can be mentioned.

The following description (B): Photopolymerization initiator. The (B) contained in the composition of the present invention is not particularly limited as long as it can be polymerized by light (A). Examples of the photopolymerization initiator (B) include an acetophenone-based compound, a benzoin-ether compound, a benzophenone-based compound, a sulfur compound, an azo compound, a peroxy compound, and a phosphine oxide compound. . Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyl acetoin, toluoin, and diphenyl. Ethylenedione, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α,α-dimethoxy-α-phenylacetophenone, glyoxylic acid Phenyl phenyl ester, ethyl phenyl glyoxylate, 4,4'-bis(dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2 a carbonyl compound such as 2-dimethoxy-1,2-diphenylethane-1-one or 1-hydroxycyclohexyl phenyl ketone; tetramethylthiocarbamate monosulfide, tetramethylammonium disulfide a sulfur compound such as thiocarbamine; an azo compound such as azobisisobutyronitrile or azobis-2,4-dimethylvaleronitrile; and a peroxy compound such as benzamidine peroxide or di-tert-butyl peroxide. Wait.

Among them, from the viewpoints of photostability, photocracking efficiency, surface hardenability, compatibility, low volatility, and low odor, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl group are preferred. 1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one.

(B) may be used alone or in combination of two or more.

The amount of (B) is preferably from 0.5 to 12 parts by mass, more preferably from 3 to 9 parts by mass, per 100 parts by mass of (A).

The component (C) will be described below. The component (C) contained in the composition of the present invention is a blue light absorber containing a compound having a naphthoquinone imine skeleton and/or a compound having an anthracene skeleton.

The compound having a naphthoquinone imine skeleton is not particularly limited. The naphthylquinone imine skeleton may also have a substituent. The naphthylquinone imine skeleton is represented by the following chemical formula.

In the above formula, the nitrogen atom may be bonded, for example, to a hydrogen atom, and a hydrocarbon group which may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. The hydrocarbon group is synonymous with the above.

As a commercial item of the compound having a naphthoquinone imine skeleton, Lumogen F Violet 570 (made by BASF Corporation) is mentioned, for example.

The compound having a naphthoquinone imine skeleton is preferred because it absorbs a region on the low-wavelength side (385 to 420 nm) of blue light and is excellent in transparency.

(C) When it is only a compound having a naphthoquinone imine skeleton, it is excellent in its anti-blue light function, and the color of the cured film is not yellow, and it is excellent in transparency.

The compound having an anthracene skeleton is not particularly limited. The anthracene skeleton may also have a substituent. The ruthenium skeleton is shown by the following chemical formula.

As a commercial product of a compound having an anthracene skeleton, for example, Lumogen F Yellow 083 (manufactured by BASF Corporation) is listed.

A compound having an anthracene skeleton absorbs a region on the longer wavelength side of blue light (420 to 495 nm) than a compound having a naphthylquinone imine skeleton.

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 also have a substituent. The benzotriazole skeleton is represented by the following chemical formula.

In the above formula, the nitrogen atom at the 2-position may be bonded to, for example, a hydrogen atom, and a hydrocarbon group which may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom. The hydrocarbon group is synonymous with the above.

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

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

In view of the superiority of the anti-blue light function, (C) preferably contains at least a compound having an anthracene skeleton. In this case, the amount of the compound having a naphthoquinone imine skeleton and/or the compound having a benzotriazole skeleton, preferably 0.0 to 0.0 part by mass of the compound having an anthracene skeleton, is considered to be the same as the above. 50.0 parts by mass, more preferably 1.0 to 45.0 parts by mass.

Here, regarding "the combination of a naphthylquinone imine skeleton And the amount of the compound having a benzotriazole skeleton, when any compound having a naphthoquinone imine skeleton and a compound having a benzotriazole skeleton is used as the component (C), The content of the compound; when both the compound having a naphthylquinone imine skeleton and the compound having a benzotriazole skeleton are used as the component (C), it means the total amount of the compounds.

In the present invention, in view of the fact that the anti-blue light function is excellent and the transparency and the solubility are excellent, the component (C) is 0.7 to 2.0% by mass of the amount of the nonvolatile component contained in the composition of the present invention.

Here, the "nonvolatile content" means a component which does not volatilize after heating at 105 ° C for 1 hour under normal pressure, and contains the nonvolatile components (A), (B), and (C) contained in the composition of the present invention. When an additive such as (D) cerium oxide or a filler of any of the following components is used, it means that the components of the non-volatile components are also contained.

In this case, the amount of the component (A) is preferably from 60 to 98% by mass, more preferably from 80 to 95, in view of the fact that the anti-blue light function is more excellent, the hardness of the cured film is high, and the adhesion is excellent. quality%.

The amount of the component (B) is preferably from 0.5 to 12% by mass, more preferably from 2 to 8% by mass, based on the viewpoint that the anti-blue light function is more excellent, the hardness of the cured film is high, and the hardenability is excellent.

The amount of the component (C) is preferably from 1.0 to 2.0% by mass based on the amount of the nonvolatile component, from the viewpoint of further excellent anti-blue light function, excellent transparency and solubility, and no loss of adhesion.

When the composition of the present invention further contains the following (D) cerium oxide, it is considered that the anti-blue light function is more excellent, the hardened film is high in hardness, and the adhesion is good. In view of excellent properties, the amount of the component (A) is preferably from 60 to 98% by mass, more preferably from 75 to 90% by mass, based on the amount of the nonvolatile component.

The amount of the component (B) is preferably from 0.5 to 12% by mass, more preferably from 2 to 8% by mass, based on the viewpoint that the anti-blue light function is more excellent, the hardness of the cured film is high, and the hardenability is excellent.

The amount of the component (C) is preferably from 1.0 to 2.0% by mass based on the amount of the nonvolatile component, from the viewpoint of further excellent anti-blue light function, excellent transparency and solubility, and no loss of adhesion.

Considering the anti-blocking property of the coating film, the recoatability, and the excellent adhesiveness in the next step, the amount of the component (D) is preferably from 1 to 20% by mass based on the amount of the nonvolatile component. More preferably 5 to 15% by mass.

The composition of the present invention preferably further contains (D): cerium oxide, in view of the coating film anti-adhesive property, recoatability, and excellent adhesion workability in the next step. Cerium dioxide is not particularly limited. Examples thereof include wet cerium oxide, dry cerium oxide, fumed silica, and diatomaceous earth. The cerium oxide may be used singly or in combination of two or more.

Considering the viewpoint of excellent transparency, (D) cerium oxide preferably contains smog.

Considering the anti-adhesiveness, recoatability, and adhesion of the film in the next step, the adsorption specific surface area of the (D) cerium oxide by BET (nitrogen) method is preferably 20 to 400 m ² / g, more preferably 40 to 300 m ² /g.

In addition, the primary particle size of the cerium oxide (D) is preferably 5~ from the viewpoint of the anti-stick property of the coating film, the recoatability, and the excellent adhesiveness in the next step, and the transparency of the coating film can be exhibited. 100 nm, more preferably 10 to 70 nm.

As (D) cerium oxide, those in which (D) cerium oxide is previously dispersed in part or all of the polyfunctional (meth) acrylate (A) can be used. According to this method, the particulate and easily polymerized cerium oxide (D) is more suitably dispersed in the matrix, and the transparency of the obtained coating film is good. Specifically, for example, it is preferred to disperse (D) cerium oxide in part or all of the polyfunctional (meth) acrylate (A) in advance, and after obtaining the master batch, mixing the master batch with the remaining ingredient.

Considering the anti-adhesiveness of the coating film, the recoatability, and the excellent adhesiveness in the next step, and the transparency of the coating film can be exhibited, (D) the amount of cerium oxide relative to 100 parts by mass of the component (A) It is preferably 1 to 20 parts by mass, more preferably 8 to 18 parts by mass.

In view of the fact that (C) is easily dissolved in the composition and the coatability is also excellent, the composition of the present invention preferably further contains a solvent.

The solvent is not particularly limited as long as it can dissolve (C). Examples thereof include ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; and alcohols such as propylene glycol monomethyl ether propionate (PGME) and isopropyl alcohol (IPA); a cycloalkane such as cyclohexane; and an aromatic hydrocarbon compound such as toluene, xylene or benzyl alcohol. Among them, cyclohexanone and MIBK are preferred from the viewpoints of excellent solubility, drying property, and paintability.

Solvents may be used alone or in combination of two or more. use.

In view of the fact that (C) is easily dissolved in the composition and the coating property is excellent, the amount of the solvent is preferably 60 to 300 parts by mass based on 1 part by mass of the component (C).

The amount of the solvent may be 85 to 5% by mass based on the total amount of the composition.

The composition of the present invention may contain no infrared absorbing agent (in this case, the infrared absorbing dose is 0% by mass in the composition). When the composition of the present invention contains an infrared ray absorbing agent, the amount thereof may be 0.1 to 10% by mass or less based on the total amount of the composition. The infrared absorber is not particularly limited as long as it can absorb infrared rays (near infrared rays, medium infrared rays, and far infrared rays). For example, those well known in the past can be mentioned.

The composition of the present invention may contain, without departing from the object of the present invention, for example, an ethylenic compound other than (A), a blue light absorber other than (C), an ultraviolet absorber, and a filler other than (D). Additives such as aging agents, antistatic agents, flame retardants, adhesion improvers, dispersants, antioxidants, defoamers, leveling agents, matting agents, light stabilizers, dyes, pigments, etc.

Examples of the leveling agent include a polyfluorene-based leveling agent, an acrylic leveling agent, an ethylene-based leveling agent, and a fluorine-based leveling agent.

The production of the composition of the present invention is not particularly limited. For example, it can be produced by uniformly mixing (A), (B), (C), and (D), a solvent which can be used as needed. It is also possible to dissolve (C) in a solvent before use.

The composition of the present invention can be used, for example, as a composition for forming a mold having a blue light-resistant function, a plastic surface protectant, and a hard coat layer. Coatings, hard coating agents, UV curable coatings, and primer compositions.

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

The plastic to which the composition of the present invention can be applied may be any of a thermosetting resin and a thermoplastic resin. Examples of the plastic include polyethylene terephthalate (PET), a cycloolefin polymer (including a homopolymer, a copolymer, and a hydride such as COP and COC), and polymethyl methacrylate. Inadhesiveness of resin (PMMA resin), polycarbonate resin, polystyrene resin, acrylonitrile-styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, and polyamide resin Resin.

The COC is a copolymer (cycloolefin copolymer) of an olefin such as tetracyclododecene and ethylene. Further, COP is a polymer (cycloolefin polymer) obtained by ring-opening polymerization and hydrogenation of a norbornene. The structural examples of COC and COP are as follows.

n: degree of polymerization, m, m': copolymer content molar ratio

R: lower alkyl, R', R": same or different lower alkyl

The substrate may also have been subjected to a surface treatment such as corona treatment.

The method of applying the composition of the present invention to a substrate (application method) is not particularly limited, and for example, a well-known coating method such as brush coating, flow coating, dip coating, spray coating, or spin coating can be employed.

As a hardening method of the composition of this invention, the hardening method by ultraviolet-ray is mentioned. When the composition of the present invention is cured by ultraviolet irradiation, the ultraviolet irradiation amount (accumulated light amount) used for curing the composition of the present invention is preferably 200 to 3,000 mJ from the viewpoint of quick-curing property and workability. Cm ² . The means for irradiating ultraviolet rays is not particularly limited. For example, those well known in the past can be mentioned. When hardening, heating can also be used together.

The composition of the present invention is excellent in anti-blue light function, and the cured film obtained has high hardness and excellent adhesion and optical properties (transparency).

After the composition of the present invention is cured on the PET film at a film thickness of 10 μm, the average light absorption rate in the region of 385 to 495 nm is preferably 7% or more, more preferably 15% or more.

After the composition of the present invention is cured on the PET film with a film thickness of 10 μm, the pencil hardness is preferably HB or more, more preferably F or more.

When the composition of the present invention is cured on a PET film or a COP film with a film thickness of 10 μm, the transparency is preferably 85% or more of the total light transmittance, less than 10% of the haze value, and more preferably 90% or more of the total light transmittance. The haze value is less than 5%.

The laminate of the present invention will be described below.

The laminate of the present invention (film with a cured film) has a film and a cured film obtained by using the ultraviolet curable resin composition of the present invention on the film.

The film used in the laminate of the present invention and the ultraviolet curable resin composition are the same as described above.

The production of the laminate of the present invention is not particularly limited. For example, it can be obtained by applying the composition of the present invention to a film and hardening it.

The laminate of the present invention will be described below with reference to the drawings. this invention It is not limited to the drawings. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a laminate of the present invention. In FIG. 1, the laminate 100 has a film 102 and a hardened film 104. The thickness of the film and the cured film is not particularly limited. The film thickness can be 50 to 300 μm. The thickness of the hardened film may be from 0.1 to 100 μm.

The laminate of the present invention has a cured film which is excellent in anti-blue light function, high in hardness, and excellent in adhesion and optical properties.

The method for producing the laminate of the present invention includes, for example, a method in which the ultraviolet curable resin composition of the present invention is applied onto a film, dried, and irradiated with ultraviolet rays.

When the ultraviolet curable resin composition is applied to the film, the coating method is not particularly limited. For example, the same application method as described above can be cited.

When the composition is dried after coating, the temperature may be from 20 to 110 °C.

When the ultraviolet ray is irradiated after drying, the method and conditions for irradiating the composition with ultraviolet rays are not particularly limited. For example, the same hardening method as mentioned above can be mentioned.

The laminate of the present invention can be used, for example, in an electronic image display device and an ophthalmic lens.

Examples of the electronic image display device include a computer, a television, and an electronic device component for display use such as a touch panel.

The laminate of the present invention may be incorporated or externally (for example, externally attached, etc.) to an electronic image display device or the like. When the laminate of the present invention is placed in an electronic image display device or the like, it can be applied to, for example, a portion other than the reflector. Specifically, for example, it can be applied to a lens sheet, a diffuser sheet, and a light guide. board.

The composition of the present invention can be directly applied to an electronic image display device to form a hardened film.

[Examples]

The embodiments are described below to specifically illustrate the invention. However, the invention is not limited thereto.

<Manufacture of composition>

The components shown in the table are mixed according to the amounts (parts by mass) shown in the following Table 1 to prepare a composition.

<Manufacture of laminates>

First, the composition (coating) obtained above was applied to a polyethylene terephthalate film (PET texture: trade name) using a bar coater at a film thickness of 10 μm after drying. U46, manufactured by Toray Industries, 125 μm thick or corona-treated cycloolefin film (COP texture: trade name: ZF16-100, manufactured by Zeon Co., Ltd., thickness: 100 μm), dried at 80 ° C for 1 minute. The GS UV SYSTEM manufactured by Kawaguchi Spring Co., Ltd. was irradiated with ultraviolet rays (UV) (UV irradiation conditions: illuminance: 300 mW/cm ² , cumulative light amount: 300 mJ/cm ² , and UV irradiation device was a high-pressure mercury lamp), and the composition was hardened to obtain a layer. Fit.

<evaluation>

The following evaluation was carried out using the composition or laminate manufactured as above. The results are shown in Table 1.

(average reduction ratio of blue light of hardened film)

The laminated body produced as above was irradiated with light of a region wavelength of 385 nm to 495 nm using a Hitachi spectrophotometer 3900H as a device, and the average transmittance (%) thereof was measured. The average transmittance of the PET film texture (separate) and the COP texture (individually) were also measured (the results were 12.0% and 10.3%, respectively), and the results were put into the following formula to calculate the average reduction ratio of the blue light of the laminate. .

Average reduction ratio (%) of blue light of hardened film = (average transmittance of laminate) - (average transmittance of PET film or COP texture alone)

The average reduction ratio of blue light of the cured film is 15% or more, ◎, 7% or more but less than 15% is ○, less than 7% is Δ, and 0% is ×.

The absorption spectra of only the substrate (PET film), Comparative Example 3, and Examples 1, 3, 6, and 7 are shown in the graph of FIG.

(pencil hardness)

Using the obtained laminate, the pencil hardness of the coating film was measured in accordance with JIS K5600-5-4: 1999 (condition: laminate tilt angle 45°, pressure 9.8 N, tip end diameter 1.8 mm, tip end length 3.0 mm).

(adhesion)

On the hardened film of the laminate obtained above, 100 (10×10) 2 mm checkerboards were prepared, and the cellophane tape was completely attached to the checkerboard, and then the tape was placed at a right angle to the laminate at one end, and directly Pull it open and check the number of remaining checkers that have not been completely stripped. In the table, the number of remaining checkerboards is numerator, and the total number of checkerboards (100) is used as the denominator, and the result is recorded.

(total light transmittance and haze)

The total light transmittance and haze of the laminate were measured using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.). The results are shown as the average of the number of samples n=3.

The total light transmittance can be more than 85%, and the haze value of the haze is less than 10%. The evaluation criteria are: when the total light transmittance is 85% or more but less than 90% and the haze value is 5% or more but less than 10%, it is slightly better "○"; the total light transmittance is 90% or more and the haze value is 5%. In the following, it is shown as "◎"; when the total light transmittance is 90% or more and the haze value is 1.3% or less, it is excellent as "◎◎".

(solubility)

After mixing all the components, the appearance of the composition after standing at room temperature for 2 hours was observed, (C) was ○ when dissolved in the composition, and × when (C) was not dissolved.

The components shown in Table 1 are as follows.

‧A1: Dipentaerythritol hexaacrylate (DPHA), trade name Miramer M600, manufactured by Toyo Chemicals

‧A2: urethane acrylate, trade name NX103-161, main component containing dipentaerythritol hexaacrylate (DPHA) hydroxy (meth) acrylate and hexamethylene diisocyanate at 81/19 (mass ratio The reaction product obtained by the reaction, manufactured by Asia Minor Industries Co., Ltd. (net content of urethane acrylate ^* is 79.4% by mass of the solid component)

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

‧d1: smoked sputum (corresponding to (D) component. Powder. The adsorption specific surface area measured by the BET (nitrogen) method is 130 m ² /g, and the average primary particle diameter is 16 nm, trade name Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) and DPHA (corresponding to (A) component. Trade name Miramer M600, manufactured by Toyo Chemicals Co., Ltd.) Disperse (master batch) obtained by mixing smog/DPHA=20/80 (mass ratio)

‧ Leveling agent: non-ionic fluorine-based surfactant, trade name FTX-218 dispersion, made by Neos

‧C1: blue light absorber, compound with naphthoquinone imine skeleton, Lumogen F Violet 570, manufactured by BASF

‧C2: blue light absorber, compound with anthracene skeleton, Lumogen F Yellow 083, manufactured by BASF

‧C3: blue light absorber, compound with benzotriazole skeleton, Tinuvin Carbo protect, manufactured by BASF

‧ Solvent 1: methyl isobutyl ketone (MIBK)

‧ solvent 2: cyclohexanone

As is clear from the results shown in the first table, Comparative Example 3 and Comparative Example 5 which do not contain a compound having a naphthoquinone imine skeleton and/or a compound having an anthracene skeleton do not have a blue light-resistant function. In Comparative Example 1 which does not contain a compound having a naphthoquinone imine skeleton and/or a compound having an anthracene skeleton, the anti-blue light function is inferior in Comparative Example 1 containing a compound having a benzotriazole skeleton. In Comparative Example 2 in which the amount of the component (C) was less than 0.7% by mass of the nonvolatile component of the composition, the blue light resistance was poor. In Comparative Example 4 in which the amount of the component (C) exceeded 2.0% by mass of the nonvolatile component of the composition, sedimentation was observed in the solution, and a coating material satisfying the coating requirements could not be obtained.

On the other hand, Examples 1 to 9 were excellent in the anti-blue light function. In particular, when the component (C) is only a compound having a naphthylquinone imine skeleton (Examples 1, 2, and 9), the transparency evaluation result (total light transmittance/haze) can also be clearly known, and hardening The film is not colored, and the transparency is excellent. Further, when the component (C) contains a compound having a naphthoquinone imine skeleton and a compound having an anthracene skeleton (Examples 3, 5, 6, and 7), the blue light-resistant function is more excellent.

Fig. 2 is a graph showing a UV-visible absorption spectrum of a laminate. In Fig. 2, "substrate only" means a single polyethylene terephthalate film used in the production of a laminate in the examples. As is clear from the results shown in Fig. 2, Examples 1, 3, 6, and 7 can absorb blue light as compared with only the substrate and Comparative Example 3. Further, in comparison with Examples 3, 6, and 7, Example 1 did not absorb the long wavelength region in the blue light, and was excellent in transparency. Examples 3, 6, and 7 absorb a wide range of blue light in the blue light field.

100‧‧‧Layer

102‧‧‧film

104‧‧‧ hardened film

Claims (11)

An ultraviolet curable resin composition comprising the following components (A) to (C), wherein the amount of the component (C) is 0.7 to 2.0% by mass of the nonvolatile component; (A): polyfunctional (meth) acrylate (B): Photopolymerization initiator (C): A blue light absorber containing a compound having a naphthoquinone imine skeleton and/or a compound having an anthracene skeleton. The ultraviolet curable resin composition of claim 1, wherein the component (C) further contains a compound having a benzotriazole skeleton. The ultraviolet curable resin composition according to claim 1 or 2, wherein the component (C) contains at least a compound having an anthracene skeleton. The ultraviolet curable resin composition of claim 3, wherein the compound having a naphthylquinone imine skeleton and/or the benzotriazole is 1.0 part by mass of the compound having an anthracene skeleton The amount of the compound of the skeleton is 0.0 to 50.0 parts by mass. The ultraviolet curable resin composition of claim 1, wherein the component (C) is only a compound having a naphthylquinone imine skeleton. The ultraviolet curable resin composition according to any one of the items 1 to 5, further comprising (D): cerium oxide. The ultraviolet curable resin composition according to any one of claims 1 to 6, further comprising a solvent. The ultraviolet curable resin composition according to any one of claims 1 to 7, which does not contain an infrared absorbing agent. A laminate comprising a film, and a cured film obtained by using the ultraviolet curable resin composition according to any one of claims 1 to 8 on the film. The laminate of the ninth aspect of the patent application, which is characterized in that the ultraviolet curable resin composition of any one of claims 1 to 8 is coated on a film and dried, and then irradiated with ultraviolet rays. obtain. The laminate of claim 9 or 10 is used in an electronic image display device.