JP6026550B2 - Laminate - Google Patents

Description

  The present invention relates to a UV curable resin composition and a laminate having a cured film formed using the same.

A light source (e.g., an LED backlight) of an electronic image display device widely used in recent years emits light having a wavelength near 385 to 495 nm, so-called blue light. It has been pointed out that this blue light has an adverse effect on humans, such as symptoms such as eyestrain and dry eye; reduced retinal function; and inhibition of melatonin secretion that promotes sleep, so that the biological clock is displaced. is there.
For example, Patent Document 1 describes, as an optical filter capable of cutting at least a part of visible light of 380 to 500 nm, "an optical article characterized by containing fullerenes as an absorption component of blue light". ([Claim 1] [0009]).

Japanese Patent Application Publication No. 2007-093927

The present inventors examined fullerenes described in Patent Document 1 and found that the blue light cut function was not sufficient.
Then, this invention makes it a subject to provide the ultraviolet curable resin composition which can form the cured film which is excellent in a blue light cut function.

The present inventors have intensively studied to solve the above problems, and as a result, it is an ultraviolet ray curable type containing a nematic liquid crystal compound (A) having a polymerizable functional group, a chiral agent (B) and a photopolymerization initiator (C). The inventors have found that the cured film formed using the resin composition is excellent in the blue light cut function, and completed the present invention.
That is, the present inventors have found that the above problems can be solved by the following configuration.

[1] A laminate having a substrate and a cured film, which is used after being attached to an electronic image display device,
The cured film is a nematic liquid crystal compound having a polymerizable functional group (A), is formed with a chiral agent (B) and a photopolymerization initiator (C) an ultraviolet-curable resin composition containing a color difference ( L * a * b * Ri cured coating der the b * value of 2.0 or less by color system),
The nematic liquid crystal compound (A) is a compound represented by the following formula (2a) or the following formula (2b), and the above chiral agent (B) is represented by any of the following formulas (3a) to (3c) Compounds, and
The content of the chiral agent (B) is, Ru 1.0 to 30.0% by mass relative to the total weight of the nematic liquid crystal compound (A) and the chiral agent (B), the laminate.




(In the formula (2a), n represents an integer of 2 to 5 and in the formula (3a), m represents an integer of 2 to 5)
[ 2 ] The laminate according to [1 ], further containing a compound (D) having a naphthalimide skeleton represented by the following formula (1).

(In formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may have a hetero atom, R ² represents a hydrogen atom or an organic group, and a plurality of R ² are the same. May also differ.)
[ 3 ] The laminate according to [1] or [2] , further comprising a compound (E1) having a benzotriazole skeleton and / or a compound (E2) having a hydroxyphenyltriazine skeleton.
[ 4 ] A resin layer is further provided between the substrate and the cured film,
The laminated body in any one of [1]-[ 3 ] whose said resin layer is an acrylic resin layer whose surface tension is 32 mN / m or more.

ADVANTAGE OF THE INVENTION According to this invention, the ultraviolet curable resin composition which can form the cured film which is excellent in a blue light cut function can be provided.
Moreover, since the laminated body of this invention has a cured film formed using the ultraviolet curable resin composition of this invention, it is excellent in a blue light cut function.

FIG. 1 is a cross-sectional view schematically showing an example of the laminate of the present invention. FIG. 2 is a graph showing the UV-visible light absorption spectrum of the laminate.

[UV-curable resin composition]
The ultraviolet ray curable resin composition of the present invention (hereinafter, also simply referred to as "the composition of the present invention") is a nematic liquid crystal compound (A) having a polymerizable functional group, a chiral agent (B) and a photopolymerization initiator (C) containing and reducing the transmittance of at least part of light in the wavelength range of 385 nm to 495 nm, and curing with ab * value of 2.0 or less according to color difference (L * a * b * color system) It is an ultraviolet curable resin composition for forming a film.

In the present invention, as described above, a curing formed by using a composition containing a nematic liquid crystal compound (A) having a polymerizable functional group, a chiral agent (B) and a photopolymerization initiator (C) The film has a blue light cut function.
Although this is not clear in detail, a predetermined concavo-convex pattern is formed on the surface of the cured film due to the predetermined alignment (twist) state of the nematic liquid crystal compound caused by the addition of the chiral agent, and the blue light region (385 nm) It is considered that at least a part of the light of a wavelength range of-495 nm is reflected. Further, it is considered that such reflection makes it possible to reduce the problem of the yellowishness of the cured film becoming strong by the reflection of blue light in natural light despite having the blue light cut function.
In addition, since the mechanism mentioned above is our guess, even if it differs from an actual mechanism, when it has all the invention specific matters of this invention, it is natural to belong to the technical scope of this invention. .
The nematic liquid crystal compound (A) having a polymerizable functional group, the chiral agent (B), the photopolymerization initiator (C) and other optional components will be described in detail below.

<Nematic Liquid Crystalline Compound (A)>
The nematic liquid crystal compound (A) contained in the composition of the present invention is a nematic liquid crystal compound having a polymerizable functional group, and in combination with a chiral agent (B) described later, a compound exhibiting a blue light cut function It is not particularly limited as long as
Here, examples of the polymerizable functional group include ethylenic double bonds such as (meth) acryloyloxy group, vinyl group and allyl group, and among them, (meth) acryloyloxy group is preferable. Note that "(meth) acryloyloxy group" shall mean a acryloyloxy groups (CH ₂ = CHCOO-) or methacryloyloxy group _{(CH 2 = C (CH 3} ) COO-).

As such a nematic liquid crystal compound, for example, a rod-like liquid crystal compound having two or more polymerizable functional groups in one molecule is preferable, and specifically, it is represented by the following formula (I) Preferably it is a compound.
R ³ -C ³ -D ³ -C ⁵ -M-C ⁶ -D ⁴ -C ⁴ -R ^4- Formula (I)
(Wherein, R ³ and R ⁴ are polymerizable functional groups, and each of which is independently a (meth) acrylic group, (thio) epoxy group, oxetane group, thietanyl group, aziridinyl group, pyrrole group, vinyl group, allyl group) , A fumarate group, a cinnamoyl group, an oxazoline group, a mercapto group, an iso (thio) cyanate group, an amino group, a hydroxyl group, a carboxyl group, and an alkoxysilyl group, D ³ and D ⁴ each being a group A group selected from the group consisting of a single bond, a linear or branched alkyl group having 1 to 20 carbon atoms, and a linear or branched alkylene oxide group having 1 to 20 carbon atoms single bond, -O is .C ³ -C ⁶ representing a -, - S -, - S -S -, - CO -, - CS -, - OCO -, - CH 2 -, - OCH 2 -, - C = N-N = C-, -NHC O -, - OCOO -, - CH 2 COO-, and .M represents a group selected from the group consisting of -CH ₂ OCO- represents a mesogenic group, specifically, having a substituted or unsubstituted group Azomethines, azoxys, phenyls, biphenyls, terphenyls, naphthalenes, anthracenes, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, -O-, -S-, -S-S-, -CO-, 2 to 4 skeletons selected from the group consisting of alkoxy-substituted phenyl pyrimidines, phenyl dioxanes, tolanes and alkenylcyclohexyl benzonitriles -CS -, - OCO -, - CH 2 -, - OCH 2 -, - C = N-N = C -, - NHCO -, - OCOO-, CH ₂ COO-, and is formed are joined by a linking group of -CH ₂ OCO-, and the like.)

As the nematic liquid crystal compound represented by the above formula (I), it is easy to adjust the alignment (twist) state by a chiral agent (B) described later, and polymerization using a photopolymerization initiator (C) described later It is preferable that it is a compound represented by following formula (2a) from the reason of being easy to advance.
(In the formula (2a), n represents an integer of 2 to 5).

Specifically as a nematic liquid crystalline compound (A) other than the compound represented by the said Formula (2a), the compound shown below is mentioned, for example.

Among these, a compound represented by the following formula (2b) and a compound represented by the following formula (2c) are preferable.

<Chiral agent (B)>
The chiral agent (B) contained in the composition of the present invention is not particularly limited as long as it is a compound that exhibits a blue light cut function in combination with the above-described nematic liquid crystal compound (A).

In the present invention, the chiral agent (B) has a polymerizable functional group because of excellent paintability, leveling properties (including compatibility with other components), and optical properties (total light transmittance / haze). Is preferred.
Here, as a polymerizable functional group, the thing similar to what was demonstrated in the nematic liquid crystalline compound (A) mentioned above is mentioned.
The polymerizable functional group which may be possessed by the chiral agent (B) preferably has the same polymerizable functional group as the polymerizable functional group possessed by the nematic liquid crystal compound (A). It is more preferable that both the liquid crystal compound (A) and the chiral agent (B) be a (meth) acryloyloxy group.

As such a chiral agent, for example, a compound having an isosorbide skeleton structure is preferable, and specifically, a compound represented by the following formula (II) is preferable.
(Wherein, P ¹ and P ² each independently represent a hydrocarbon group having a carbon number of 10 to 20 containing one 1,4-cyclohexylene group, and an oxygen atom or ester having ether bondability in the group may have a bond, a hydrogen atom in the group may be substituted by a fluorine atom. However, one of P ¹ and P ² are P1 and P2, including the further polymerizable functional group.)

As the chiral agent represented by the above formula (II), the blue light cut function of the cured film cured with the liquid crystal compound represented by the above formula (2a) is better, the following formula (3a) It is preferable that it is a compound represented by these.
(In the formula (3a), m represents an integer of 2 to 5).

Specifically as a chiral agent (B) other than the compound represented by the said Formula (3a), the compound shown below is mentioned, for example.

Specifically as a chiral agent (B) other than the compound represented by said Formula (3a), the compound represented by a following formula (3b), the compound represented by a following formula (3c), for example Is preferably mentioned.

  Examples of chiral agents (B) other than the compounds represented by the above formulas (3a) to (3c) include, for example, JP-A-2005-289881, JP-A-2004-115414, and JP-A-2003-66214. JP-A-2003-313187, JP-A-2003-342219, JP-A-2000-290315, JP-A-6-072962, U.S. Pat. No. 6,468,444, WO 98/00428, etc. In addition, commercially available products such as LC756 available from BASF Palio Color and CNL 617 R and CNL-686 L available from ADEKA can also be used appropriately.

In the present invention, the content of the chiral agent (B) is the total mass of the nematic liquid crystal compound (A) and the chiral agent (B) because the blue light cut function of the cured film is better. The proportion is preferably 1.0 to 30.0% by mass.
In particular, when the compound represented by the formula (2a) is used as the nematic liquid crystal compound (A) and the compound represented by the formula (3a) is used as the chiral agent (B), the chiral The content of the agent (B) is preferably 4.0 to 6.5% by mass with respect to the total mass of the nematic liquid crystal compound (A) and the chiral agent (B).

<Photoinitiator (C)>
The photopolymerization initiator (C) contained in the composition of the present invention is not particularly limited as long as it can polymerize the nematic liquid crystal compound (A) and the chiral agent (B) by light.
Examples of the photopolymerization initiator (C) include acetophenone compounds, benzoin ether compounds, benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, phosphine oxide compounds and the like.
Specifically, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, acetoin, butyroin, toluoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, α, α-dimethoxy-α-phenylacetophenone Methylphenyl glyoxylate, ethyl phenyl glyoxylate, 4,4'-bis (dimethylaminobenzophenone), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1, Carbonyl compounds such as 2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; azobis Azo compounds such as sobutyronitrile and azobis-2,4-dimethyl valero; peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide; and the like. These may be used alone or in combination. The above may be used in combination.

  Among these, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenyl from the viewpoints of photostability, high efficiency of photocleavage, surface curability, compatibility, low volatility, low odor, etc. -Propan-1-one and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one are preferred.

  In the present invention, the content of the photopolymerization initiator (C) is 0.5 to 20 parts by mass with respect to a total of 100 parts by mass of the nematic liquid crystal compound (A) and the chiral agent (B). It is preferably present, and more preferably 3 to 9 parts by mass.

<Compound (D) Having Naphthalimide Skeleton>
The composition of the present invention can absorb the short wavelength side region (385 to 420 nm) in the blue light region, and the blue light cut function becomes better as a whole, as represented by the following formula (1) It is preferred to contain a compound (D) having a phthalimide skeleton.
(In formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may have a hetero atom, R ² represents a hydrogen atom or an organic group, and a plurality of R ² are the same. May also differ.)

Examples of the hydrocarbon group which may have a hetero atom represented by R ¹ in the above formula (1) include, for example, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and the like Combinations may be mentioned and may have unsaturated bonds.
The organic group represented by R ^2, for example, an amino group, a functional group such as a hydroxyl group; a combination of these, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, hydrocarbon groups and aromatic hydrocarbon groups And hydrocarbon groups; The hydrocarbon group may have a hetero atom or a double bond.
The hydrocarbon group represented by R ¹ is preferably a linear or branched alkyl group, and preferably has 1 to 12 carbon atoms.
Further, among the organic groups represented by R ² , the hydrocarbon group is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group.

  The content of the compound (D) having a naphthalimide skeleton is 0.05 to 10 parts by mass with respect to a total of 100 parts by mass of the nematic liquid crystal compound (A) and the chiral agent (B). It is preferably present, and more preferably 1.0 to 3.0 parts by mass.

<Compound (E1) / Compound (E2)>
The composition of the present invention can absorb a short wavelength region (385 to 430 nm) in the blue light region, and the compound having a benzotriazole skeleton (E1) and a benzotriazole skeleton because the blue light cut function is better as a whole It is preferable to contain the compound (E2) which has / or a hydroxyphenyl triazine skeleton.

As a compound (E1) which has a benzotriazole frame, the compound represented by following formula (4) is mentioned, for example.
(In formula (4), R ³ represents a hydrogen atom or a hydrocarbon group which may have a hetero atom.)

Examples of the hydrocarbon group which may have a hetero atom represented by R ³ in the above formula (4) include, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and the like Combinations may be mentioned and may have unsaturated bonds.

  As a commercial item of the compound (E1) which has such a benzotriazole frame | skeleton, tinuvin Carbo protect (made by BASF Corporation), tinuvin 384-2 (made by BASF Corporation) etc. are mentioned, for example.

  The content of the compound (E1) having a benzotriazole skeleton is 0.05 to 10 parts by mass with respect to a total of 100 parts by mass of the nematic liquid crystal compound (A) and the chiral agent (B). It is preferably present, and more preferably 1.0 to 3.0 parts by mass.

On the other hand, as a compound (E2) which has a hydroxyphenyl triazine skeleton, the compound etc. which are represented by following formula (5) are mentioned, for example.
(In formula (5), R ⁴ represents a hydrocarbon group which may have a hetero atom. R ⁵ represents a hydrogen atom or an organic group, and a plurality of R ⁵ are all the same. R ⁶ may represent a hydrogen atom or an organic group, and a plurality of R ⁶ may be the same or different.

Examples of the hydrocarbon group which may have a hetero atom represented by R ⁴ in the above formula (5) include, for example, aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, and the like Combinations may be mentioned and may have unsaturated bonds. Among them, an aliphatic hydrocarbon group which may have a hetero atom or a hydroxy group is preferable.
Examples of the organic group represented by R ⁵ in the above formula (5) include functional groups such as amino group and hydroxyl group; hydrocarbons such as aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group Groups; hydrocarbon groups combining these; Among them, an aliphatic hydrocarbon group (particularly an alkyl group) is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group or an ethyl group is further preferable.
Examples of the organic group represented by R ⁶ in the above formula (5) include functional groups such as amino group and hydroxyl group; hydrocarbons such as aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group Groups; hydrocarbon groups combining these; The hydrocarbon group may have a hetero atom or a double bond. Among them, aliphatic hydrocarbon groups (especially, alkyl groups and alkoxy groups) and aromatic hydrocarbon groups (especially phenyl groups) are preferable.

  As a commercial item of the compound (E2) which has such a hydroxyphenyl triazine skeleton, for example, tinuvin 400 (manufactured by BASF), tinubin 405 (manufactured by BASF), tinuvin 460 (manufactured by BASF), tinuvin 477 (BASF) And Tinuvin 479 (BASF).

  The content of the compound (E2) having a hydroxyphenyltriazine skeleton is 0.05 to 10 parts by mass with respect to 100 parts by mass in total of the nematic liquid crystal compound (A) and the chiral agent (B). Is preferable, and 1.0 to 3.0 parts by mass is more preferable.

<Solvent>
The composition of the present invention preferably further contains a solvent from the viewpoint of improving the coatability.
The solvent is not particularly limited as long as it can dissolve the components described above. For example, ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone; alcohols such as propylene glycol monomethyl ether (PGME), isopropyl alcohol (IPA); cycloalkanes such as cyclohexane; toluene, xylene And aromatic hydrocarbon compounds such as benzyl alcohol. Among them, cyclohexanone and MIBK are preferable from the viewpoint of excellent solubility, drying property and paintability.
The solvents may be used alone or in combination of two or more.

  In the present invention, the content of the optional solvent is preferably 85 to 5% by mass in the total amount of the composition from the viewpoint of coatability.

<Leveling agent>
The composition of the present invention preferably further contains a leveling agent because the blue light cut function of the cured film is better.
As a leveling agent, a silicone type leveling agent, an acrylic type leveling agent, a vinyl type leveling agent, a fluorine type leveling agent etc. are mentioned, for example.
Among these, it is preferable to use an acrylic leveling agent because the uniformity of the cured film is improved and as a result, the transparency of the cured film is improved.

  In the present invention, the content of any leveling agent is preferably 0.01 to 3% by mass in the total amount of the composition from the viewpoint of coatability.

  The composition of the present invention is, for example, UV absorbers, fillers, anti-aging agents, antistatic agents, flame retardants, adhesion-imparting agents, dispersants, antioxidants, and light-emitting agents as long as the object of the present invention is not impaired. It can further contain additives such as foaming agents, matting agents, light stabilizers, dyes, pigments.

  The method for producing the composition of the present invention is not particularly limited, and the above-described nematic liquid crystal compound (A), chiral agent (B) and photopolymerization initiator (C), and optional compound (D), compound (E1), It can manufacture by mixing a compound (E2), a solvent, a leveling agent, and an additive uniformly.

[Laminate]
A layered product of the present invention is a layered product which has a substrate and a hardened film, and the hardened film is formed using the composition of the present invention mentioned above.
The laminate of the present invention has a cured film formed using the composition of the present invention, and thus is excellent in the blue light cut function.

Next, the configuration of the laminate of the present invention will be described with reference to FIG.
A laminate 100 shown in FIG. 1 has a substrate 102 and a cured film 104 formed using the composition of the present invention.
Here, the thickness of the substrate and the cured film is not particularly limited, but the thickness of the substrate is preferably about 50 to 300 μm, and the thickness of the cured film is preferably about 0.1 to 100 μm .

<Base material>
The said base material is not specifically limited, As a constituent material, plastic, rubber, glass, metal, ceramics, etc. are mentioned, for example.
Here, the plastic may be any of a thermosetting resin and a thermoplastic resin. Specific examples thereof include polyethylene terephthalate (PET), cycloolefin polymer (homopolymer, copolymer, hydrogenation Such as COP and COC), polymethyl methacrylate resin (PMMA resin), polycarbonate resin, polystyrene resin, acrylonitrile / styrene copolymer resin, polyvinyl chloride resin, acetate resin, ABS resin, polyester resin, polyamide resin, etc. Can be mentioned.
Moreover, the said base material may be surface-treated like corona treatment, for example.
The form of the substrate is not particularly limited, but is preferably in the form of a film.

Here, COC is a copolymer (cycloolefin copolymer) of tetracyclododecene and an olefin such as ethylene. Further, COP is a polymer (cycloolefin polymer) obtained by ring-opening polymerization of norbornenes and hydrogenation.
Below, the example of the structure of COC and COP is shown.

<Resin layer>
In the laminate of the present invention, between the base and the cured film, the alignment (twist) state of the liquid crystal compound constituting the cured film is improved and the adhesion to the substrate is also improved. It is preferable to have a resin layer.
In the present invention, when the resin layer is provided, the resin layer is preferably an acrylic resin layer having a surface tension of 32 mN / m or more.
Here, the surface tension is obtained by applying a wet pen (pen number 30, 32, 34, 36, 38, 40, 42 and 44 mN / m set, Alcotest) to the cured acrylic resin layer. After 2 to 5 seconds after painting, the condition of the pen streaks is visually confirmed, and the largest pen number not causing ink repulsion is selected and judged.

Such an acrylic resin layer is abbreviated as, for example, a UV curable resin composition (hereinafter, “hard coat resin composition”) used for a conventionally known hard coat, as long as the surface tension is 32 mN / m or more. It is preferable that it is an acrylic resin layer formed using In addition, adjustment of surface tension can be performed by containing the conventionally well-known leveling agent, surfactant, a hydrophilicity or lipophilicity imparting agent, etc.
Here, as the resin composition for hard coat, for example, a composition containing a multifunctional (meth) acrylate (a) described later, a photopolymerization initiator (b) and the like can be used.

(Multifunctional (meth) acrylate (a))
The polyfunctional (meth) acrylate (a) is not particularly limited as long as it is a compound having two or more (meth) acryloyloxy groups.
The (meth) acryloyloxy group can be bonded to an organic group. As an organic group, the hydrocarbon group which may have hetero atoms like 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 linear or branched and may have an unsaturated bond.
The multifunctional (meth) acrylate (a) has a (meth) acryloyloxy group of 4 to 5 because the hardness of the resulting acrylic resin layer is high and the adhesion between the base and the cured film becomes better. It is preferable to have twelve.

As polyfunctional (meth) acrylate (a), the (meth) acrylic acid ester of polyhydric alcohol, urethane (meth) acrylate is mentioned, for example.
Examples of (meth) acrylic acid esters of polyhydric alcohols include trifunctional systems such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol tri (meth) acrylate; A tetrafunctional system such as (meth) acrylate, dipentaerythritol tetra (meth) acrylate, tripentaerythritol tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol Penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol o Data (meth) 5 or higher functional systems such as acrylate.

Examples of urethane (meth) acrylates include (meth) acrylic esters of polyhydric alcohols (in this case, examples of (meth) acrylic esters of polyhydric alcohols include those having at least one hydroxy group). And a polyisocyanate compound.
As a (meth) acrylic acid ester of polyhydric alcohol used when manufacturing urethane (meth) acrylate, the thing similar to the above is mentioned, for example.
As a polyisocyanate compound used when manufacturing urethane (meth) acrylate, for example, tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, tolidine diisocyanate 1,4,5-naphthalene diisocyanate, aromatic polyisocyanate such as triphenylmethane triisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, transcyclohexane-1,4-diisocyanate, isophorone diisocyanate, bis (Isocyanate methyl) Cyclohexane, (including linear and / or cycloaliphatic systems.) Aliphatic polyisocyanates such as dicyclohexylmethane diisocyanate; these isocyanurate, biuret body, an adduct; and the urethane prepolymer.

(Photoinitiator (b))
On the other hand, the photopolymerization initiator (b) is not particularly limited as long as it can polymerize the polyfunctional (meth) acrylate (a) by light, and the photopolymerization contained in the composition of the present invention An initiator (C) similar to the initiator (C) can be appropriately selected and used.

The above hard coat resin composition is, for example, an ultraviolet absorber, a filler, an antiaging agent, an antistatic agent, a flame retardant, an adhesion imparting agent, a dispersing agent, an antioxidant, as long as the object of the invention is not impaired The composition may further contain additives such as antifoaming agents, leveling agents, matting agents, light stabilizers, dyes and pigments.
As a leveling agent, a silicone type leveling agent, an acrylic type leveling agent, a vinyl type leveling agent, a fluorine type leveling agent etc. are mentioned, for example.

  The thickness of the resin layer is preferably about 0.1 to 100 μm, and more preferably 1 to 5 μm, because the adhesion between the base and the cured film is further improved. .

<Hard coat layer>
The laminate of the present invention may have a hard coat layer on the surface of the cured film opposite to the substrate.
Here, the hard coat layer is preferably an acrylic resin layer formed using the resin composition for hard coat described in the resin layer described above, and the method for forming the hard coat layer is the method for forming the resin layer described above and Similar methods can be mentioned.
When the hard coat layer is provided, the thickness is not particularly limited, but is preferably about 0.01 to 50 μm, and more preferably 1 to 5 μm.

<Manufacturing method>
The method for producing a laminate of the present invention is, for example, a step of applying the composition of the present invention on a film-like substrate (in the case of having the above resin layer, the above resin layer), drying and irradiating ultraviolet light. And the like.
Here, the method of coating the composition of the present invention on a substrate is not particularly limited, and, for example, known coating methods such as brush coating, flow coating, dip coating, spray coating and spin coating can be adopted.
Moreover, it is preferable that the temperature made to dry after application is 20-110 degreeC.
In addition, the ultraviolet irradiation after drying is 50 to 3,000 mJ / cm ² as the irradiation amount (integrated light quantity) of the ultraviolet light used when curing the composition of the present invention from the viewpoint of fast curing and workability. preferable. The apparatus used to irradiate ultraviolet light is not particularly limited. For example, conventionally known ones can be mentioned. Heating may be used in combination with curing.
In addition, the formation method of the said resin layer can be formed by the process of applying on a base material, drying, and irradiating an ultraviolet-ray by the method similar to the composition of this invention.

The laminate of the present invention can be used, for example, in an electronic image display device, a spectacle lens, a protective cover for illumination (particularly, LED illumination), a solar cell module member, and the like.
Examples of the electronic image display device include display-use electronic device parts such as personal computers, televisions, touch panels, wearable terminals (for example, computer terminals that can be worn on the body such as glasses and watches).
The laminate of the present invention can be incorporated or retrofitted (for example, attached from the outside) in an electronic image display device or the like. When the laminate of the present invention is incorporated 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 diffusion sheet, and a light guide plate.
The composition of the present invention can be applied directly to an electronic image display to form a cured film.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these.

[Examples 1 to 18 and Comparative Examples 1 to 2]
<Preparation of composition>
The components shown in Table 1 below were mixed using the stirrer with the composition (parts by mass) shown in Table 1 to prepare a composition.
<Production of laminates>
Each composition obtained as described above is 1.5 μm in film thickness after drying using a bar coater on a polyethylene terephthalate film (PET fabric: trade name U46, manufactured by Toray Industries, Inc., 125 μm thick) After applying with a clearance setting and drying this for 1 minute under conditions of 80 ° C., it is irradiated with ultraviolet rays (UV) using a GSUV SYSTEM manufactured by Kawaguchi Spring Mfg. Co. (UV irradiation conditions: illuminance 300 mW / cm ² An integrated light amount of 300 mJ / cm ² , a UV irradiation device was a high pressure mercury lamp), and the composition was cured to prepare a laminate.

[Evaluation]
The following evaluation was performed using the manufactured laminated body. The results are shown in Table 1.

<Average cut rate of blue light of hardened film>
The laminate manufactured as described above was irradiated with light in the 800-300 nm region using a Hitachi spectrophotometer 3900H as an apparatus, and the average transmittance (%) in the 385 nm-495 nm region was measured. The measurement result was applied to the following equation to calculate the average cut rate of blue light of the laminate.
Average cut rate of blue light of cured film (%) = 100-(average transmittance in the 385 to 495 nm region)
Here, the absorption spectra of only the substrate (PET film), Examples 1, 4 and 10 and Comparative Example 1 are shown in the graph of FIG.

<Yellowish>
With regard to the color difference (L * a * b * color system) of the produced laminate, using a handy type simple type spectrocolorimeter CM-500 (manufactured by Konica Minolta Co., Ltd.) according to the method defined in JIS Z8730: 2009 It was measured. The measurement results of b * value are shown in Table 1 below.

The details of each component shown in Table 1 are as follows.
-Nematic liquid crystalline compound A-1: compound represented by the above formula (2a) (n = 4)
-Nematic liquid crystalline compound A-2: a compound represented by the above formula (2b)-non liquid crystalline compound X-1: hydroxy (meth) acrylate containing dipentaerythritol hexaacrylate (DPHA) as a main component [trade name: Reactant obtained by reacting NX103-161, solid content 85%: manufactured by Sub-industry Co., Ltd.] with hexamethylene diisocyanate at a mass ratio (81/19). Chiral agent B-1: represented by the above formula (3a) Compound (m = 4)
Chiral agent B-2: compound represented by the above formula (3b) Chiral agent B-3: compound represented by the above formula (3c) Photopolymerization initiator C-1: Irgacure 184 (manufactured by BASF AG)
Compound D-1: compound having a naphthalimide skeleton (R ¹ in the above formula (1) is —CH ₂ CH (CH ₂ CH ₂ CH ₃ ) ₂ and R ² is —O—CH ₃ Compound)
Compound E1-1: Compound having a benzotriazole skeleton (Tinuvin Carbo protect, manufactured by BASF)
-Compound E1-2: a compound having a benzotriazole skeleton (tinuvin 384-2, manufactured by BASF)
Compound E2-1: a compound having a hydroxyphenyltriazine skeleton (tinuvin 477, manufactured by BASF)
Compound E2-2: Compound having a hydroxyphenyl triazine skeleton (Tinuvin 479, manufactured by BASF)
-Methyl ethyl ketone: Solvent-Cyclohexanone: Solvent-Leveling agent: Acrylic-based leveling agent (BYK 361N, manufactured by BIC Chemie Japan)

As apparent from the results shown in Table 1, the composition of Comparative Example 1 prepared by blending a non-liquid crystal compound without blending a nematic liquid crystal compound (A) having a polymerizable functional group is a blue light It turned out that it is inferior to a cut function (comparative example 1).
Moreover, it turned out that the composition of the comparative example 2 prepared without mix | blending a chiral agent (B) has a blue light cut function inadequate (comparative example 2).

On the other hand, the composition prepared by blending the nematic liquid crystal compound (A) having a polymerizable functional group, the chiral agent (B) and the photopolymerization initiator (C) is all cured with a blue light cut function. It was found that a film could be formed, and all b * values were 2.0 or less, and it was found that the yellowness was very low despite having the blue light cut function (Examples 1 to 1) 18). In addition, in a commercially available blue light cut film, it can be seen that even when the b * value is in the range of 7 to 25 in general, the effect is remarkable.
In particular, together with the nematic liquid crystal compound (A) and the chiral agent (B), a compound (D) having a naphthalimide skeleton, a compound (E1) having a benzotriazole skeleton, or a compound (E2) having a hydroxyphenyltriazine skeleton The compositions of Examples 2-8, 11-12, 14 and 16-18 used in combination were found to further improve the blue light cut function.

  FIG. 2 is a graph showing the UV-visible light absorption spectrum of the laminate. "Base material only" in FIG. 2 means the polyethylene terephthalate film alone used for producing the laminate in the examples. As is clear from the results shown in FIG. 2, it can be seen that Examples 1, 4 and 10 do not transmit blue light from the substrate alone or Comparative Example 1.

[Examples 19 to 34]
Laminates A and B were produced by the methods shown below using the compositions prepared in Examples 1 to 3 and 8 and the adhesion of the cured film was evaluated by the methods shown below.

<Production of Laminate A-Base Material (PET Film)>
After drying the acrylic resin composition (all are Yokohama Rubber Co., Ltd. product number) shown in Table 2 below on a polyethylene terephthalate film (PET fabric: trade name U46, manufactured by Toray Industries, Inc., 125 μm thick) using a bar coater The coating was applied at a clearance setting of 1.5 μm in film thickness, dried for 1 minute at 80 ° C., and then subjected to ultraviolet light (UV) using GSUV SYSTEM manufactured by Kawaguchi Spring Mfg. Co. It was cured by irradiation (UV irradiation condition: illumination intensity: 300 mW / cm ² , integrated light amount: 300 mJ / cm ² , UV irradiation device: high pressure mercury lamp) to form an acrylic resin layer on the PET substrate. The formed acrylic resin layer is coated with a wet pen (pen set of 30, 32, 34, 36, 38, 40, 42 and 44 mN / m, Alcotest Co., Ltd.) for 2 to 5 seconds after painting When it passed, the state of the pen streaks was visually confirmed, and the largest pen number to which the ink does not repel was selected, and the surface tension was determined.
Next, each composition prepared in Examples 1 to 3 and 8 is applied to the above acrylic resin layer using a bar coater at a clearance setting of 1.5 μm after drying, and this is applied After drying at 80 ° C. for 1 minute, it is irradiated with ultraviolet rays (UV) using a GSUV SYSTEM manufactured by Kawaguchi Spring Mfg. Co. (UV irradiation conditions: illuminance 300 mW / cm ² , integrated light amount 300 mJ / cm ² , The UV irradiation device was a high pressure mercury lamp) to cure the composition, and a laminate was produced.

<Production of Laminate B-Substrate (Cycloolefin)>
A laminate B was prepared by the same method as the laminate A, except that a cycloolefin film (COP fabric: trade name ZF16-100, manufactured by Nippon Zeon, thickness 100 μ) to which corona treatment was applied was used as a substrate. Was produced.

<Adhesiveness>
The produced laminates A and B were subjected to a cross-cut peeling test based on JIS K5400 to evaluate adhesion.
Specifically, using a cutter, cut at 1 mm pitch only in the cured film portion and the resin layer portion of each laminate to make 100 substrates (10 × 10), and adhere cellophane adhesive on the substrate The tape (width 18 mm) was completely attached, and one end of the tape was instantaneously pulled while keeping the end perpendicular to the substrate, and the number of substrates remaining without being completely peeled off was examined. When the number of the remaining base was 75 or more, it was evaluated as "o" as excellent in adhesion, and when less than 75, it was evaluated as "x" as slightly inferior in adhesion. The results are shown in Table 2 below.

  From the results shown in Table 2, when a resin layer is provided between the substrate and the cured film as a laminate, the surface tension of the acrylic polymer constituting the resin layer is 32 mN / m or more, It was found that the adhesion to the cured film was good.

100 laminate 102 base material 104 cured film

Claims (4)

What is claimed is: 1. A laminate having a substrate and a cured film, which is used after being attached to an electronic image display device,
The cured coating is a nematic liquid crystal compound having a polymerizable functional group (A), is formed with a chiral agent (B) and a photopolymerization initiator (C) an ultraviolet-curable resin composition containing a color difference ( L * a * b * Ri cured coating der the b * value of 2.0 or less by color system),
The nematic liquid crystal compound (A) is a compound represented by the following formula (2a) or the following formula (2b), and the chiral agent (B) is represented by any of the following formulas (3a) to (3c) Compounds, and
The content of the chiral agent (B) is, Ru 1.0 to 30.0% by mass relative to the total weight of the nematic liquid crystal compound (A) and the chiral agent (B), the laminate.




(In the formula (2a), n represents an integer of 2 to 5 and in the formula (3a), m represents an integer of 2 to 5) Further contains a compound having a naphthalimide skeleton represented by the following formula (1) (D), the laminate according to claim 1.

(In formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group which may have a hetero atom, R ² represents a hydrogen atom or an organic group, and a plurality of R ² are the same. May also differ.) Furthermore, compounds having a benzotriazole skeleton (E1) and / or a compound having a hydroxyphenyl triazine skeleton containing (E2), the laminated body according to claim 1 or 2. A resin layer is further provided between the substrate and the cured film,
The laminate according to any one of claims 1 to 3 , wherein the resin layer is an acrylic resin layer having a surface tension of 32 mN / m or more.