JP5235762B2 - Resin composition for hard coat - Google Patents

Description

  The present invention relates to a resin composition for hard coat containing a near-infrared absorbing dye having absorption in the near-infrared light region. More specifically, the present invention has excellent near-infrared absorptivity and excellent heat resistance, moisture resistance, and light resistance. Hard coat resin composition, hard coat material using the hard coat resin composition, heat ray blocking film using the hard coat material, antireflection film, antiglare film, thin display optical filter, etc. It relates to a near-infrared shielding filter.

  In recent years, plasma display panels (hereinafter, abbreviated as “PDP”) have become widespread as demands for larger and thinner displays have increased. Since near infrared rays are emitted from the PDP and an electronic device using the near infrared remote controller malfunctions, it is necessary to block the near infrared rays with a filter containing a near infrared absorber. Moreover, since the optical semiconductor element used for a CCD camera etc. has high sensitivity in the near infrared region, it is necessary to remove the near infrared ray. Furthermore, near-infrared absorbers show solar heat ray absorption effects and are used as heat ray shielding films in applications such as glass for automobiles and glass for building materials, in order to prevent output reduction due to temperature rise in solar cell modules. However, it is necessary to cut off the heat ray. The near-infrared shielding filter used for these applications can effectively absorb the near-infrared light region while transmitting the visible light region, and is further required to have heat resistance stability, moisture resistance stability and light resistance stability.

  As the near-infrared absorbing dye as a near-infrared absorbing agent, conventionally, cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particles, etc. Is used. Among these, diimonium dyes are frequently used because they have a high near-infrared absorption ability and high transparency in the visible light region (see, for example, Patent Document 1). This document exemplifies various kinds of near-infrared absorbing dyes based on diimonium salt compounds. As a near-infrared absorbing dye having relatively excellent heat resistance and moisture resistance, for example, the anion component is bis (hexafluoroantimonic acid). Certain N, N, N ′, N′-tetrakis {p-di (n-butyl) aminophenyl} -p-phenylenediimonium salts are known.

  However, the diimonium salt compound disclosed in Patent Document 1 has insufficient heat resistance and moisture resistance, and the dye decomposes during use, so that the near-infrared absorption ability decreases, and the aminium produced by the decomposition Since salt absorbs in the visible light region, there is a problem that the visible light transmittance is lowered and the color tone is deteriorated due to yellow coloration.

Incidentally, an optical filter used for a thin display such as a PDP is usually provided with an antireflection layer, an antiglare layer, a hard coat layer and the like in addition to a near infrared absorption layer. (For example, see Patent Document 2)
In the configuration of a normal optical filter, a near infrared absorption layer and a hard coat layer are provided separately. For example, since the near-infrared absorbing layer disclosed in Patent Document 3 is not a hard coat layer, it is necessary to separately prepare a near-infrared absorbing layer and a hard coat layer when obtaining an optical filter with low scratch resistance. is there.
When the hard coat layer also has near-infrared absorbing ability, it is possible to reduce the number of films to be used and to omit processes, and therefore attempts have been made to include a near-infrared absorbing dye in the hard coat layer.

Patent Document 4 discloses a resin molded product having a hard coat layer containing a near infrared absorber provided by coating on at least one surface of a transparent resin layer, and the near infrared absorber is an imonium compound. A near-infrared absorbing resin molded article characterized by being two or more near-infrared absorbers containing at least one of a diimonium compound and an aminium compound is disclosed.
Here, the hard coat layer is formed by irradiating the hard coat resin with active energy rays such as ultraviolet rays. Therefore, when a near-infrared absorber is contained in the hard coat layer, the active energy ray is also irradiated to the near-infrared absorber. It has been found that the conventional diimonium salt compound disclosed in Patent Document 4 is easily decomposed by ultraviolet rays, and the near-infrared absorption ability is greatly reduced by this decomposition. Furthermore, there has been a problem that the curing of the resin is inhibited by a side reaction between the curing accelerator such as a polymerization initiator and the diimonium salt compound.

  Patent Document 5 discloses one using a phthalocyanine compound or a naphthalocyanine compound as a near infrared absorber. However, phthalocyanine compounds or naphthalocyanine compounds have a narrow near-infrared absorption region, and in order to obtain sufficient near-infrared absorption ability, a plurality of types of near-infrared absorption dyes having different absorption wavelengths must be used.

JP-A-10-180922 JP 2006-201443 A JP 2004-309655 A Japanese Patent No. 3788652 JP 2008-268267 A

An object of the present invention is to provide a resin composition for a near-infrared absorbing hard coat containing a diimonium salt compound as a near-infrared absorbing dye, having active energy ray curability and transparency, and having a near-infrared absorbing ability. It is to provide an excellent resin composition for hard coat.
It is another object of the present invention to provide a hard coat material having high visible light transmittance, excellent durability, and excellent near-infrared shielding effect using the hard coat resin composition. The provision of such a hard coating material contributes to the production of a near-infrared shielding filter such as a heat ray shielding film, an antireflection film, an antiglare film, an optical filter for a thin display, and a thin display that are cheaper and have higher performance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that diimonium salt compounds that are in an associated state and have specific absorption characteristics are contained in an active energy ray-curable resin in a fine particle dispersed state so that they are irradiated with ultraviolet rays. It was found that the decomposition of the salt compound did not occur, and further, no inhibition of curing of the active energy ray curable resin occurred, and the present invention was completed.

That is, the present invention is a hard coat resin composition comprising a near infrared absorber and having transparency and active energy ray curability, wherein the near infrared absorber is represented by the following general formula (1). A hard coat resin composition comprising an association product of compounds.
Here, the specific absorption characteristic indicates an absorption characteristic described later.

In the above formula, R _{1 to} R ₈ each represents an organic group which may be the same or different, and X ⁻ represents an anion.

The present invention is also a hard coat resin composition having excellent near-infrared absorption ability, wherein the near-infrared absorber is dispersed in an active energy ray-curable resin in an associated state.
Here, the said meeting state shows the state which can be confirmed directly or indirectly by the method mentioned later.

Moreover, this invention is a hard-coat material formed by hardening | curing the said resin composition for hard-coats. This hard coat material has an excellent near infrared absorption ability. A preferred hard coat material has a transparent base material and a hard coat layer containing the hard coat resin composition.
As the transparent substrate, glass, a PET film, a TAC film, a resin film having a lactone structure, or an electromagnetic wave shielding film is preferable. The PET film may have an easy adhesion layer.

  Moreover, this invention is a near-infrared shielding filter which uses the hard-coat material which hardened the said resin composition for hard-coats.

  The near-infrared shielding filter includes a heat ray shielding film, an antireflection film, an antiglare film, a thin display optical filter, and the like.

  The antireflection film is an antireflection film using a hard coat material obtained by curing the hard coat resin composition, and the antireflection film according to the present invention includes the hard coat material and the hard coat material. And a hard coat layer having a refractive index different from that of the hard coat layer.

  The antiglare film is an antiglare film using a hard coat material obtained by curing the resin composition for hard coat.

  Moreover, the said optical filter for thin displays is what uses the said hard-coat material, and may use the said antireflection film or the said anti-glare film.

The near-infrared absorber used in the present invention has characteristic absorption characteristics different from conventional diimonium salts in a dissolved or dispersed state, and can exist stably in an associated state. It can exist very stably in a fine particle dispersed state in the product.
Furthermore, since degradation and degradation are significantly suppressed by irradiation with active energy rays during hard coat resin curing, a resin composition for hard coat having transparency and active energy ray curability can be provided.
The hard coat material using the hard coat resin composition is extremely excellent in heat resistance, moisture resistance, and light resistance.
As a result, the hard coat material using the hard coat resin composition of the present invention is a manufacturing process in the production of near-infrared shielding filters such as heat ray shielding films, antireflection films, antiglare films, and optical filters for thin displays. And cost reduction.

In Test Example 1, it is an absorption spectrum of a dispersion or solution having a concentration of 100 mg / L of the dimonium salt compound obtained in Production Examples 1 to 3 and Production Comparative Examples 1 and 2. In Test Example 1, it is the molar extinction coefficient of the dispersion or solution of each concentration of the diimonium salt compound obtained in Production Example 1. In Test Example 1, it is the molar extinction coefficient of the dispersion liquid of each concentration of the dimonium salt compound obtained in Production Example 2. In Test Example 1, the molar extinction coefficient of a solution obtained by diluting the diimonium salt compound obtained in Production Example 2 with methylene chloride to a concentration of 10 mg / L. In Test Example 1, the molar extinction coefficient of the dispersion or solution of each concentration of the diimonium salt compound obtained in Production Example 3. In Test Example 1, it is the molar extinction coefficient of the dispersion liquid having a concentration of 5 mg / L of the dimonium salt compound obtained in Production Comparative Example 1. In Test Example 1, it is the molar extinction coefficient of a solution obtained by diluting the diimonium salt compound obtained in Production Comparative Example 1 with methylene chloride to a concentration of 10 mg / L. In Test Example 1, it is the molar extinction coefficient of a solution having a concentration of 100 mg / L of the dimonium salt compound obtained in Production Comparative Example 2. In Example 1, it is an absorption spectrum before and behind ultraviolet irradiation of the coating film at the time of near-infrared shielding filter preparation. In Example 2, it is an absorption spectrum before and behind ultraviolet irradiation of the coating film at the time of near-infrared shielding filter preparation. In comparative example 1, it is an absorption spectrum before and behind ultraviolet irradiation of a coating film at the time of near-infrared interception filter preparation. In comparative example 2, it is an absorption spectrum before and behind ultraviolet irradiation of a coating film at the time of near-infrared interception filter preparation.

The present invention is a near-infrared absorptive hard coat resin composition that provides a hard coat material having low scratch resistance and excellent near-infrared absorptivity in a heat-resistant, moisture-resistant, and light-resistant environment.
A near-infrared shielding filter provided with a hard coat layer formed from such a hard coat resin composition has a high visible light transmittance and an excellent near-infrared absorbing ability.

[Near infrared absorber]
The near-infrared absorber used in the near-infrared absorbing hard coat resin composition according to the present invention contains a diimonium salt compound. In the present specification, near infrared means light having a wavelength in the range of 750 to 2000 nm.
The near-infrared absorber includes fine particles of a diimonium salt compound, and the fine particles are an association of a diimonium salt compound. Although details of the aggregate will be described later, the diimonium salt compound to be an aggregate is represented by the following general formula (1).

The organic groups represented by R _{1 to} R _{8 in} the general formula (1) may be the same or different from each other, and are not particularly limited as long as they form an aggregate. Preferred organic groups include , which may be substituted with a halogen atom or a linear or branched _{C 1-10} alkyl _group, a cycloalkyl group of _{C 3-12,} optionally _{C 3-12} cycloalkyl -C be cycloalkyl ring is optionally substituted _{A 1-10} alkyl group etc. can be illustrated. At least one of R _{1 to} R ₈ may be any of these organic groups, but all of R _{1 to} R ₈ are the same, and the cationic structure is symmetric by being one of these organic groups, This is preferable from the viewpoint of easy molecular arrangement necessary for the formation of the aggregate.

As a C _1-10 linear or branched alkyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group N-amyl group, iso-amyl group, 1-methylbutyl group, 2-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 2-dimethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, n- A hexyl group etc. can be illustrated. Of these, branched C _3-6 alkyl groups such as an iso-propyl group, an iso-butyl group, and an iso-amyl group are preferable in that a molecular arrangement necessary for forming an aggregate is obtained. Is preferred.

_Examples of the C _3-12 cycloalkyl group include a cyclopentyl group and a cyclohexyl group.
The C _3-12 cycloalkyl-C _1-10 alkyl group may be substituted or unsubstituted on the cycloalkyl ring. Examples of the substituent that can be substituted include an alkyl group, a hydroxyl group, a sulfonic acid group, and an alkyl group. A sulfonic acid group, a nitro group, an amino group, an alkoxy group, a halogenated alkyl group, or a halogen atom can be exemplified, but preferably an unsubstituted cycloalkyl-alkyl group represented by the following general formula (2): This is preferable because it facilitates the molecular arrangement necessary for forming the aggregate.

In the formula, A represents a linear or branched alkyl group having 1 to 10 carbon atoms, and m represents an integer of 3 to 12.
In the general formula (2), the carbon number of A is preferably 1 to 4, and m is preferably 5 to 8, and particularly preferably 5 to 6. In such a range, the intermolecular interaction required for the association increases. Specifically, cyclopentylmethyl group, 2-cyclopentylethyl group, 2-cyclopentylpropyl group, 3-cyclopentylpropyl group, 4-cyclopentylbutyl group, 2-cyclohexylmethyl group, 2-cyclohexylethyl group, 3-cyclohexylpropyl group 4-cyclohexylbutyl group, etc., among them, cyclopentylmethyl group, cyclohexylmethyl group, 2-cyclohexylethyl group, 2-cyclohexylpropyl group, 3-cyclohexylpropyl group, 4-cyclohexylbutyl group are preferable, and more preferable. Are a cyclopentylmethyl group and a cyclohexylmethyl group, with a cyclohexylmethyl group being particularly preferred.

Examples of the linear or branched C _1-10 alkyl group substituted with a halogen atom include a 2-halogenoethyl group, a 2,2-dihalogenoethyl group, a 2,2,2-trihalogenoethyl group, 3 -Halogenopropyl group, 3,3-dihalogenopropyl group, 3,3,3-trihalogenopropyl group, 4-halogenobutyl group, 4,4-dihalogenobutyl group, 4,4,4-trihalogenobutyl group And halogenated alkyl groups such as a 5-halogenopentyl group, a 5,5-dihalogenopentyl group, and a 5,5,5-trifluoropentyl group. Among these, a monohalogenated alkyl group represented by the following general formula (3) is preferable.

In the above formula, n represents an integer of 1 to 9, and Y represents a halogen atom.
In the general formula (3), n is preferably 1 to 4, and Y is particularly preferably a fluorine atom. In such a range, the intermolecular interaction required for the association increases. Specific examples include monofluoroalkyl groups such as a 2-fluoroethyl group, a 3-fluoropropyl group, a 4-fluorobutyl group, and a 5-fluoropentyl group. A 3-fluoropropyl group, a 4-fluorobutyl group, and a 5-fluoropentyl group are more preferable, and a 3-fluoropropyl group is particularly preferable.

Since the compound having an organic group has a strong intermolecular interaction and exhibits a strong associating property in a dispersed state, it can exist extremely stably in the resin.
By using such a compound, it is possible to provide a resin composition for hard coat in which the diimonium skeleton does not deteriorate even when irradiated with active energy rays when the hard coat resin composition is cured.

On the other hand, X ⁻ in the general formula (1) is an anion necessary for neutralizing the charge of the diimonium cation, and an organic acid anion, an inorganic anion, or the like can be used, but the inorganic anion reduces the solubility of the diimonium salt. This is preferable. Specific examples of inorganic anions include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion, perchlorate ion, periodate ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonic acid. And ions. In particular, hexafluorophosphate ion is preferable in terms of facilitating the molecular arrangement necessary for aggregate formation.

By selecting the anion, the diimonium salt is likely to exhibit a stable fine particle dispersion state. This is considered that the said anion is a molecular size preferable for the aggregate formation in the crystal | crystallization of a diimonium salt. Furthermore, the above-mentioned salt of the diimonium cation having a substituent of R _{1 to} R ₈ and the anion is particularly preferably considered to easily form a molecular arrangement of a stable aggregate.

  A preferred near-infrared absorber contained in the hard coat resin composition of the present invention is an aggregate of the diimonium salt compound (1) thus obtained. This aggregate of diimonium salt compounds is characterized by exhibiting absorption in the wavelength region of 750 nm to 1300 nm and exhibiting a maximum absorption wavelength in the range of 1110 nm to 1250 nm. The aggregate of the diimonium salt compound has a maximum absorption wavelength shifted from the maximum absorption wavelength of the dissolved state of the diimonium salt compound to the long wavelength side of 15 to 200 nm.

  That is, it is known that a dye compound forms an so-called aggregate band in an associated state (a state in which the pigment compound is dispersed as an aggregate), and exhibits an absorption spectrum different from the dissolved state (for example, Photographic Science and Engineering, Vol. .18, No. 323-335 (1974)), generally, the absorption band in the associated state moves to the longer wavelength side than the dissolved state. Conventionally known diimonium salt compounds generally exhibit a maximum absorption wavelength between 1050 nm and 1095 nm in a dissolved state, but the near-infrared absorber used in the present invention shifts to a longer wavelength side of 15 nm to 200 nm due to the formation of aggregates. The absorption maximum is shown at 1110 nm to 1250 nm. If the amount of change due to shift is too large, near infrared absorption near 900 nm to 1100 nm may be insufficient, and the amount of change is preferably 15 nm to 100 nm.

The aggregated absorption wavelength region and the maximum absorption wavelength of the aggregate are as follows: the diimonium salt compound is dispersed in the dispersion medium at a concentration of at least 50 mg / L as particles of 0.001 μm to 10 μm (10 ⁻⁹ m to 10 ⁻⁵ m). It is obtained from an absorption spectrum measured in a floating or suspended state (hereinafter sometimes referred to as “dispersed state”). This particle size is measured by a Microtrac particle size analyzer. More specifically, after adding 0.5 parts of a diimonium salt compound, 9.5 parts of toluene, and 70 parts of zirconia beads having a particle size of 0.3 mm to a 50 ml glass container and shaking with a paint shaker for 2 hours, The liquid obtained by filtering the zirconia beads is determined from the absorption spectrum measured with a spectrophotometer for the diimonium salt compound dispersion diluted with toluene so that the concentration of the diimonium salt compound is 100 mg / L. On the other hand, the maximum absorption wavelength in the dissolved state can be obtained from the absorption spectrum measured with a spectrophotometer for a solution having a concentration obtained by diluting the dimonium salt compound dispersion prepared in this manner with toluene.

Furthermore, the diimonium salt compound may be in the above-mentioned dispersed state as a crystal rather than an aggregate, but in the associated state, the half-value width (wavelength region showing an absorbance at half the absorbance at the absorption maximum) is larger than that in the crystalline dispersed state. A steep absorption band with a small (width) is shown. In the crystal dispersion state, the amount of change in the maximum absorption wavelength with respect to the dissolved state is large and shifts to a longer wavelength side than 1250 nm, and the molar extinction coefficient at the maximum absorption wavelength is 70,000 mol ⁻¹ · L · cm in the associated state. ⁻¹ or more (L means the cell length), but in the crystal dispersion state, it is less than 40,000 mol ⁻¹ · L · cm ^−1, so that the near infrared absorption ability is lower than that in the association state. It will be extremely inferior.

  As described above, whether the diimonium salt compound is in an associated state or a dissolved state is determined by comparing the absorption spectrum measured in the dispersed state with the absorption spectrum measured in the dissolved state. Can be determined from the amount. On the other hand, whether the diimonium salt compound is in an associated state or a crystal dispersed state can be determined by comparing the maximum absorption wavelength of the absorption spectrum measured in the dispersed state and its molar extinction coefficient.

  Therefore, in the hard coat resin composition of the present invention, the near-infrared absorber is dispersed in the resin in an associated state because the hard coat resin composition of the present invention is cured. It can be confirmed by measuring the absorption spectrum and having the absorption characteristics described above.

  The diimonium salt compound (1) used in the present invention can be produced by the following method.

That is, an amino compound represented by the following formula (4) obtained by the Ullmann reaction and the reduction reaction is converted to N-methyl-2-pyrrolidone (hereinafter abbreviated as “NMP”), dimethylformamide (hereinafter referred to as “DMF”). In a polar solvent such as abbreviation), an iodide corresponding to R _{1 to} R ₈ and an alkyl metal carbonate as a deiodizing agent are added and reacted at 30 to 150 ° C., preferably 70 to 120 ° C. Then, an alkyl-substituted product represented by the following formula (5) is obtained. For example, when all of R _{1 to} R ₈ are cyclohexylmethyl groups, a cyclohexylalkane iodide is reacted as the corresponding iodide, and when all of R _{1 to} R ₈ are 3-fluoropropyl groups, a fluoroalkane iodide is reacted. Let On the other hand, when R _{1 to} R ₈ are two or more kinds of different organic groups, the iodides in the number of moles corresponding to the number of the respective organic groups are sequentially reacted in the same manner as described above, or these are simultaneously reacted. It is obtained by adding and reacting. For example, when R _{1 to} R ₈ are a cyclohexylmethyl group and another organic group, a mole number of cyclohexylalkane iodide corresponding to the number of substituents is added, and after the reaction, a corresponding number of moles of iodine are sequentially added. (E.g., fluoroalkane iodide; iodoalkane; alkoxyiodide; benzene iodide; phenyl-1-iodoalkane such as benzyl iodide, phenethyl iodide, etc.) Can be obtained by simultaneously adding and reacting.

In the above formula, R _{1 to} R ₈ have the above-mentioned meanings.

Then, the anion X in which the alkyl substituents and the corresponding as to the above formula (5) ^- a silver salt, NMP, DMF, an organic solvent such as acetonitrile at a temperature 30 to 150 ° C., is reacted preferably at 40 to 80 ° C. After the precipitated silver is filtered off, a solvent such as water, ethyl acetate, hexane or the like is added and the resulting precipitate is filtered to obtain the diimonium salt compound (1).

  The aggregate of the diimonium salt compound can be obtained as a solid fine particle dispersion by using the diimonium salt compound (1) obtained as described above using a known disperser. Examples of the disperser include a ball mill, a vibrating ball mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill, and a roller mill. The dispersers described in JP-A-52-92716 and International Publication No. 88/074794 are used. You can also. Among these, a vertical or horizontal medium disperser is preferable. In dispersing the diimonium salt compound (1), it is not necessary to use a dispersion medium, but it is preferably performed in the presence of the dispersion medium. As a dispersion medium, water or an organic solvent can be used, but for reasons of mixing with a hard coat resin, an organic solvent is preferable, and a coating resin such as toluene, ethyl acetate, or methyl isobutyl ketone is particularly preferable. It is a good solvent. Further, a surfactant may be used, and conventionally known anionic surfactants, anionic polymers, nonionic surfactants and cationic surfactants can be used. In this way, a near-infrared absorber containing the diimonium salt compound (1) in an associated state in the dispersion medium is obtained.

  The mixing ratio of the near-infrared absorber to the hard coat resin composition is not particularly limited. The blending ratio may be adjusted so as to achieve desired properties, particularly efficient near-infrared absorption ability, excellent transparency in the visible light region, heat resistance, and heat-and-moisture resistance. For example, when the dry film thickness of the resin composition for hard coat is set to 1 to 20 μm, the preferable blending ratio of the diimonium salt compound is 0.1 to 30 mass with respect to 100 mass parts of the solid content of the hard coat resin component. Parts, more preferably 0.5 to 20 parts by mass, most preferably 1 to 15 parts by mass. When this blending ratio is less than 0.1 parts by mass, it is difficult to obtain an excellent near-infrared absorbing ability, and conversely, when the blending ratio exceeds 30 parts by mass, the above-described improvement in performance commensurate with the addition amount is not recognized. It is not economical and the transparency in the visible region may be lost. In addition, the mixture ratio of a diimonium salt compound can be changed with the setting of the transmittance | permeability of visible and near-infrared region in the target hard coat material etc., and the thickness of the resin composition layer for hard coats.

[Hard coat resin component]
The resin composition for hard coats according to the present invention has transparency and active energy ray curability. Furthermore, the resin composition for hard coat contains a near-infrared absorber and a resin serving as a base material.
The base resin (hard coat resin component) of the hard coat resin composition is not particularly limited as long as it has transparency and active energy ray curability. This hard coat resin component has active energy curability. That is, the hard coat resin component can be cured by irradiation with active energy rays. The active energy rays are not particularly limited, and examples thereof include electron beams, ultraviolet rays, visible rays, and infrared rays. From the viewpoint of high energy amount and easy curing of the resin, the preferable active energy ray is ultraviolet ray or electron beam, and more preferably ultraviolet ray.
From the viewpoint of active energy ray curability, a preferred hard coat resin component is a radical polymerizable resin. This radical polymerizable resin is not particularly limited, and a radical polymerizable resin having two or more carbon-carbon double bonds in the molecule is preferable. Examples of such radically polymerizable resins include polyester resins, acrylic resins, polyamide resins, polyurethane resins, polyolefin resins, and the like.
The hard coat resin component in the present invention preferably contains a radical polymerizable resin having two or more carbon-carbon double bonds in the molecule, but may be reacted as desired within the range not departing from the object of the present invention. An energy ray-curable radically polymerizable resin other than the above can be blended as a reactive diluent.

[Polymerization initiator]
The resin composition for hard coat of the present invention preferably contains a polymerization initiator. The polymerization initiator is preferably an energy ray-sensitive radical polymerization initiator, and examples thereof include ketone compounds such as acetophenone compounds, benzyl compounds, benzophenone compounds, and thioxanthone compounds.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl. 2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azide Benzalacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1, ben Examples thereof include zoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, and benzoin isobutyl ether.

Examples of the benzyl compound include benzyl and anisyl.
Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like. .

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.
These polymerization initiators can be used alone or in combination of two or more according to the desired performance. Moreover, as a compounding quantity of a polymerization initiator, it is 0.05-20 mass% with respect to hard coat resin component whole quantity, Preferably it is 0.1-20 mass%. When the blending amount of the polymerization initiator is less than 0.05% by mass, the composition may not be cured sufficiently. On the other hand, if the blending amount of the polymerization initiator exceeds 20% by mass, the physical properties of the cured product will not be further improved, rather adversely affected and the economy may be impaired.

[solvent]
The resin composition for hard coats of the present invention may contain a solvent. From the viewpoint of improving the coatability, it is preferable to use a solvent when the hard coat resin composition is applied. This solvent is not particularly limited, and alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol; glycols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene copolymer Solvents: ether glycol solvents such as the glycol solvents monomethyl ether, monoethyl ether, monopropyl ether, monoisopropyl ether, monobutyl ether, etc .; the glycol solvents dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, di Butyl ether, methyl ethyl ether, methyl propyl ether, methyl isopropyl ether, methyl butyl ether Polyether solvents such as ethyl propyl ether, ethyl isopropyl ether and ethyl butyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; hexane, heptane and octane And hydrocarbon solvents such as cyclopentane, cyclohexane, toluene and xylene. These solvent may be used by 1 type and may be used as 2 or more types of mixed solvents. An organic solvent having a boiling point of 200 ° C. or lower is preferable. The water content of the solvent is desirably 5% by mass or less.

[Monofunctional polymerizable compound]
The hard coat resin composition of the present invention may further contain a suitable monofunctional polymerizable compound depending on the purpose. Specific examples of the monofunctional polymerizable compound include acrylamide, (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylate, and isobornyloxyethyl (meth). Acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) Acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide Tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (Meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone phenoxy Ethyl (meth) acrylate, brooxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, bornyl (meth) acrylate, methyl triethylene diglycol (meth) acrylate.

  The hard coat resin composition of the present invention may contain a (meth) acrylic resin depending on the purpose. (Meth) acrylic resin refers to a (meth) acrylic polymer polymerized using (meth) acrylic acid ester as a monomer. The (meth) acrylic polymer may be polymerized using one type of (meth) acrylic acid ester as a monomer, or may be polymerized using two or more types of (meth) acrylic acid ester as a monomer. Alternatively, polymerization may be performed using (meth) acrylic acid ester and a compound copolymerizable with (meth) acrylic acid ester (hereinafter also referred to as “copolymerizable compound”) as monomers. Specific examples of the (meth) acrylic acid ester used as a monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl ( (Meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) C1-C20 alkyl (meth) acrylates such as acrylate and 2-ethylhexyl (meth) acrylate and substituted products thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl Hydroxyl group-containing (meth) acrylates such as (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; carboxyl group-containing (meth) acrylates such as (meth) acrylic acid; phenyl (meth) acrylate, benzyl (meth) ) Aryl (meth) acrylates such as acrylates; alkoxyalkyls such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxypropyl (meth) acrylate, etc. ) Acrylate; oxyalkylene of alcohol such as ethoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenol ethylene oxide (EO) adduct (meth) acrylate, nonylphenol propylene oxide (PO) adduct (meth) acrylate, etc. Examples include (meth) acrylates of adducts; cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, etc. However, (meth) acrylic acid esters other than these compounds may be used. The acrylic acid ester may be used alone or in the form of a mixture of two or more.As the copolymerizable compound used as a monomer as necessary, for example, ethylenic The compound which has an unsaturated bond is mentioned. Here, the compound having an ethylenically unsaturated bond means a compound in which a hydrogen atom of ethylene (CH2 = CH2) is substituted. Other compounds may be used as monomers as long as they can be copolymerized with (meth) acrylic acid esters and do not interfere with the effects of the present invention. Other examples of the copolymerizable compound include aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, vinyl naphthalene, and halogenated styrene; vinyl ester monomers such as vinyl acetate; vinyl chloride, Vinyl halide monomers such as vinylidene chloride; (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, etc. Examples thereof include amide group-containing vinyl monomers; nitrile group-containing monomers such as (meth) acrylonitrile; vinyl ether monomers.

[Additive]
The hard coat resin composition of the present invention may contain an appropriate additive depending on the purpose. Specific examples of additives include leveling agents, pigments, pigment dispersants, UV absorbers, antioxidants, viscosity modifiers, light stabilizers, metal deactivators, peroxide decomposing agents, fillers, and reinforcement. Materials, plasticizers, lubricants, anticorrosives, rust inhibitors, emulsifiers, mold demolding agents, fluorescent whitening agents, organic flameproofing agents, inorganic flameproofing agents, anti-dripping agents, melt flow modifiers, electrostatic Examples thereof include an inhibitor, a slipping imparting agent, an adhesion imparting agent, an antifouling agent, a surfactant, an antifoaming agent, a polymerization inhibitor, a photosensitizer, a surface improver, and a silane coupling agent. In addition, when using a ultraviolet absorber, it cannot be overemphasized that this ultraviolet absorber is used in the quantity of the grade which does not inhibit the superposition | polymerization (hardening) reaction of composite microparticles and a polyfunctional polymerizable compound.

  The resin composition for hard coats of the present invention may contain any appropriate organic fine particles or inorganic fine particles. Typically, these organic fine particles or inorganic fine particles are used for imparting functions according to the purpose (for example, refractive index adjustment, conductivity, antiglare property). Specific examples of the fine particles useful for increasing the refractive index and imparting conductivity of the hard coat resin composition include zinc oxide, titanium oxide, zirconium oxide, aluminum oxide, tin oxide, tin-doped indium oxide, and antimony-doped tin oxide. Indium-doped zinc oxide, indium oxide, antimony oxide and the like. Specific examples of the fine particles useful for lowering the refractive index of the layer made of the resin composition for hard coat include magnesium fluoride, silica, hollow silica and the like. Specific examples of the fine particles useful for imparting antiglare properties include inorganic particles such as calcium carbonate, barium sulfate, talc and kaolin; silicon resin, melamine resin, benzoguanamine resin, acrylic resin, polystyrene resin and the like in addition to the above fine particles. Organic fine particles such as a copolymer resin. These fine particles may be used alone or in combination of two or more.

[Near-infrared absorbing hard coat material]
The near-infrared absorptive hard coat material which concerns on this invention contains the said resin composition for hard coats, and has near-infrared absorptivity. This hard coat material may consist only of a hard coat resin composition, or may have a hard coat resin composition and a substrate. The hard coat material can be used for, for example, a plastic optical component, a touch panel, a film type liquid crystal element, a plastic molded body, and the like. A transparent base material is illustrated as said base material contained in a hard-coat material.

  In this hard coat material, the hard coat layer itself also has a near-infrared absorbing ability, and therefore it is not necessary to separately provide a hard coat layer and a near-infrared absorbing layer. When the hard coat layer and the near infrared absorption layer are provided separately, a base film such as a PET film is required between the near infrared absorption layer and the hard coat layer. However, in the present invention, this base film is unnecessary. It can be said.

[Transparent substrate]
A preferred hard coat material according to the present invention has a transparent substrate. More preferably, the hard coat material has a transparent substrate and a hard coat layer. The transparent substrate is not limited. As the transparent substrate, a sheet-like, film-like or plate-like transparent substrate can be used. Examples of the material of the transparent substrate include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); triacetyl cellulose (TAC); acrylic resins such as methyl methacrylate copolymers; styrene resins; polysulfone resins Polyethersulfone resin; polycarbonate resin; vinyl chloride resin; polymethacrylimide resin; glass and the like.

The transparent substrate may be subjected to easy adhesion treatment. For example, the PET film may be a film subjected to an easy adhesion treatment (easy adhesion PET film). The easy adhesion treatment is preferably performed on at least the surface on which the hard coat layer is provided. Examples of the easy adhesion treatment include a treatment for providing an easy adhesion layer and a treatment for applying a corona treatment to the substrate surface. Examples of the easy adhesion layer include a resin layer for easy adhesion.
Particularly preferred transparent substrates are glass, polyethylene terephthalate (PET) film, triacetyl cellulose (TAC) film or electromagnetic wave shielding film.
The electromagnetic wave shielding film is a film that can shield electromagnetic waves. The electromagnetic wave shielding film can suppress adverse effects on living bodies and electronic devices due to electromagnetic waves generated from a display device, for example. The electromagnetic wave shielding film contains, for example, a metal that can shield electromagnetic waves. A more preferable electromagnetic wave shielding film has an electromagnetic wave shielding layer capable of shielding electromagnetic waves on the surface of the resin film. Examples of the electromagnetic wave shielding layer include a thin film and a metal mesh layer. Examples of the thin film include metal or metal oxide thin films such as silver, copper, indium oxide, zinc oxide, indium tin oxide, and antimony tin oxide. These thin films can be produced by a known method such as a vacuum deposition method, an ion plating method, a sputtering method, a CVD method, or a plasma chemical vapor deposition method. The metal mesh layer is a metal layer provided with mesh-like holes. An example of the metal mesh layer is a metal mesh layer made of copper, silver, or the like. The most typical electromagnetic wave shielding layer is a thin film of indium tin oxide (sometimes abbreviated as ITO). As another electromagnetic wave shielding layer, a laminate in which dielectric layers and metal layers are alternately laminated on a substrate is also suitable. As the dielectric layer, transparent metal oxides such as indium oxide and zinc oxide are suitable, and silver or silver-palladium alloy is generally used as the metal layer. The laminated body is usually laminated so as to be an odd layer between about 3 to 13 layers starting from the dielectric layer.
As a specific example of the electromagnetic wave shielding film, an electromagnetic wave shielding material in which a thin film conductive layer formed by vapor deposition of metal or metal oxide is formed on a transparent substrate (JP-A-1-278800 or JP-A-5-323101). See), an electromagnetic shielding material in which good conductive fibers are embedded in a transparent substrate (see Japanese Patent Laid-Open No. 5-327274 or Japanese Patent Laid-Open No. 5-269912), and a conductive resin containing metal powder or the like on the transparent substrate. An electromagnetic shielding material formed by direct printing (see Japanese Patent Laid-Open No. 62-57297 or Japanese Patent Laid-Open No. 2-52499), a transparent resin layer is formed on a transparent substrate, and copper is formed thereon by electroless plating. Examples thereof include an electromagnetic wave shielding material formed with a mesh pattern (see Japanese Patent Laid-Open No. 5-288989).

[Heat ray blocking film]
The heat ray shielding film which is an example of the near-infrared shielding filter according to the present invention can be produced by a known production method such as a casting method of the hard coat resin composition of the present invention on the transparent substrate.

  In producing the heat ray blocking film, it is possible to use only one or two or more near infrared absorbers. If the near infrared blocking performance near the wavelength of 850 nm is slightly insufficient, phthalocyanine dyes are further used. Further, known dyes such as dithiol-based metal complexes may be added. Further, in order to improve light resistance, an ultraviolet absorbing dye such as benzophenone or benzotriazole may be further added. If necessary, the color tone may be adjusted by adding a known dye having absorption in the visible light region.

[Antireflection film]
The antireflection film which is an example of the near-infrared shielding filter according to the present invention has an antireflection layer. The antireflection layer is usually the outermost layer. The antireflection layer constitutes the surface of the antireflection film.
As an antireflection layer, (1) a layer formed by alternately stacking a layer made of a high refractive index material and a layer made of a low refractive index material, and (2) an intermediate refractive index between the low refractive index material and the high refractive index material. A layer composed of a medium refractive index material, a layer composed of a high refractive index material, and a layer composed of a low refractive index material, (3) a single layer composed of a low refractive index material, etc. can be used. . In the case of an antireflection layer comprising a plurality of layers, the “high refractive index”, “medium refractive index”, and “low refractive index” indicate the magnitude relationship of the refractive index between the layers in the antireflection layer. Specific antireflection layers include, for example, a single layer of a low refractive index layer, a layer having a two-layer structure in which a high refractive index layer / a low refractive index layer are laminated in this order, a high refractive index layer / a low refractive index layer / a high refractive index. Examples thereof include a four-layer structure layered in the order of refractive index layer / low refractive index layer and a three-layer structure layered in the order of medium refractive index layer / high refractive index layer / low refractive index layer. Any antireflection layer may be employed as long as the average reflectance is low and the antireflection performance and visibility are excellent depending on the optical design.

  The antireflection layer preferably comprises the hard coat layer. In this case, the hard coat layer can also function as an antireflection layer. A preferred antireflection layer includes a hard coat layer and a layer having a refractive index different from that of the hard coat layer (hereinafter also referred to as a different refractive index layer). The refractive index difference layer may constitute at least one layer of the antireflection layer. A more preferable antireflection film includes a hard coat layer and a low refractive index layer laminated on the outside of the hard coat layer and having a refractive index lower than that of the hard coat layer. In this case, an antireflection layer is formed by the high refractive index layer composed of the hard coat layer and the low refractive index layer laminated on the outside thereof. The antireflection layer may be provided separately from the hard coat layer.

From the viewpoint of reducing the reflectance, the low refractive index layer preferably has a refractive index of 1.5 or less.
As the low refractive index layer, MgF ₂ (refractive index; about 1.4), SiO ₂ (refractive index; about 1.2 to 1.5), LiF (refractive index; about 1.4), 3NaF · AlF ₃ (refractive index; about 1.4), Na ₃ AlF ₆ (refractive index: about 1.33), or the like can be used. In addition, as the low refractive index layer, those in which fine particles such as MgF ₂ and SiO ₂ are dispersed in ultraviolet and electron beam curable resin or silicon alkoxide matrix can be used, but are not limited thereto. .

  As a method for forming the low refractive index layer, when the low refractive index layer is formed using the matrix containing the low refractive fine particles, the matrix containing the low refractive fine particles is applied so that the film thickness is 0.01 to 1 μm. Thus, a method of performing a drying process, an ultraviolet irradiation process, or an electron beam irradiation process can be employed.

As a method for coating the low refractive index layer, a known method can be used. For example, a method using a rod or a wire bar, or various coating methods such as a micro gravure, a gravure, a die, a curtain, a lip, or a slot can be used. Can do.
The low refractive index layer may be formed by a method such as a vacuum deposition method, a sputtering method, a reactive sputtering method, an ion plating method, or an electroplating method.
In addition, the high refractive index layer includes TiO ₂ (refractive index; 2.3 to 2.7), Y ₂ O ₃ (refractive index; 1.9), La ₂ O ₃ (refractive index; 2.0), ZrO ₂ (refractive _{index; 2.1), Al 2 O 3} ( refractive _{index; 1.6), Nb 2 O 3} ( refractive _{index; 1.9~2.1), In 2 O 3} ( refractive index: 1 .9 to 2.1), Sn ₂ O ₃ (refractive index; 1.9 to 2.1), In—Sn composite oxide (ITO refractive index; 1.9 to 2.1), and the like can be used. As the high refractive index layer, these _{TiO 2, Y 2 O 3,} La 2 O 3, ZrO 2, Al 2 O 3, Nb 2 O 3, In 2 O 3, Sn 2 O 3, In-Sn compound oxide or the like The thing which disperse | distributed the microparticles | fine-particles which consist of in a matrix is illustrated. Examples of the matrix include ultraviolet curable resins, electron beam curable resins, silicon alkoxide compounds, and the like in addition to the hard coat resin component. The hard coat resin composition containing these fine particles may be a high refractive index layer.

In the case of forming with a matrix containing the high refractive fine particles, the high refractive index layer is coated with a matrix containing high refractive fine particles so that the film thickness is 0.01 to 1 μm.
It can be formed by performing a drying process, an ultraviolet irradiation process, and an electron beam irradiation process. In addition, as a coating method, the method similar to the said low-refractive-index layer can be used.
The high refractive index layer may be formed by a method such as a vacuum deposition method, a sputtering method, a reactive sputtering method, an ion plating method, or an electroplating method.
As the medium refractive index layer, a substance having an intermediate refractive index between the low refractive index material and the high refractive index material used can be used. The method for forming the medium refractive index layer is the same as the method for forming the low refractive index layer or the high refractive index layer.

In the antireflection film, another functional layer may be further provided. As the functional layer, for example, a contamination prevention layer, an antistatic layer, an electromagnetic wave shielding layer, a neon light correction layer, and the like can be provided. These functional layers can be formed by a known method using a known material. One layer may have a plurality of functions. These functional layers can be used for the antiglare film and the optical film for thin displays according to the present invention. In particular, when used for display applications, it is preferable to provide the anti-contamination layer on the surface side of the antireflection layer.
Moreover, when the said antireflection film is used for a plasma display use, it is preferable to provide any one or more or all of an electromagnetic wave shielding layer and a neon light correction layer in the antireflection film. The arrangement of these layers is not limited. However, in consideration of visibility and the like, it is preferable to provide the substrate on the side opposite to the side on which the antireflection layer is provided. These electromagnetic wave shielding layers or neon light correction layers can also be used for the antiglare film and the optical film for thin displays.

[Anti-glare film]
The antiglare film which is an example of the near-infrared shielding filter of the present invention uses the above hard coat material. The antiglare film has, for example, the hard coat resin composition having fine particles and a transparent substrate. By adding the fine particles, the antiglare property can be imparted to the layer (hard coat layer) made of the hard coat resin composition. By adding the fine particles, the hard coat layer can also function as an antiglare layer. An antiglare layer may be provided separately from the hard coat layer.
The fine particles for imparting antiglare properties are not particularly limited. Preferably, the fine particles have transparency. Organic fine particles or inorganic fine particles can be used as the fine particles. Preferred fine particles are organic fine particles. The organic fine particles are not particularly limited, and examples thereof include plastic beads. Specific examples of plastic beads include styrene beads (refractive index 1.59), melamine beads (refractive index 1.57), acrylic beads (refractive index 1.49), acrylic-styrene beads (refractive index 1.54), polycarbonate. Examples thereof include beads and polyethylene beads. Silica beads are exemplified as the inorganic fine particles. Further, organic-inorganic composite fine particles disclosed in JP-A-10-330409 and JP-A-2004-307644 may be used. From the viewpoint of further increasing the refractive index of the antiglare layer, it is preferable to use an oxide of at least one metal selected from the group consisting of titanium, zirconium, aluminum, indium, zinc, tin and antimony. In this case, an inorganic filler having an average particle size of 0.2 μm or less, preferably 0.1 μm or less may be used.

  For the antiglare layer, a leveling agent, an ultraviolet absorber, an ultraviolet stabilizer, a fluorescent brightening agent, an antistatic agent, an anti-fingerprint agent and the like can be used. As the leveling agent, a leveling agent generally used in a coating film-forming composition such as a paint can be used.

[Optical filter for thin display]
An optical filter for a thin display, which is an example of the near-infrared shielding filter of the present invention, uses the hard coat material, the antireflection film, or the antiglare film.
The resin composition for hard coat of the present invention is suitable for an optical filter. Due to the association of the dimonium salt compound, the optical filter can effectively absorb near infrared rays. In this optical filter, the total light transmittance in the visible region is preferably 40% or more, and more preferably 50% or more. In this optical filter, the transmittance of near infrared rays having a wavelength of 800 to 1100 nm is preferably 30% or less, more preferably 15% or less.
In addition to the hard coat layer, the optical filter may be provided with a color adjusting layer, a support such as glass, and the like.
The configuration of each layer of the optical filter can be arbitrarily selected. In a preferred optical filter, the antireflection layer or the antiglare layer is the outermost layer (human side). When laminating each layer, physical treatment such as corona treatment or plasma treatment may be performed, or a known high-polarity polymer such as polyethyleneimine, oxazoline-based polymer, polyester or cellulose is used as an anchor coating agent. Also good.
An electromagnetic wave shielding layer may be provided separately from the hard coat layer. Examples of the electromagnetic wave shielding layer include a thin film and a metal mesh layer. Examples of the thin film include metal or metal oxide thin films such as silver, copper, indium oxide, zinc oxide, indium tin oxide, and antimony tin oxide. These thin films can be produced by a known method such as a vacuum deposition method, an ion plating method, a sputtering method, a CVD method, or a plasma chemical vapor deposition method. The metal mesh layer is a metal layer provided with mesh-like holes. An example of the metal mesh layer is a metal mesh layer made of copper, silver, or the like. The most typical electromagnetic wave shielding layer is a thin film of indium tin oxide (sometimes abbreviated as ITO). As another electromagnetic wave shielding layer, a laminate in which dielectric layers and metal layers are alternately laminated on a substrate is also suitable. As the dielectric layer, transparent metal oxides such as indium oxide and zinc oxide are suitable, and silver or silver-palladium alloy is generally used as the metal layer. The laminated body is usually laminated so as to be an odd layer between about 3 to 13 layers starting from the dielectric layer.

  The thin display optical filter may be installed away from the display device or may be directly attached to the display device. When installing away from the display device, glass is preferably used as the support. In the case of directly bonding to a display device, an optical filter that does not use glass is preferable.

  Near-infrared blocking filters such as the above-mentioned hard coat materials, antireflection films, antiglare films, and thin display optical filters can be used in various applications that require blocking of near infrared rays. Specifically, it can be used, for example, as a near-infrared absorption filter for PDP, a near-infrared cut-off filter for automobile glass or building material glass, and can be suitably used as a near-infrared cut-off filter for PDP.

  Conventionally, when a near-infrared absorber containing a diimonium salt compound is used as a near-infrared blocking filter for PDP or the like, a substituent is often devised to use the diimonium salt compound in a dissolved state. Such near-infrared absorbers are often inferior in durability, which is an obstacle to practical use. In addition, there is an example in which a diimonium salt compound is used as a crystal dispersion state, but the crystal becomes coarse due to poor dispersion stability, and its absorption band has a large half-value width and a low absorption coefficient of absorption maximum. For this reason, when used as a near-infrared blocking filter, a sufficient near-infrared absorption effect cannot be obtained, and the crystal is coarse, so that light is scattered and the filter becomes cloudy.

  In contrast, the near-infrared absorber used in the present invention forms an aggregate. A so-called aggregate band is formed to show a steep absorption band with a small half-width of the absorption band, and has an excellent near-infrared absorption ability with a high extinction coefficient of the absorption maximum. Further, the near-infrared absorber used in the present invention is considered to be a molecular assembly formed of several to several tens of molecules, and when used as a near-infrared blocking filter, light scattering is small and transparent. A near-infrared shielding filter with excellent properties can be obtained. Furthermore, when the dimonium salt compound is decomposed, an aminium salt compound that absorbs in the visible light region (around 480 nm) and turns yellow is produced. Since it is stabilized by the interaction between molecules rather than the state, that is, the dissolved state, this aminium salt compound is unlikely to be produced, and is considered to be excellent in heat resistance, moisture resistance and light resistance.

  This aggregate is also suitable as a near-infrared absorber to be included in a near-infrared absorbing hard coat resin composition because it is less likely to deteriorate due to the above-described reasons even when irradiated with active energy rays irradiated during hard coating agent curing. It is.

  EXAMPLES Hereinafter, an Example is given and this invention is demonstrated in detail. In addition, this invention is not limited at all by this Example.

Production Example 1
Preparation of hexafluorophosphate-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium:
To 100 parts of DMF, 10 parts of N, N, N ′, N′-tetrakis (p-aminophenyl) -p-phenylenediamine, 63 parts of cyclohexylmethyl iodide and 30 parts of potassium carbonate were added and reacted at 120 ° C. for 10 hours. . Next, the reaction solution is added to 500 parts of water, and the resulting precipitate is filtered, washed with 500 parts of methyl alcohol, dried at 100 ° C., and N, N, N ′, N′-tetrakis {p-di ( 24.1 parts of (cyclohexylmethyl) aminophenyl} -p-phenylenediamine were obtained.
To 24.1 parts of the obtained N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediamine, 200 parts of DMF and 7.9 parts of silver hexafluorophosphate were added. The mixture was reacted at 60 ° C. for 3 hours, and the produced silver was filtered off. Next, 200 parts of water was added to the filtrate, and the resulting precipitate was filtered and dried to give hexafluorophosphate-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl. } -P-phenylene dimonium 27.0 parts were obtained.

Production Example 2
Preparation of hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p-di (3-fluoropropyl) aminophenyl} -p-phenylenediimonium:
Instead of 63 parts of cyclohexylmethyl iodide, hexafluorophosphoric acid -N, N, N ', N'- was prepared in the same manner as in Production Example 1, except that 1-iodo-3-fluoropropane having the same mole number was used. 18 parts of tetrakis {p-di (3-fluoropropyl) aminophenyl} -p-phenylenediimonium were obtained.

Production Example 3
Preparation of hexafluorophosphate-N, N, N ′, N′-tetrakis {p-di (iso-butyl) aminophenyl} -p-phenylenediimonium:
Instead of 63 parts of cyclohexylmethyl iodide, hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p-dioxide was prepared in the same manner as in Production Example 1 except that isobutyl iodide having the same number of moles was used. 18 parts of (iso-butyl) aminophenyl} -p-phenylene dimonium were obtained.

Production Comparative Example 1
Preparation of hexafluoroantimonic acid-N, N, N ′, N′-tetrakis {p-di (n-propyl) aminophenyl} -p-phenylenediimonium:
Instead of 63 parts of cyclohexylmethyl iodide, N, N, N ′, N′-tetrakis {p-di (n-propyl) was prepared in the same manner as in Production Example 1 except that 1-iodopropane having the same mole number was used. ) 24.1 parts of aminophenyl} -p-phenylenediamine were obtained.
To 24.1 parts of the obtained N, N, N ′, N′-tetrakis {p-di (n-propyl) aminophenyl} -p-phenylenediamine, 200 parts of DMF and 12.9 parts of silver hexafluoroantimonate were added. In addition, the mixture was reacted at 60 ° C. for 3 hours, and the produced silver was separated by filtration. Next, 200 parts of water was added to the filtrate, and the resulting precipitate was filtered and dried to give hexafluoroantimonic acid-N, N, N ′, N′-tetrakis {p-di (n-propyl) amino. Phenyl} -p-phenylenediimonium (28.0 parts) was obtained.

Production Comparative Example 2
Preparation of tetrafluoroboric acid-N, N, N ′, N′-tetrakis {p-di (n-propyl) aminophenyl} -p-phenylenediimonium:
N, N, N ′, N′-tetrakis {p-di (n-propyl) aminophenyl} -p-phenylenediamine obtained in the same manner as in Production Comparative Example 1 was added with 250 parts of acetone and silver tetrafluoroborate 14 .5 parts was added and reacted at 60 ° C. for 3 hours, and the resulting silver was filtered off. Subsequently, 200 parts of water was added to the filtrate, and the produced precipitate was filtered and dried, followed by tetrafluoroboric acid-N, N, N ′, N′-tetrakis {p-di (n-propyl) amino. 29.9 parts of a near-infrared absorbing dye of phenyl} -p-phenylenediimonium was obtained.

Test example 1
0.5 part of hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium obtained in Production Example 1 and 9.5 parts of toluene And 70 parts of zirconia beads having a particle size of 0.3 mm were added to a 50 ml glass container and shaken with a paint shaker for 2 hours, and then the zirconia beads were separated by filtration to prepare a diimonium salt compound dispersion. This dispersion was diluted with toluene, prepared to have concentrations of 5, 20, 50 and 100 mg / L, and the absorbance was measured with a spectrophotometer U-4100 (manufactured by Hitachi High-Tech). Absorbance was measured in the same manner for the diimonium salt compounds obtained in Production Examples 2-3 and Production Comparative Examples 1-2. FIG. 1 shows the absorbance of each dimonium salt compound at a dimonium salt compound concentration of 100 mg / L. The diimonium salt compounds of Production Example 2 and Production Comparative Example 1 were not dissolved even when diluted to 5 mg / L, and were almost insoluble in toluene. The compound concentration was adjusted to 10 mg / L. The molar extinction coefficient of each dispersion or solution of each concentration of each dimonium salt compound is shown in FIGS. Table 1 shows the maximum absorption wavelength in the dissolved state and the associated state of each dimonium salt compound, the amount of change in the long wavelength shift, the molar extinction coefficient and the half width at the maximum absorption wavelength in the dispersed state.

※結晶分散状態

* Crystal dispersion state

From Table 1, it was shown that the diimonium salt compounds of Production Examples 1 to 3 formed an aggregate, and the maximum absorption wavelength shifted to a longer wavelength side of about 20 nm to 150 nm than the dissolved state. On the other hand, the diimonium salt compound of Production Comparative Example 1 was in a crystal dispersion state, and its maximum absorption wavelength was 1356 nm, which was shifted to the longer wavelength side of 284 nm compared to the dissolved state. Since this amount of change is large, the near-infrared absorption effect is extremely poor. The diimonium salt compound of Production Comparative Example 2 was in a dissolved state with a maximum absorption wavelength of 1070 nm even at a concentration of 100 mg / L. Further, even when the concentration was increased, the shift of the maximum absorption wavelength toward the long wavelength side was not shown.
Further, as can be seen from FIG. 1, the dispersions of the diimonium salt compounds of Production Example 1, Production Example 2 and Production Example 3 have a small half-value width and a steep absorption band as compared with the dispersion liquid of Production Comparative Example 1. It was shown to be excellent in the near-infrared absorption effect.

Example 1
Infrared blocking filter production:
1 part of hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium obtained in Preparation Example 1, 9 parts of toluene, and particle size After adding 70 parts of 0.3 mm zirconia beads to a 50 ml glass container and shaking with a paint shaker for 2 hours, the zirconia beads were separated by filtration to obtain a diimonium salt compound dispersion. 14 parts of this dimonium salt compound dispersion in a solution of 28 parts UV curable hard coat agent UN-3320HC (manufactured by Negami Kogyo Co., Ltd.), 28 parts methyl isobutyl ketone, and 28 parts toluene are mainly composed of urethane acrylate resin. In addition, Irgacure 184 (manufactured by Ciba Specialty), which is a photopolymerization initiator, was added to obtain an ink. This was applied to a 50 μm thick PET film (A4300, manufactured by Toyobo Co., Ltd.), which is a transparent substrate, with a bar coater No. 12 was applied and dried at 100 ° C. for 1 minute. Thereafter, the coating film was polymerized and cured by irradiating ultraviolet rays so as to be 60 mJ / cm ² , thereby obtaining a near-infrared shielding filter.

Example 2
Hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium instead of hexafluorophosphoric acid-N, N obtained in Production Example 2 , N ′, N′-tetrakis {p-di (3-fluoropropyl) aminophenyl} -p-phenylenediimonium was used to produce a near-infrared cut-off filter in the same manner as in Example 1.

Comparative Example 1
Hexafluorophosphoric acid-N, N, N ′, N′-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium instead of hexafluoroantimonic acid-N obtained in Production Comparative Example 1, A near-infrared blocking filter was prepared in the same manner as in Example 1 except that N, N ′, N′-tetrakis {p-di (n-propyl) aminophenyl} -p-phenylenediimonium was used.

Comparative Example 2
Hexafluorophosphoric acid-N, N, N ', N'-tetrakis {p-di (cyclohexylmethyl) aminophenyl} -p-phenylenediimonium tetrafluoroboric acid-N obtained in Production Comparative Example 2, A near-infrared shielding filter was prepared in the same manner as in Example 1 except that N, N ′, N′-tetrakis {p-di (n-propyl) aminophenyl} -p-phenylenediimonium was used. It was impossible to form a film.

Test example 2
Performance evaluation of near infrared filter:
The haze (turbidity) of the near-infrared shielding filters obtained in Examples 1-2 and Comparative Examples 1-2 was measured with a turbidimeter NDH5000 (Nippon Denshoku Industries Co., Ltd.). Moreover, the pencil scratch test was done based on JIS-K5400, and the evaluation by an abrasion was performed. These near-infrared cut-off filters were stored in an atmosphere at a temperature of 80 ° C. and subjected to a heat resistance test, and the transmittance at a wavelength of 1000 nm and 480 nm after a predetermined time was measured with a spectrophotometer. Furthermore, it was stored in an atmosphere at a temperature of 60 ° C. and a humidity of 95% to conduct a moist heat resistance test, and the transmittance at wavelengths of 1000 nm and 480 nm was measured in the same manner as the heat resistance test. The haze measurement and pencil scratch test results are shown in Table 2, the heat resistance test results are shown in Table 3, and the moist heat resistance test results are shown in Table 4, respectively.

＊８０℃耐熱性試験結果

* 80 ° C heat resistance test results

＊６０℃／９５％耐湿熱性試験結果

* 60 ° C / 95% wet heat resistance test results

  As is clear from Table 2, the near-infrared cutoff filters of Examples 1 and 2 containing the diimonium salt compound as an aggregate are more transparent than the filter of Comparative Example 1 contained in a crystal dispersion state, In Comparative Example 2, which was in a dissolved state, it was impossible to form a film due to inhibition of curing of the resin.

From the results shown in FIGS. 9 to 12, the near-infrared blocking filters of Examples 1 and 2 do not show any degradation of the dye due to ultraviolet irradiation during film formation. Is partially decomposed, suggesting that the near infrared absorption ability is deteriorated.
As shown in Tables 3 and 4, it was revealed that the near-infrared cut-off filters of Examples 1 and 2 had higher near-infrared absorbing ability than Comparative Example 1, and were excellent in heat resistance and moist heat resistance.

  The near-infrared absorbing hard coat resin composition of the present invention is excellent in heat resistance and moisture resistance, has high visible light permeability, and does not decrease near-infrared absorption over a long period of time. The near-infrared blocking filter provided with the hard coat resin composition can be used for various applications such as for PDP, automotive glass, and building glass, and is particularly suitable as a near-infrared blocking filter for PDP.

Claims (7)

A hard coat resin composition comprising a near-infrared absorber containing an aggregate of a compound represented by the following general formula (1) dispersed in an active energy ray-curable resin , the hard coat resin composition comprising: A hard coat resin composition , wherein an absorption spectrum of a hard coat layer obtained by curing exhibits an absorption maximum at 1110 nm to 1250 nm .

(In the formula, R _{1 to} R ₈ each represents an organic group which may be the same or different, and X ⁻ represents an anion.) The R _{1 to} R ₈ in the general formula (1) are all at least one organic group selected from the group consisting of a cyclohexylmethyl group, a 3-fluoropropyl group, and an iso-butyl group. 2. The resin composition for hard coat according to 1.   The active energy ray-curable resin is at least one resin selected from the group consisting of a polyester resin, an acrylic resin, a polyamide resin, a polyurethane resin, and a polyolefin resin. 2. The resin composition for hard coat according to 2.   The near-infrared absorptive hard-coat material which comprised the hard-coat layer formed by hardening | curing the resin composition for hard-coats of Claim 1 thru | or 3 by active energy ray irradiation.   The near-infrared absorbing hard coat material according to claim 4, wherein the hard coat layer is formed on at least one surface of a transparent substrate.   6. The near-infrared absorbing hard coat material according to claim 5, wherein the transparent substrate is at least one transparent substrate selected from the group consisting of glass, PET film, TAC film and electromagnetic wave shielding film.   The near-infrared shielding filter which uses the near-infrared absorptive hard-coat material in any one of Claims 4-6.

Images