KR101304626B1 - Pressure-sensitive adhesive optical film and pressure-sensitive adhesive composition - Google Patents

Abstract

assignment
In the adhesion layer containing a dimonium pigment | dye, the means for improving the durability of a pigment | dye is provided.
Solution
It has an acrylic polymer, a near-infrared absorption adhesive layer containing a dimonium pigment | dye, and a base material layer, The needle-shaped optical film characterized by the needle-like aggregate of the said dimonium pigment being scattered in the said near-infrared absorption adhesive layer. do..

Description

Adhesive type optical film and adhesive composition {PRESSURE-SENSITIVE ADHESIVE OPTICAL FILM AND PRESSURE-SENSITIVE ADHESIVE COMPOSITION}

TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive optical film and a pressure-sensitive adhesive composition, and more particularly, to a pressure-sensitive adhesive optical film having a near-infrared absorptive pressure-sensitive adhesive layer and a pressure-sensitive adhesive composition used for forming the pressure-sensitive adhesive layer.

Plasma displays emit electromagnetic waves, neon lights, or near-infrared rays simultaneously with visible light due to the light emission principle. They need to be shielded because they have an undesirable effect. Thus, an optical film is used.

In addition to the above functions, in order to increase the image quality, in order to have various functions such as reflection prevention on the viewer side and improvement of contrast, an optical film having a plurality of layers laminated thereon has been used. However, in recent years, there is a demand for the simplification of these optical films, and there is a tendency to reduce the cost by simplifying the layer configuration of the film. Therefore, it is proposed to have various functions in the adhesion layer used for an optical film.

An optical film containing a near infrared absorber has been proposed as a means of shielding near infrared rays. Although various substances are proposed as this near-infrared absorber, the dimonium pigment | dye with a wide near-infrared absorption wavelength range is used frequently, and what mix | blends the said immonium pigment | dye in an adhesive is proposed (patent document 1).

The dimonium pigment | dye may be inferior in durability, and may raise the problem of the fall of near-infrared absorptivity, or coloring. In order to solve this problem, the adhesive composition which mixed the dimonium pigment | dye of the association state disperse | distributed to the solvent to the adhesive is proposed (patent document 2).

Japanese Patent Laid-Open No. 2008-58472 Japanese Patent Application Laid-Open No. 2010-18773

This invention aims at providing the means for improving the durability of a pigment | dye in the adhesion layer containing a dimonium pigment | dye.

This invention (1) has a near-infrared absorption adhesive layer and base material layer containing an acrylic polymer and a dimonium pigment | dye,

It is a pressure-sensitive adhesive optical film, wherein needle-like aggregates of the dimonium pigment are scattered in the near-infrared absorption adhesive layer.

In the present invention (2), the adhesive optical film is coated with a coating liquid containing the acrylic polymer, the dimonium pigment, and the solvent on the base material layer, and the aging of the near-infrared absorption adhesive layer obtained by drying is performed. It is obtained by forming the acicular aggregate of an immonium pigment | dye, It is the adhesive optical film of the said invention (1) characterized by the above-mentioned.

The present invention (3) is characterized in that the near-infrared absorption adhesive layer contains a crosslinking agent or a combination of two or more crosslinking agents as long as the near-infrared absorbent layer is selected from the group consisting of an epoxy crosslinking agent, an isocyanate crosslinking agent, an imine crosslinking agent, and a peroxide crosslinking agent. It is the adhesive optical film of invention (1) or (2).

This invention (4) is the adhesive optical film in any one of said invention (1)-(3) which the said near-infrared absorption adhesive layer contains a rust preventive agent.

This invention (5) is the adhesive optical film in any one of said invention (1)-(4) characterized by the metal mesh film sticking to the said near-infrared absorption adhesive layer.

This invention (6) is a plasma display panel in which the adhesive optical film in any one of said invention (1)-(5) is affixed on the surface.

The present invention (7) contains an acrylic polymer and a dimonium pigment,

The content of the amine additive is 10 parts by weight or less based on 100 parts by weight of the acrylic polymer,

The acid value of the said acrylic polymer is 7-50 mgKOH / g, It is a near-infrared absorption adhesive composition characterized by the above-mentioned.

The present invention (7-2) contains an acrylic polymer and a dimonium pigment,

The acid value of the said acrylic polymer is 15-50 mgKOH / g, It is a near-infrared absorption adhesive composition characterized by the above-mentioned. By setting it as the acid value of the said range, it is easy to form the acicular aggregate of a dimonium pigment | dye, and the adhesive optical film with high durability of a pigment | dye can be obtained.

This invention (8) is the near-infrared absorption adhesive composition of the said invention (7) characterized by the said acrylic polymer containing the alkyl (meth) acrylate monomer and carboxyl group-containing monomer which have 4-12 carbon atoms of an alkyl group.

In the present invention (9), the dimonium pigment is a dimonium cation of the following formula (1),

(Formula (1) of, R ¹ ~R ⁸ are may be the same or different and each represents a hydrogen atom, a halogen group, an alkyl group, a halogenated alkyl group, a cyano group, an aryl group, a hydroxyl group, a phenylalkyl group or alkoxy)

The near-infrared absorption adhesive composition of the said invention (7) or (8) which consists of counteranions of following formula (2).

(In Formula (2), R ^<a> , R <^b> may be same or different and represents a fluorine atom or a fluorinated alkyl group.)

The invention (10) is characterized in that it further contains a crosslinking agent or a combination of two or more crosslinking agents as long as it is selected from the group consisting of an epoxy crosslinking agent, an isocyanate crosslinking agent, an imine crosslinking agent, and a peroxide crosslinking agent. It is a near-infrared absorption adhesive composition in any one of (9).

This invention (11) is a near-infrared absorption adhesive composition in any one of said invention (7)-(10) characterized by containing a rust preventive agent.

According to this invention, since a dimonium pigment | dye forms an aggregate, the adhesive optical film with which the said pigment | dye has high durability can be obtained. Moreover, since the adhesive layer can be made to have an infrared absorption function, the number of layer structures as an optical film can be reduced.

Moreover, the adhesive optical film which has higher pigment | dye durability can be obtained by making a dimonium pigment | dye aggregate after apply | coating and drying the coating liquid containing an acrylic polymer.

In addition, the content of the amine additive is 10 parts by weight or less (preferably 1 part by weight or less, more preferably 0 part by weight) with respect to 100 parts by weight of the acrylic polymer, and an infrared ray having an acid value of the acrylic polymer in a predetermined range. An adhesive composition has the effect that it is easy to form needle aggregate especially at the time of aging after drying of the coating liquid containing this adhesive composition.

BRIEF DESCRIPTION OF THE DRAWINGS It is the microscope picture seen from the surface of the near-infrared absorption adhesion layer of the adhesive optical film manufactured in the Example.
FIG. 2 is a micrograph which further enlarges the surface of the near-infrared absorption adhesive layer of the adhesive optical film manufactured in the Example.
3 is a transmission spectrum obtained as a result of the measurement by the spectrophotometer of the test sample according to Example 1 ((a) is the spectrum before and after the heat resistance test, and (b) is the spectrum before and after the heat and humidity resistance test.
4 is a transmission spectrum obtained as a result of the measurement by the spectrophotometer of the test sample according to Example 2 ((a) is the spectrum before and after the heat resistance test, and (b) is the spectrum before and after the heat and humidity resistance test.
5 is a transmission spectrum obtained as a result of the measurement by the spectrophotometer of the test sample according to Example 3 ((a) is the spectrum before and after the heat resistance test, and (b) is the spectrum before and after the heat and humidity resistance test.
6 is a transmission spectrum obtained as a result of the measurement by the spectrophotometer of the test sample according to Example 4 ((a) is the spectrum before and after the heat resistance test, and (b) is the spectrum before and after the heat and humidity resistance test.

[Adhesive Optical Film]

The adhesive optical film which concerns on this invention has a near-infrared absorption adhesive layer and base material layer containing an acrylic polymer and a dimonium pigment | dye. The present invention is characterized in that needle-like aggregates of dimonium pigments are scattered in the near-infrared absorption adhesive layer. Thus, the dimonium pigment | dye aggregates and the durability of a dimonium pigment | dye becomes high.

(Near infrared absorption adhesion layer)

BRIEF DESCRIPTION OF THE DRAWINGS It is the microscope picture seen from the surface of the near-infrared absorption adhesion layer of the adhesive optical film of Example 4 manufactured in the Example. The slight blur in the picture is the scattering of needle aggregates. In addition, white spots are dust mixed in at the time of manufacture or observation. 2 is a micrograph showing the surface of the near-infrared absorption adhesive layer further enlarged. In this way, the near-infrared absorption adhesion layer which concerns on this invention can confirm that the needle aggregate is scattered. The agglomerates have respective nuclei, and a large number of acicular agglomerates are scattered radially around the nucleus, and when observed from the surface of the near-infrared absorbing adhesive layer, it can be observed macroscopically as a circular aggregate ( The lines 1, 2 and 3 in the figure represent the diameters of the corresponding circular aggregates). Thus, when aggregate of a dimonium pigment | dye is formed, since these pigment | dyes become difficult to decompose, durability of a pigment | dye improves.

As mentioned later, the near-infrared absorption adhesive layer which concerns on this invention aggregates a dimonium pigment | dye by aging after forming and drying the coating film of an adhesive composition, not the method of using a dispersion liquid or agglomerating in a liquid state. Through this process, needle-like aggregates as shown in FIG. 2 are formed, whereby high immonium stability is exhibited.

Moreover, 10-500 micrometers is preferable, as for the average diameter when observed from the upper surface of the near-infrared absorption adhesion layer of the circular aggregate of aggregate, 30-400 micrometers is more preferable, 50-300 micrometers is still more preferable. Although it is not certain, it is thought that the needle aggregate aggregates grow in the vertical direction to the ground surface more than the center of the circular aggregate shown in FIG. 2, and gradually turns in the horizontal direction to form the needle aggregate aggregate radially. In such a case, the length of the acicular aggregate is considered to be a value close to the numerical range of the circular aggregate.

Although the thickness of a near-infrared absorption adhesion layer is not specifically limited, 5-100 micrometers is preferable, 10-50 micrometers is more preferable, 15-35 micrometers is still more preferable.

(Adhesive Composition)

It is preferable to form the near-infrared absorption adhesive layer which concerns on this invention with the adhesive composition containing an acrylic polymer and a dimonium pigment | dye. It is preferable that content of an amine additive is 10 weight part or less with respect to 100 weight part of said acrylic polymers, and the acid value of the said acrylic polymer is 7-50 mgKOH / g. Under conditions where the amine additive is hardly contained (content of the amine additive is 10 parts by weight or less with respect to 100 parts by weight of the acrylic polymer), by aging the pressure-sensitive adhesive composition after coating and drying the adhesive composition within the above range. Aggregates tend to form. In particular, when content of an amine additive is contained more than 10 weight part with respect to 100 weight part of acrylic polymer, a dimonium pigment | dye will react with an amine and will decompose | disassemble before forming the aggregate of the said pigment | dye. In the above range, the higher acid value tends to form aggregates. However, even if the lower acid value does not contain an amine additive, by providing a high temperature for a long time (for example, 3 days or more at 35 ° C), the aggregates Can be obtained to obtain an infrared absorbing pressure-sensitive adhesive layer having high durability.

Moreover, 15-50 mg KOH / g is preferable and, as for an acid value, 20-40 mg KOH / g is more preferable. By setting it as such a range, aggregate is more easily formed and the near-infrared absorption adhesion layer which has a high durability for a dimonium pigment | dye can be obtained.

Moreover, although the adhesive composition which concerns on this invention can add various additives, it is preferable that it does not contain an amine additive. When an amine substance is added, in the manufacturing process of the near-infrared absorption adhesion layer mentioned later, before a needle aggregate of a dimonium pigment | dye is formed, a dimonium pigment | dye and an amine may react and this pigment | dye may decompose | disassemble. An amine additive means the substance which has a non-covalent electron pair which has aggressiveness on nitrogen atoms, such as a primary amine, a secondary amine, or a tertiary amine. An amine-containing tackifier is mentioned as an amine additive. The amine additive is preferably 50 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 1 part by weight, even more preferably 0.1 parts by weight or less, and no content at all based on 100 parts by weight of the acrylic polymer. Not particularly preferred.

Acrylic system Polymer

It is preferable that the acryl-type polymer which concerns on this invention contains an alkyl (meth) acrylate monomer at least, and is obtained by superposing | polymerizing at least 1 sort (s) chosen from a carboxyl group-containing monomer and a hydroxyl-containing monomer, and the said alkyl (meth) acrylate monomer. It is more preferable. Among these polymers, it is preferable to use an acrylic polymer which is polymerized by containing an alkyl (meth) acrylate {(meth) acrylic acid alkyl ester} monomer having 4 to 12 carbon atoms of an alkyl group and a carboxyl group-containing monomer. It is preferable that 50 weight part or more of acrylic polymers are contained with respect to 100 weight part of near-infrared absorption adhesion layer solid content components, and the range of 60-99.9 weight part is more preferable.

Although it does not restrict | limit especially as alkyl (meth) acrylate (alkyl acrylate, acryl methacrylate), For example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate , t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (Meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acryl The rate etc. are mentioned. Moreover, the alkyl (meth) acrylate as a monomer component can be used individually or in combination of 2 or more types. Among these acrylates, the single-unit of n-butyl (meth) acrylate is particularly preferable. Although content of alkyl (meth) acrylate should just be 1-100 weight% in 100 weight part of acrylic polymers, 50-99% is preferable and 70-98% is more preferable.

Although it does not specifically limit as a carboxyl group-containing monomer, For example, (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. are mentioned. Moreover, the anhydride of these carboxyl group-containing monomer can also be used as a carboxyl group-containing monomer. Although the ratio of a carboxyl group-containing monomer can be arbitrarily set according to the value of said acid value, 1-24 weight% is preferable in 100 weight part of acrylic polymers, for example, 3-20 weight% is more preferable.

Although the monomer component of an acryl-type polymer was demonstrated, it is preferable not to have a hydroxyl group (OH group) among these compositions. By not having a hydroxyl group in this way, the dimonium pigment | dye in an adhesive composition becomes difficult to decompose and the durability of this pigment | dye increases. Although not specifically limited, it is preferable that the hydroxyl-containing monomer contained in the adhesive composition of this invention is 10 weight% or less in 100 weight part of acrylic polymers, It is more preferable that it is 1 weight% or less, It is further more preferable that it is 0.1 weight% or less, Particularly preferred is not included.

Although an acryl-type polymer can be manufactured by a well-known polymerization method, For example, the solution polymerization method, an emulsion polymerization method, the bulk polymerization method, the polymerization method by ultraviolet irradiation, etc. are mentioned. Moreover, the polymerization initiator, chain transfer agent, etc. which are used at the time of superposition | polymerization can use a well-known thing suitably.

100,000-2 million are preferable, as for the weight average molecular weight of an acrylic polymer, 300,000-1,500,000 are more preferable, and 400,000-1,200,000 are still more preferable.

Dimonium  Pigment

The adhesive composition which concerns on this invention contains a dimonium pigment | dye. It is preferable to have a dimonium cation represented by following formula (1) also in a dimonium pigment | dye.

However, in formula (1), R <^1> -R <^8> may be same or different and represents a hydrogen atom, a halogen group, an alkyl group, a halogenated alkyl group, a cyanoalkyl group, an aryl group, a hydroxyl group, a phenylalkylene group, or an alkoxy group. The R ¹ to R ⁸ group is not particularly limited as long as it is the above substituent, but an alkyl group having 1 to 20 carbon atoms (preferably 1 to 8) or a linear or branched chain, a C 3 to 12 cyclic alkyl group, a cyanoalkyl group or an alkoxy group Halogenated alkyl groups etc. are preferable. As an aryl group, a C6-C14 aryl group is preferable.

More specific examples of general formula R include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, t Linear or branched alkyl groups such as -pentyl group, n-hexyl group, n-octyl group, cyclopentylmethyl group, cyclohexylmethyl group, 2-cyclopentylethyl group, 2-cyclopentylpropyl group, 3-cyclopentylpropyl group, 4 Cycloalkyl groups, such as cyclopentyl butyl group, 2-cyclohexylethyl group, 2-cyclohexylpropyl group, 3-cyclohexylpropyl group, and 4-cyclohexyl butyl group, cyanomethyl group, 2-cyanoethyl group, 3-cya Nopropyl group, 2-cyanopropyl group, 4-cyanobutyl group, 3-cyanobutyl group, 2-cyanobutyl group, 5-cyanopentyl group, 4-cyanopentyl group, 3-cyanopentyl group, Cyano substituted (C1-C8) alkyl groups such as 2-cyanopentyl group, 6-cyanohexyl group, 5-cyanohexyl group, 4-cyanohexyl group, 3-cyanohexyl group, 2-cyanohexyl group, phenyl group, naph Tilt , Anthracenyl group, methoxymethyl, 2-methoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 4-methoxybutyl, 3-methoxybutyl, 2-methoxybutyl, 5-methoxypentyl , 4-methoxypentyl, 3-methoxypentyl, 2-methoxypentyl, 6-methoxyhexyl, ethoxymethyl, 2-ethoxyethyl, 3-ethoxypropyl, 2-ethoxypropyl, 4-e Methoxybutyl, 3-ethoxybutyl, 5-ethoxypentyl, 4-ethoxypentyl, 6-ethoxyhexyl, propoxymethyl, 2-propoxyethyl, 3-propoxypropyl, 4-propoxybutyl, 5 Linear or branched alkoxy alkyl groups such as propoxypentyl, trifluoromethyl groups, 2,2,2-trifluoroethyl groups, 3,3,3-trifluoropropyl groups, 4,4,4-trifluoro Butyl group, 5,5,5-trifluoropentyl group, 6,6,6-trifluorohexyl group, 8,8,8-trifluorooctyl group, 2-methyl-3,3,3-tri Fluoropropyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluorohexyl group, perfluoro Octyl group, 2-trifluoro-propyl group, trichloromethyl group, 2,2,2-trichloroethyl group, 3,3,3-trichloroopropyl group, 4,4,4-trichlorobutyl group, 5 , 5,5-trichloropentyl group, 6,6,6-trichlorohexyl group, 8,8,8-trichlorooctyl group, 2-methyl-3,3,3-trichloropropyl group, perchloroethyl group , Perchloropropyl group, perchlorobutyl group, perchlorohexyl group, perchlorooctyl group, 2-trichloro-perchloropropyl group, tribromomethyl group, 2,2,2-tribromoethyl group, 3,3 , 3-tribromopropyl group, 4,4,4-tribromobutyl group, 5,5,5-tribromopentyl group, 6,6,6-tribromohexyl group, 8,8,8-t Libromooctyl group, 2-methyl-3,3,3-tribromopropyl group, perbromoethyl group, perbromopropyl group, perbromobutyl group, perbromohexyl group, perbromooctyl group, 2-tribromo- Although halogenated alkyl groups, such as a perbromopropyl group, are mentioned, It is not limited to this.

The kind of counter anion in dimonium pigment | dye is not specifically limited. As counter anions, for example, halogen ions such as fluorine ions, chlorine ions, bromine ions and iodine ions, perchlorate ions, periodate ions, tetrafluoroborate ions, hexafluoro phosphate ions and hexafluoro antimonic acid Ions, trifluoro methane sulfonic acid ions, toluene sulfonic acid ions, bis (trifluoromethanesulfone) imide ions, tetrakis (pentafluorophenyl) boric acid ions, tris (trifluoromethanesulfone) methide ions, And sulfonimide anions.

Among these, a sulfonimide anion is especially preferable, and especially a fluorine-containing sulfonimide anion represented by following General formula (2) is preferable. By using the fluorine-containing sulfonimide anion in this manner, it is particularly easy to form aggregates.

However, in Formula (2), R ^<a> , R <^b> may be same or different and represents a fluorine atom or an alkyl fluoride group. Although it will not specifically limit, if it is the said substituent as R ^<a> , R <^b> , C1-C8 alkyl fluoride is mentioned.

In addition, a dimonium pigment | dye can be manufactured by a well-known method, For example, bis (fluorosulfonyl) imide acid prepared by the method of Unexamined-Japanese-Patent No. 8-511274, and US Patent No. 5,874,616. The fluorinated alkanesulfonyl-fluorosulfonylimide acid prepared according to the specification is used as an anion component, and silver is applied to the bis (fluorosulfonyl) imide acid silver or the fluorinated alkanesulfonyl-fluorosulfoloy. The silver which was made into silver amide acid and reacted and precipitated the dimonium compound by reaction at the temperature of 30-150 degreeC in organic solvents, such as N-methyl- 2-pyrrolidone, dimethyl formamide, and acetonitrile, was separated by filtration. Then, it can synthesize | combine by filtering the precipitation which arose by adding solvent, such as water, ethyl acetate, or hexane.

In addition, with commercially available dimonium pigment | dye, brand name "CIR-1085" made by the Japanese carit company, brand name "CIR-1085F" made by the Japanese carit company, brand name "KAYASORB IRG-022" made by Japanese powder company, Japanese gunpowder The brand name "KAYASORB IRG-023" etc. made by the company are mentioned.

There is no restriction | limiting in particular about the addition amount with respect to solid secretion of a near-infrared absorption adhesion layer of a dimonium pigment | dye, Although it can select arbitrarily according to the performance requested | required, it is 0.1-20 weight part with respect to 100 weight part of near-infrared absorption adhesion layer solid components. desirable.

Optional ingredient

Although various well-known additives can be added to the adhesive composition which concerns on this invention, The filler which consists of a crosslinking agent, a tackifier, a plasticizer, glass fiber, glass beads, metal powder, other inorganic powder, etc., a pigment, a coloring agent, Fillers, antioxidants, ultraviolet absorbers, silane coupling agents and the like can also be used. Moreover, it is good also as a near-infrared absorption adhesion layer etc. which contain microparticles | fine-particles and show light diffusivity. Another near-infrared absorbing pigment may be added to the adhesive composition which concerns on this invention. Moreover, the visible light absorbing dye for adjusting a color tone may be added. In addition, it is preferable that the rust preventive agent is added.

Cross-linking agent

Moreover, it is preferable that the adhesive composition which concerns on this invention contains a crosslinking agent. Examples of the crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, an imine crosslinking agent, and a peroxide crosslinking agent. Among these, an epoxy crosslinking agent and an isocyanate crosslinking agent are preferable.

An epoxy crosslinking agent contains an epoxy compound, and a glycerol diglycidyl ether etc. are mentioned as an epoxy compound, for example. The usage-amount of an epoxy type crosslinking agent is 0.001-2 weight part, Preferably it is 0.01-1 weight part, More preferably, it is 0.02-0.5 weight part with respect to 100 weight part of acrylic polymer. When the usage-amount of an epoxy compound is less than 0.001 weight part, it is unpreferable from the point of adhesiveness with an optical film, or durability.

Isocyanate-based crosslinking agent contains an isocyanate compound, and examples of the isocyanate compound include tolylene diisocyanate, chlorophenylenedi isocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate and diphenylmethane. Isocyanate monomers, such as diisocyanate and hydrogenated diphenylmethane diisocyanate, and the adduct isocyanate compound, isocyanurate compound, biuret type compound which added these polyisocyanate monomers with polyhydric alcohols, such as trimethylol propane, The urethane prepolymer type isocyanate etc. which addition-reacted the well-known polyether polyol, polyester polyol, acryl polyol, polybutadiene polyol, polyisoprene polyol, etc. are mentioned. Among these isocyanate compounds, adduct isocyanate compounds such as xylylene diisocyanate are preferred from the viewpoint of improving the adhesion to the optical film.

The amount of isocyanate-based crosslinking agent used is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, and more preferably 0.02 to 2.5 parts by weight with respect to 100 parts by weight of the acrylic polymer. If the amount of the isocyanate compound used is less than 0.001 part by weight, it is not preferable in terms of adhesion to the optical film and durability.

Other Near infrared  Absorbing pigment

Other near-infrared absorbing dyes that can be used in combination include known cyanine dyes, polymethine dyes, scarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, dimonium dyes, and inorganic oxide particles. Etc. can be mentioned.

Preferred other dyes (dyes other than the dimonium dye) are dyes capable of exhibiting a cuenza effect with respect to the dimonium dye. The cuenza effect is the effect of de-exciting the active molecule in an excited state. In the case of the present invention, other pigments having the effect of de-exciting and stabilizing a dimonium pigment molecule, a dimonium anion or a dimonium cation are preferable. From the viewpoint of the Cuenza effect, phthalocyanine-based dyes are preferred as other dyes.

Silane Coupling agent

In addition, it is preferable to add a silane coupling agent. Examples of the silane coupling agent include silicon having an epoxy structure, such as 3-glycidoxypropyltrimethoxy silane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane (Meth) acryl group-containing silane coupling agents such as 3-chloropropyltrimethoxysilane, acetoacetyl group-containing trimethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane And isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane. In particular, 3-glycidoxypropyltrimethoxysilane and acetoacetyl group-containing trimethoxysilane are preferably used because they can effectively prevent peeling. The silane coupling agent can impart durability, in particular the effect of inhibiting peeling under a humidified environment. The usage-amount of a silane coupling agent is 1 weight part or less with respect to 100 weight part of acrylic polymers, Furthermore, it is 0.001-1 weight part, Preferably it is 0.002-0.6 weight part. When the usage-amount of a silane coupling agent increases, adhesive force may increase too much and it may affect reworkability.

Visible light absorbing pigment

Moreover, in order to adjust the color tone of an adhesive composition, you may add the visible light absorbing dye for color tone adjustment. Although the kind of pigment | dye for color tone adjustment is not specifically limited, 1: 2 chromium complex, 1: 2 cobalt complex, copper phthalocyanine, anthraquinone, diketopyrrolopyrrole, etc. can be used. Specifically, orazolblue GN (product made in Chiba specialty chemicals), orazolblue BL (product made in Chiba specialty chemicals), orazolred 2B (product made in Chiba specialty chemicals), orazolred G (chiba Specialty chemicals), orazol black CN (product made in Chiba specialty chemicals), orazolero 2GLN (product made in Chiba specialty chemicals), orazolero 2RLN (product made in Chiba specialty chemicals), micro Rolls DPP Red BK (made by Chiba Specialty Chemicals) etc. are mentioned.

In order that the adhesive composition concerning this invention may absorb unnecessary neon light emission, it is preferable to use together the visible absorption pigment | dye whose maximum absorption wavelength is 550-650 nm. The neon light-emitting absorbing dye is not particularly limited, and examples thereof include cyanine dyes and tetraazaporphyrin dyes. In commercially available neon light-emitting absorbing dye, Adeka acrylic TY-102 (product of Asahi Telephone Co., Ltd.), Adeka acrylic TY-14 (made by Asahi Telephone Co., Ltd.), Adeka acrylic TY-15 (made by Asahi Telephone Co., Ltd.) , TAP-2 (product of Yamada Chemical Co., Ltd.), TAP-18 (product of Yamada Chemical Co., Ltd.), TAP-45 (product of Yamada Chemical Co., Ltd.), brand name NK-5451 (product of Hayashibaru Biochemistry Research Institute), NK-5532 (hayashibaru Biochemical research institute), NK-5450 (made by Hayashibaru Biochemical Research Institute), PD-320 (made by Yamamoto Chemical Co., Ltd.), etc. are mentioned. Although the addition amount of a neon light-emitting absorbing dye changes with kinds of pigment | dye, it is preferable to add so that the transmittance | permeability in a maximum absorption wavelength may be about 20 to 80%.

Anti-rust agent

As the rust inhibitor, both an inorganic rust inhibitor and an organic rust inhibitor can be used. As an inorganic type rust inhibitor, sodium nitrite, sodium chromate, etc. are mentioned, for example. Moreover, benzotriazole, octadecylamine, etc. are mentioned as an organic type rust inhibitor, for example. It is preferable to use a benzotriazole compound among these rust inhibitors, and it is more preferable to use 1,2, 3- benzotriazole.

(Substrate layer)

Although it does not specifically limit as a base material, For example, a peeling base material and a translucent base material are mentioned. Moreover, the light transmissive base material may be provided in one side of a near-infrared absorption adhesive layer, and the peeling base material may be provided in the opposite surface, and the peeling base material layer may be provided in both surfaces of a near-infrared absorption adhesive layer. Although it does not specifically limit as a peeling base material, Glassine paper, the graft paper laminated with the siliconized polyethylene, the silicon-treated polyethylene terephthalate (PET), etc. are mentioned.

Although it does not specifically limit as a translucent base material, For example, olefin polymers, such as glass, cyclopolyolefin, and amorphous polyolefin, methacryl polymers, such as polymethylmethacrylate, vinyl polymers, such as vinyl acetate and a vinyl halide, PET Polyvinyl acetals, such as polyester, polycarbonate, butyral resin, a polyaryl ether system resin, a lactone ring containing resin film, a triacetyl cellulose (TAC), etc. are mentioned. The light-transmitting substrate may be coated with a surface treatment according to a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, or an anchor coat agent or primer. Moreover, a well-known additive, heat resistant antiaging agent, a lubricating agent, an antistatic agent, etc. may be mix | blended with the base resin which comprises the said translucent base material. The light-transmissive substrate is molded into a film or sheet shape using a known injection molding, T die molding, calender molding, compression molding, or the like by melting and casting in an organic solvent. The base material constituting such a light-transmissive base material may be unstretched or stretched or may be laminated with another base material.

As a light-transmissive base material in the case of obtaining a near-infrared absorbing film by a coating method, PET film is preferable and the PET film which gave the reverse adhesion process especially is preferable. Specifically, Cosmo Shine A4300 (Toyo Spinning Agent), Lumir U34 (Toray Industries), Merinex 705 (made by Teijin Dupont), etc. are mentioned. Moreover, functional films, such as a TAC (triacetyl cellulose) film, an antireflection film, an anti-glare film, an impact absorption film, an electromagnetic shield film (including a mesh film), and an ultraviolet absorbing film, can also be used as a translucent base material. Thereby, the optical filter for thin displays and optical semiconductor elements can be manufactured simply. It is preferable that a translucent base material is a film.

Among these, glass, a PET film, a lactone ring-containing resin film, a reverse adhesive PET film, a TAC film, an antireflection film, and an electromagnetic shield film are preferably used as the light transmitting substrate. Although the thickness of a base material layer is not specifically limited, 0.1 micrometer-10 mm are preferable.

In addition, although an arbitrary layer may be formed as an arbitrary layer, it is preferable that a metal mesh film can be affixed in order to shield an electromagnetic wave on the surface of a near-infrared absorption adhesion layer. Although it does not specifically limit as a metal mesh film, For example, the metal mesh film made from copper is mentioned. Here, when the mesh film affixed on the surface of a near-infrared absorption adhesive layer is affixed in the form embedded in the said adhesive layer, since another layer can be laminated | stacked, it is more preferable.

Although the heat resistance of the adhesive optical film which concerns on this invention is not specifically limited in the rising value of the transmittance | permeability in the wavelength of 850 nm when it is left to stand at 80 degreeC for 500 hours, 20% or less is preferable, 15% or less is more preferable, 10% or less is more preferable, and the rise value of the transmittance at a wavelength of 950 nm is not particularly limited, but is preferably 15% or less, more preferably 10% or less, further preferably 5% or less. Moreover, it is preferable that the rising value of the transmittance | permeability in 850 nm when it is left to stand for 500 hours under conditions of 60 degreeC and 90% of humidity of the adhesive optical film is 20% or less, It is preferable that it is 15% or less, 10 It is preferable that it is% or less. Although the rise value of the transmittance | permeability in the wavelength of 950 nm is not specifically limited, 15% or less is preferable, 10% or less is more preferable, 5% or less is further more preferable.

[Manufacturing method]

Although the adhesive optical film which concerns on this invention is not specifically limited, For example, the coating process which coats the coating liquid containing an adhesive composition and a solvent on a base material, The drying process which dries the coating film formed by the said coating process, The said A near-infrared absorption adhesive layer can be formed by the aging process of aging the film | membrane obtained by the drying process.

Coating process

In a coating process, the coating liquid containing an adhesive composition is apply | coated on a base material. Here, the adhesive composition and the solvent may be contained in the coating liquid. Moreover, the said crosslinking agent and a silane coupling agent may be contained in the coating liquid. Although a well-known solvent can be used as a solvent, For example, methyl ethyl ketone, acetone, ethyl acetate, tetrahydrofuran, dioxane, cyclohexanone, n-hexane, toluene, xylene, methanol, ethanol, n-pro Panol, isopropanol, etc. are mentioned. These solvents may be used independently, and may mix and use 2 or more types. Although it can coat by a well-known method as a coating method, it can coat, for example using an applicator.

Drying process

In a drying process, the solvent contained in the coating film obtained by the coating process is removed and dried. Although a drying method can use a well-known method, it does not specifically limit, For example, it can dry using oven.

Aging  fair

In an aging process, a dimonium pigment | dye aggregates in needle shape by aging (aging) the obtained film | membrane. Here, aging is performed under the conditions heated to 35 degreeC or more. If it is 35 degreeC or more, the formation rate of an aggregate will improve depending on a heating temperature and a heat time. For example, in the case of curing at 40 ° C., when cured for about 1 day or more, aggregates are formed. If it is 35 degreeC or more, it is preferable to cure for 3 days or more, and if it is 40 degreeC or more, it is more preferable to set it as 3 days or more.

As described above, since the dimonium pigment is aggregated in the state where the solvent is removed after the drying step, the aggregate is needle-like, unlike the case where the near-infrared absorption adhesive layer is formed by using the dimonium pigment dispersed in the coating liquid state. Is formed. Moreover, since agglomeration is carried out after removing a solvent in this way, a dimonium pigment | dye has high durability.

[How to use]

The obtained adhesive optical film is used for a plasma display panel. That is, it can be used as a near-infrared absorption filter by affixing and using on the glass panel surface of a plasma panel display. Especially according to the adhesive optical film which concerns on this invention, the dimonium pigment | dye has the high durability, and also shows the effect that an absorption spectrum and a hue in a visible light region are hard to change. Moreover, since it is possible to give a near-infrared absorptivity to an adhesion layer, the laminated constitution of an optical film can be reduced and a lower cost optical film can be obtained.

When using for a plasma display, you may have a neon cut function as well as a near-infrared absorption ability. That is, what is necessary is just to add a neon light absorbing dye to an adhesive composition.

In addition, in order to cut an electromagnetic wave, when using for a plasma display, a copper mesh film may be used, and this mesh film and the near-infrared absorption adhesion layer of an adhesion film may be used together as an optical filter member, but By using it, it becomes possible to prevent oxidation of copper. In this use, a benzotriazole compound is particularly preferable as a rust inhibitor, and it is more preferable to use 1,2,3-benzotriazole.

[Example]

<Manufacture example 1: adhesive resin A>

Butyl acrylate (412.7 g), methyl acrylate (117.9 g), and acrylic acid (10.4 g) were weighed and mixed as a monomer, and the polymerizable monomer mixture (A1) was obtained. 160 g of ethyl acetate and 300 g of a polymerizable monomer mixture (A1) were placed in a flask. In addition, 300 g of a polymerizable monomer mixture (A1), 16 g of ethyl acetate, and 0.15 g of Naifer BMT-K40 (polymerization initiator, manufactured by Ilyou Co., Ltd.) were added to the dropping lot, and mixed well to prepare a dropping mixture (A2). . The inner temperature of the flask was raised to 95 ° C while flowing nitrogen gas at 20 ml / min, and Naper BMT-K40 (0.15 g), which was a polymerization initiator, was charged to the flask to initiate a polymerization reaction. The dripping of the dripping mixture (A1) from the dripping lot was dripped over 90 minutes. After completion of the dropwise addition of the dropwise mixture (A1), aging was carried out for 6 hours while diluting with ethyl acetate as the viscosity increased, thereby obtaining an acrylic polymer. After completion of the reaction, 59.0 g of SK Dyne MD5 (amine-containing tackifier, Soken Chemicals) was added and mixed well. The weight average molecular weight 600,000 and the adhesive resin A of the acid value 8 were obtained.

<Manufacture example 2: adhesive resin B>

Butyl acrylate (458.6 g), methyl acrylate (131.0 g) and acrylic acid (10.4 g) were weighed and mixed as a monomer, and the polymerizable monomer mixture (B1) was obtained. 160 g of ethyl acetate and 300 g of a polymerizable monomer mixture (B1) were placed in a flask. In addition, 300 g of a polymerizable monomer mixture (B1), 16 g of ethyl acetate, and 0.15 g of Naifer BMT-K40 (polymerization initiator, manufactured by Ilyou Co., Ltd.) were added to the dropping lot, and mixed well to prepare a dropping mixture (B2). . The internal temperature of the flask was raised to 95 ° C while flowing nitrogen gas at 20 ml / min, and Napa BMT-K40 (0.15 g), which was a polymerization initiator, was added to the flask to initiate a polymerization reaction. The dripping of the dripping mixture (B1) from the dripping lot was dripped over 90 minutes. After the dropwise addition of the dropwise mixture (B1) was completed, aging was carried out for 6 hours while diluting with ethyl acetate as the viscosity increased, thereby obtaining an acrylic polymer. The weight average molecular weight 600,000 and the adhesive resin B of the acid value 8 were obtained after completion | finish of reaction.

<Manufacture example 3: adhesive resin C>

Butyl acrylate (409.1 g), methyl acrylate (116.9 g), and acrylic acid (15.6 g) were weighed and mixed as a monomer, and the polymerizable monomer mixture (C1) was obtained. 160 g of ethyl acetate and 300 g of a polymerizable monomer mixture (C1) were placed in a flask. In addition, 300 g of a polymerizable monomer mixture (C1), 16 g of ethyl acetate, and 0.15 g of Naifer BMT-K40 (polymerization initiator, manufactured by Ilyou Co., Ltd.) were added to the dropping lot, and mixed well to prepare a dropping mixture (C2). . The inner temperature of the flask was raised to 95 ° C while flowing nitrogen gas at 20 ml / min, and Naper BMT-K40 (0.15 g), which was a polymerization initiator, was charged to the flask to initiate a polymerization reaction. The dripping of the dripping mixture (C1) from the dripping lot was dripped over 90 minutes. After completion of the dropwise addition of the dropwise mixture (C1), aging was carried out for 6 hours while diluting with ethyl acetate as the viscosity increased, thereby obtaining an acrylic polymer. After completion of the reaction, 58.4 g of SK Dyne MD5 (amine-containing tackifier, Soken Chemicals) was added and mixed well. The average molecular weight 600,000 and the adhesive resin C of acid value 12 were obtained.

<Manufacture example 4: adhesive resin D>

Butyl acrylate (567.5 g) and acrylic acid (32.5 g) were weighed and mixed sufficiently as a monomer, and the polymerizable monomer mixture (D1) was obtained. 160 g of ethyl acetate and 300 g of a polymerizable monomer mixture (D1) were placed in a flask. In addition, 300 g of a polymerizable monomer mixture (D1), 16 g of ethyl acetate, and 0.15 g of Naifer BMT-K40 (polymerization initiator, manufactured by Ilyou Co., Ltd.) were added to the dropping lot, and mixed well to prepare a dropping mixture (D2). . The inner temperature of the flask was raised to 95 ° C while flowing nitrogen gas at 20 ml / min, and Naper BMT-K40 (0.15 g), which was a polymerization initiator, was charged to the flask to initiate a polymerization reaction. The dripping of the dripping mixture (D1) from the dripping lot was dripped over 90 minutes. After completion of the dropwise addition of the dropwise mixture (D1), aging was carried out for 6 hours while diluting with ethyl acetate as the viscosity increased, thereby obtaining an acrylic polymer. The weight average molecular weight 600,000 and the acid value 25 adhesive resin D were obtained after completion | finish of reaction.

Various values were measured by the following method.

(Acid value)

A predetermined amount of sample is taken in a container, and the solvent is added to dissolve well.

Titration is performed with 0.1 mol / L potassium hydroxide ethanol solution using a potentiometric titration apparatus, and the inflection point of the obtained titration curve is made into an end point.

Acid value (mg KOH / g) = (A × f × 5.61) / S

A: Consumption (mL) of 0.1 mol / L potassium hydroxide solution at the end point

f: factor of 0.1 mol / L potassium hydroxide solution

S: sampling amount (g)

(Molecular Weight)

The number average molecular weight (Mn) and the weight average molecular weight (Mw) weighed a sample at 0.01 g, added it to 10 g of tetrahydrofuran (THF), it was left to stand for 24 hours, and dissolved. Each molecular weight of this solution was measured from the analytical curve prepared by standard polystyrene using the gel permeation chromatography (GPC) method.

(Measuring conditions)

Device Name: HOS-8220GPC

Sample concentration: 0.1 wt% (THF solution)

Sample injection volume: 20 μl

Eluent: THF

Flow rate: 0.300 ml / min

Measuring temperature: 40 ° C

Column: sample column; TSKguard column SuperHZ-L (1) + TSKgel SuperHZM-M (2), reference column; TSKgel SuperH-RC (1), allotropes

Detector: Differential Refractometer (RI)

<Example 1: Adhesive film using adhesive resin A>

NIR cut pigment CIR-1085F (made by Nippon Carrier: dimonium bis (trifluoromethanesulfonyl) imide) was melt | dissolved in MEK, and the solution 1 of 5% of solid content was adjusted. Moreover, epoxy-type hardening | curing agent E-AX (made by Soken Chemical) was dissolved in MEK as a crosslinking agent, and the solution 2 of 1% of solid content was adjusted. The solution 1 and the solution 2 were added and mixed so as to be 2.5 parts and 0.05 parts, respectively, with respect to 100 parts by weight of the pressure sensitive adhesive resin in a solid content ratio in the pressure sensitive adhesive resin A to obtain a near infrared absorption pressure sensitive adhesive Aa. The near-infrared absorption adhesive Aa was applied to secondary peeling PET (Toray film processing agent, BX8A) with the applicator. The thickness at the time of coating was adjusted so that the adhesive thickness after drying might be 25 micrometers. It was then dried in an oven at 80 ° C. for 2 minutes. Primary peeling PET (Toray film processing agent, BKE (RX)) was stuck together to the layer which consists of this near-infrared absorption adhesive Aa, and it hardened | cured at 40 degreeC for 3 days, and obtained the near-infrared absorption adhesive film Aa1.

When the secondary peeling PET of the near-infrared absorption adhesive film Aa1 was peeled off, and the state of the near-infrared absorption adhesive layer was observed from the near-infrared absorption adhesion layer side exposed by the optical microscope, the needle aggregate of the dimonium pigment | dye was formed. Could not confirm.

Next, the exposed near-infrared absorptive adhesion layer was stuck to the reverse adhesion optical fiber film (made by the Oriental yarn, Cosmo shine A4300), peeled off primary peeling PET again, and the test body Aa2 was created by sticking to a glass plate.

<Example 2: Adhesive film using adhesive resin B>

NIR cut pigment CIR-1085 F (made by Nippon Carrit: dimonium bis (trifluoromethanesulfonyl) imide) was dissolved in MEK, and the solution 1 of 5% of solid content was adjusted. Moreover, epoxy-type hardening | curing agent E-AX (made by Soken Chemical) was dissolved in MEK as a crosslinking agent, and the solution 2 of 1% of solid content was adjusted. The solution 1 and the solution 2 were added and mixed so as to be 2.5 parts and 0.05 parts, respectively, with respect to 100 parts by weight of the adhesive resin in a solid content ratio in the adhesive resin B to obtain a near-infrared absorbent pressure-sensitive adhesive Ba.

The near-infrared absorption adhesive Ba was coated on secondary peeling PET (Toray film processing agent, BX8A) with the applicator. The thickness at the time of coating was adjusted so that the adhesive thickness after drying might be 25 micrometers. It was then dried in an oven at 80 ° C. for 2 minutes. Primary peeling PET (Toray film processing agent, BKE (RX)) was stuck together by the layer which consists of this near-infrared absorption adhesive Ba, and it cure | cured at 40 degreeC for 3 days, and obtained the near-infrared absorption adhesive film Ba1.

When the secondary peeling PET of the near-infrared absorption adhesive film Ba1 was peeled off, and the state of the near-infrared absorption adhesive layer was observed from the near-infrared absorption adhesive layer side exposed by the optical microscope, the needle aggregate of the dimonium pigment | dye was formed. Could not confirm.

Next, the exposed near-infrared absorptive adhesion layer was bonded to the reverse adhesion optical fiber film (manufactured by Dongyang Spinning Co., Ltd., Cosmo Shine A4300), the primary peeling PET was peeled off again, and the test body Ba2 was prepared by bonding it to a glass plate.

<Example 3: Adhesive film using adhesive resin C>

NIR cut pigment CIR-1085 F (made by Nippon Carrit: dimonium bis (trifluoromethanesulfonyl) imide) was dissolved in MEK, and the solution 1 of 5% of solid content was adjusted. Moreover, epoxy-type hardening | curing agent E-AX (made by Soken Chemical) was dissolved in MEK as a crosslinking agent, and the solution 2 of 1% of solid content was adjusted. Moreover, the isocyanate hardener L-45 (made by Soken Chemical) was dissolved in ethyl acetate as a crosslinking agent, and the solution 3 of about 9% of solid content was adjusted. The solution 1, the solution 2, and the solution 3 were added and mixed so as to be 2.5 parts, 0.09 parts, and 0.99 parts, respectively, in a solid content ratio in the adhesive resin C to obtain a near-infrared absorbent pressure-sensitive adhesive Ca.

Near-infrared absorption adhesive Ca was coated on secondary peeling PET (Toray film processing agent, BX8A) with the applicator. The thickness at the time of coating was adjusted so that the adhesive thickness after drying might be 25 micrometers. It was then dried in an oven at 80 ° C. for 2 minutes. Primary peeling PET (Toray film processing agent, BKE (RX)) was stuck to the layer which consists of this near-infrared absorption adhesive Ca, and it hardened | cured at 40 degreeC for 3 days, and obtained the near-infrared absorption adhesive film Ca1.

When the secondary peeling PET of the near-infrared absorption adhesive film Ca1 was peeled off, and the state of the near-infrared absorption adhesive layer was observed from the near-infrared absorption adhesive layer side exposed by the optical microscope, the needle aggregate of the dimonium pigment | dye was formed. Could not confirm.

Next, the exposed near-infrared absorptive adhesion layer was bonded to the anti-adhesion optical PET film (Co., Ltd., Cosmoshine A4300), peeled off primary peeling PET again, and bonded to the glass plate, and the test body Ca2 was created.

<Example 4: Adhesive film using adhesive resin D>

NIR cut pigment CIR-1085 F (made by Nippon Carrit: dimonium bis (trifluoromethanesulfonyl) imide) was dissolved in MEK, and the solution 1 of 5% of solid content was adjusted. Moreover, epoxy-type hardening | curing agent E-AX (made by Soken Chemical) was dissolved in MEK as a crosslinking agent, and the solution 2 of 1% of solid content was adjusted. The solution 1 and the solution 2 were added and mixed so as to be 2.5 parts and 0.05 parts, respectively, in solid content ratio in adhesive resin D, and the near-infrared absorption adhesive Da was obtained. The near-infrared absorption adhesive Da was coated by secondary applicator PET (Toray film processing agent, BX8A) with an applicator. The thickness at the time of coating was adjusted so that the adhesive thickness after drying might be 25 micrometers. It was then dried in an oven at 80 ° C. for 2 minutes.

Primary peeling PET (Toray film processing agent, BKE (RX)) was stuck to the layer which consists of this near-infrared absorption adhesive Da, and it cure | cured at 40 degreeC for 3 days, and obtained the near-infrared absorption adhesive film Da1.

When the secondary peeling PET of the near-infrared absorption adhesive film Da1 was peeled off, and the state of the near-infrared absorption adhesive layer was observed from the near-infrared absorption adhesive layer side exposed by the optical microscope, the needle aggregate of the dimonium pigment | dye was formed. Confirmed. The results are shown in FIGS. 1 and 2. Moreover, the average diameter of the circular aggregate of the said acicular aggregate was 181 micrometers.

Next, the exposed near-infrared absorptive adhesion layer was bonded to the reverse adhesion optical fiber PET film (Co., Ltd., Cosmoshine A4300), the primary peeling PET was peeled off again, and the test body Da2 was created by bonding to a glass plate.

[Endurance Test: Spectroscopic Property Test]

Heat resistance test

After measuring the haze by the spectrophotometer (UV3150 by Shimadzu Corporation, JISZ8722), and the haze meter (Japan color agent, NDH2000: JISK7105) by using a spectrophotometer (UV3150, JISZ8722), and the haze meter (Japan colorant, NDH2000: JISK7105) obtained by the obtained test samples concerning Examples 1-4. Each test body was put into 80 degreeC oven, and it left to stand for 500 hours. After the elapse of time, the test body was subjected to the characteristic measurement in the same manner as before the input, and compared with the initial value. Each result is shown in Table 2 and FIGS.

Moisture and Heat Resistance  exam

Comparison of various spectroscopic characteristics before and after the addition of the test sample was carried out by the same method as the heat resistance test method except that the step of placing each test sample into an 80 ° C. oven was left to stand in a 60 ° C./90% constant temperature and humidity bath for 500 hours. Was performed. Each result is shown in Table 2 and FIGS.

From the said result, the difference of the spectral characteristic value before and behind a test was computed, and it is shown in following Table 3.

As described above, when the test sample according to Example 4 is used, the change in haze value is small, and the increase in light transmittance at wavelengths of 850 nm and 950 nm is hardly observed. It is 7.11% at 850 nm and 1.66% at 950 nm in the heat resistance test, and 4.86% at 850 nm and 1.07% at 950 nm in the humidity and heat resistance test. That is, it turns out that the absorption of a dimonium pigment | dye hardly changes and the said pigment | dye has high durability. In addition, it can be inferred that there is no change in the spectral spectrum in the visible light region, but the value of the color tone hardly changes (Yxy value). That is, it turns out that the test body which concerns on Example 4 has remarkably high durability.

Moreover, about Example 2 which does not contain an amine-containing tackifier, the rise of a haze was confirmed in a heat resistance test and a moisture heat resistance test. Among these, in heat resistance test, although it fell slightly compared with Example 4, it was confirmed that the increase of transmittance | permeability is suppressed small and it has high heat resistance. When the sample after the heat resistance test was observed with the optical microscope, the formation of acicular aggregate was confirmed.

Claims (11)

It has an acrylic polymer, the near-infrared absorption adhesion layer containing a dimonium pigment | dye, and a base material layer,
A needle-shaped optical film, wherein needle-like aggregates of the dimonium pigment are scattered in the near-infrared absorption adhesive layer. The method according to claim 1,
The needle-like optical film coats the coating liquid containing the acrylic polymer, the dimonium pigment, and the solvent on the base layer, and ages the needle-shaped aggregate of the dimonium pigment by aging the near-infrared absorption adhesive layer obtained by drying. It is obtained by forming, and the adhesive optical film characterized by the above-mentioned. The method according to claim 1 or 2,
A pressure-sensitive adhesive optical film, characterized in that the near-infrared absorbing pressure-sensitive adhesive layer contains a crosslinking agent or a combination of two or more crosslinking agents as long as it is selected from the group consisting of an epoxy crosslinking agent, an isocyanate crosslinking agent, an imine crosslinking agent, and a peroxide crosslinking agent. The method according to claim 1,
The near-infrared absorptive adhesion layer contains an antirust agent, The adhesive optical film characterized by the above-mentioned. The method according to claim 1,
A pressure-sensitive adhesive optical film, wherein a metal mesh film is attached to the near-infrared absorbing pressure-sensitive adhesive layer. The plasma display panel in which the adhesive optical film of Claim 1 is affixed on the surface. Containing an acrylic polymer and a dimonium pigment,
The content of the amine additive is 10 parts by weight or less based on 100 parts by weight of the acrylic polymer, and the acid value of the acrylic polymer is 7-50 mg KOH / g, wherein the near-infrared absorbent pressure-sensitive adhesive composition. The method of claim 7,
The near-infrared absorptive pressure-sensitive adhesive composition wherein the acrylic polymer contains an alkyl (meth) acrylate monomer having 4 to 12 carbon atoms of an alkyl group and a carboxyl group-containing monomer. The method according to claim 7 or 8,
The said dimonium pigment | dye is a dimonium cation of following formula (1),

(Formula (1) of, R ¹ ~R ⁸ are may be the same or different and each represents a hydrogen atom, a halogen group, an alkyl group, a halogenated alkyl group, a cyano group, an aryl group, a hydroxyl group, a phenylalkyl group or alkoxy)
Near-infrared absorptive pressure-sensitive adhesive composition comprising a counteranion of the following formula (2).

(In formula (2), R ^<a> , R <^b> may be same or different and represents a fluorine atom or an alkyl fluoride group.) The method of claim 7,
A near-infrared absorption adhesive composition further comprising a crosslinking agent or a combination of two or more crosslinking agents selected from the group consisting of an epoxy crosslinking agent, an isocyanate crosslinking agent, an imine crosslinking agent, and a peroxide crosslinking agent. The method of claim 7,
A near-infrared absorption adhesive composition containing a rust preventive agent.

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