KR20060108255A - Pressure sensitive adhesive layer functionalizing the color compensation and the near infrared (nir) ray blocking for plasma display filter - Google Patents

Abstract

The present invention relates to an adhesive film functionalizing color compensation and near infrared ray blocking and a plasma display panel filter employing the same. The present invention provides a multifunctional adhesive film for a plasma display panel comprising an acryl-based adhesive and a near infrared ray blocking dye. The present invention also provides a multifunctional adhesive film for a plasma display panel comprising an acryl-based adhesive and a neon-cut dye. The adhesive film may further comprise a near infrared ray blocking dye. The multifunctional adhesive film of the present invention has superior durability at high temperature and humidity with little transmittance change and superior thermal stability. When further comprising a near infrared ray blocking dye, it exerts both color compensation and near infrared ray blocking performances. Because the film has superior adhesivity in itself, an additional adhesive layer is unnecessary, which simplifies the manufacturing process of a plasma display panel filter and a plasma display panel.

Description

 Pressure sensitive adhesive layer functionalizing the color compensation and the near infrared (NIR) ray blocking for plasma display filter}

 1 briefly illustrates a structure of a plasma display panel.

Figure 2 shows the spectral change of the multifunctional pressure-sensitive adhesive film according to Example 4 of the present invention.

Figure 3 shows the spectral change of the multifunctional pressure-sensitive adhesive film according to Example 5 of the present invention.

Figure 4 shows the spectral change of the multifunctional pressure-sensitive adhesive film according to Example 6 of the present invention.

Figure 5 shows the spectral change after the endurance test at high temperature for the film of Comparative Example 1.

Figure 6 shows the spectral change after the durability test at high temperature and high humidity for the film of Comparative Example 1.

Figure 7 shows the spectral change for the film of Comparative Example 2.

8 is a structure of a plasma display panel filter of Embodiment 7 of the present invention.

9 is a structure of the plasma display panel filter of Embodiment 8 of the present invention.

10 is a structure of the plasma display panel filter of Comparative Example 3. FIG.

 The present invention relates to a pressure-sensitive adhesive film having a near infrared absorption function as well as a color correction function such as neon-cut, and a plasma display panel filter including the same, and more particularly, a change in transmittance at high temperature and high temperature and high humidity. The present invention relates to a multifunctional pressure-sensitive adhesive film having a low adhesive strength and excellent thermal stability, and a plasma display panel filter using the same.

 Recently, in implementing a large screen among flat panel display panels, plasma display panels (hereinafter referred to as PDPs) have been in the spotlight.

The plasma display panel can realize a large screen, and a product of about 70 inches has already been developed. For reference, FIG. 1 briefly illustrates a general cross-sectional structure of a plasma display panel structure. In FIG. 1, reference numeral 11 is a case, 12 is a driving circuit board, 13 is a panel assembly, 14 is a plasma display panel filter, and 15 is a cover.

The PDP filter compensates for the deterioration of purity of the red spectrum due to the unique orange spectrum emitted from the panel, and serves to shield near infrared rays and harmful electromagnetic waves that cause a malfunction of the remote control device. In order to play this role, the PDP filter is composed of layers having respective functions such as an anti-reflection layer, a color correction layer for correcting color purity, a near infrared absorption layer, and an electromagnetic shielding layer. The layers having the above functions are generally in the form of a film, and a method of laminating each layer using a separate adhesive is mainly used.

On the other hand, if a single film has all the functions such as color correction and near-infrared absorption, or if the number of films used is simplified to simplify the structure, defects in the lamination process can be minimized and material savings can be achieved. For example, by forming layers having different functions on both sides of the film to have three functions in one film, the number of layers in the PDP filter can be cut in half. Alternatively, the structure may be simplified by having a function as described above in the pressure-sensitive adhesive used when the film is laminated. In order to block near-infrared rays and to compensate for the color, a material that selectively absorbs them is required, and dyes are mainly used. The dyes include neon-cut dyes and near infrared absorbing dyes that absorb specific wavelength bands. A common method of applying the dyes is to coat a dye layer mixed with a binder polymer on a transparent substrate, which inserts the substrate coated with the dye layer into an arbitrary layer in the PDP filter using an adhesive. shall.

In this case, rubber, polyvinyl ether, acrylic, silicone, and the like are widely used as the general adhesive, and the rubber is poor in aging resistance, the polyvinyl ether is inferior in heat resistance, and the silicone is problematic in adhesive strength. . On the other hand, acrylic pressure-sensitive adhesives exhibit a high function in a variety of application properties are most widely used in the production of pressure-sensitive adhesive composition. The general acrylic pressure-sensitive adhesive mainly exhibits excellent adhesive properties when light pressure is applied at room temperature, because the polymer molecules constituting the pressure-sensitive adhesive has a flow characteristic and is sensitive to pressure to adhere to the adherend. However, due to such flow characteristics, dyes having a color correction or near-infrared ray blocking function included in the pressure-sensitive adhesive are inferior in heat resistance and moisture resistance to general binder polymers. Therefore, it is important to select a pressure-sensitive adhesive that can withstand the conditions of high temperature, high temperature and high humidity and a dye having high durability.

Conventionally, there are the following methods using the color correction dye and the near infrared dye.

Japanese Patent Laid-Open No. 2001-248721 discloses an optical filter using an azapopyrine-based dye of 570-605 nm. However, although the method has been disclosed that it may be contained in a transparent adhesive (acrylic adhesive) to impart tackiness, there is no specific reference to the adhesive structure and crosslinking agent, coupling agent, etc. used, the initial transmittance is 15.9% at 584 nm, but no change in transmittance before or after the endurance test.

In addition, Korean Patent Publication No. 2002-0055410 discloses a near-infrared absorbing material prepared by using a cyanine-based dye and a near-infrared dye that absorb a wavelength of 550-620 nm on a transparent substrate. In addition, Korean Patent Laid-Open Publication No. 2004-0049280 discloses a pressure-sensitive adhesive composition using an acrylic adhesive resin, a near infrared dye, an ultraviolet absorber, and a hindered amine-based light stabilizer. Japanese Patent Application Laid-Open No. 2001-207142 discloses an infrared absorbent pressure-sensitive adhesive composition using an acrylic adhesive resin, a cyanine-based infrared absorber, and a polyfunctional acrylic copolymer. Japanese Patent Laid-Open No. 2004-107566 discloses an adhesive using an acrylic resin having a specific acid value and a polymethine-based neon cut dye.

However, the Korean Patent Publication No. 2002-0055410 does not mention the specific adhesive structure and composition, or the Korean Patent Publication No. 2004-48280 does not mention the near-infrared blocking efficiency as a near-infrared absorbing film. In addition, Japanese Patent Laid-Open No. 2001-207142 and Japanese Patent Laid-Open No. 2004-107566 use cyanine-based near infrared absorbing dyes and cyanine-based neon-cut dyes, respectively, but cyanine-based dyes are poor in heat resistance and light resistance. In addition, the color correction film and the near-infrared absorbing film made by the conventional method show a difference in durability at high temperature and high temperature and high humidity depending on the type of binder and coating conditions. In addition, when the PDP filter is manufactured using these films, there are problems such as lowering of process yield and increasing unit cost by laminating several layers of film. Therefore, attempts have been made to develop a pressure-sensitive adhesive layer such as a pressure-sensitive adhesive layer including a neon-cut layer, a pressure-sensitive adhesive layer including a near-infrared shielding layer, etc., but have not obtained optimum durability at high temperature, high temperature, and high humidity.

 In order to solve the above problems in the prior art, the object of the present invention is a low transmittance change in high temperature and high temperature and high humidity conditions, excellent durability, excellent thermal stability, excellent transmittance retention ability in the visible region even after a long time and near infrared absorption rate To provide a multi-functional adhesive film having a high adhesion and color correction and a near infrared absorption function.

Another object of the present invention, including the multi-functional pressure-sensitive adhesive film, having a color correction and near-infrared absorptivity, without the need for a separate pressure-sensitive adhesive layer is possible to integrate the film plasma display panel filter, and comprising the same It is to provide a plasma display panel.

In order to achieve the above object, the present invention is an acrylic pressure-sensitive adhesive; And it provides a multifunctional pressure-sensitive adhesive film for plasma display panel comprising a near infrared absorbing dye.

In addition, the present invention is an acrylic pressure-sensitive adhesive; And it provides a multifunctional pressure-sensitive adhesive film for plasma display panel comprising a neon-cut dye. The pressure-sensitive adhesive film may further include a near infrared absorbing dye.

In addition, the present invention provides a plasma display panel filter including at least one of the above-mentioned multifunctional pressure-sensitive adhesive film to at least one layer of the layer formed on the upper and lower portions of the substrate.

In addition, the present invention provides a plasma display panel including the plasma display panel filter.

 Hereinafter, the present invention will be described in detail.

The present invention uses an acrylic pressure-sensitive adhesive having excellent adhesive strength and durability that can replace the role of a conventional adhesive (PSA) as a binder resin, and simultaneously provide high durability and adhesive function using a color correction dye and a near infrared dye. Provided is a multifunctional adhesive film for a display panel.

The film of the present invention uses a neon-cut dye that blocks the neon light generated near 590nm, to block the NIR generated near 850nm, 950nm, in order to meet the optical properties typically required for plasma display panel filters Use near infrared dyes.

In addition, the multi-functional pressure-sensitive adhesive film of the present invention effectively blocks the neon peak near 570-600 nm to emit light from the PDP module, block the near infrared region 800-1100nm region to 10% or less, and also the adhesive function It is a film having. In particular, after high temperature and high temperature and high humidity of these films, more specifically, after 500 hours high temperature test at 80 degrees, the dye concentration change rate is 10% or less at each wavelength in the visible region and near infrared region after 90% RH 500 hours at 60 degrees. In addition, the present invention can have both a color correction function or a color correction function and a near infrared absorption function on a single film, and can simplify the structure by reducing the number of films used.

It will be described in more detail with respect to the pressure-sensitive adhesive film of the present invention.

In order to block electromagnetic waves generated from driving, neon light emission, near infrared rays, and the like, and to supplement their functions, the PDP forms a filter having various functions on the front of the panel. At this time, a pressure-sensitive adhesive (PSA) is used to laminate the films, and the pressure-sensitive adhesive should not only be excellent in adhesive force but also excellent in transmittance in the visible light region (380 to 780 nm).

Therefore, the film of this invention contains an acrylic adhesive and a near-infrared absorption dye. In addition, the film of the present invention is an acrylic pressure-sensitive adhesive; And a neon-cut dye, and may further include the near-infrared absorbing dye.

In the present invention, the pressure-sensitive adhesive used as the binder resin is preferably an acrylic pressure-sensitive adhesive having a Tg of 0 degrees or less. The acrylic pressure-sensitive adhesive is 75 to 99.89% by weight of a (meth) acrylic acid ester monomer having an alkyl group having 1 to 12 carbon atoms, 0.1 to 20% by weight of an α, β unsaturated carboxylic acid monomer which is a functional monomer, or a polymerizable monomer having a hydroxyl group. 0.01 to 5% by weight can be obtained by copolymerization alone or in combination. The copolymerization method is well known to those skilled in the art and specific conditions will be omitted.

More preferably, the acrylic pressure-sensitive adhesive, a copolymer of butyl acrylate (BA) / hydroxy ethyl methacrylate (HEMA), or butyl acrylate / acrylic acid (AA: acrylic acid) copolymer may have an excellent absorption function in the visible region and near infrared region of the film compared to other acrylic pressure-sensitive adhesives.

The near-infrared absorbing dye may be one that is commonly used, and is not particularly limited. For example, a diionium-based dye may be used, and a metal-complex dye or a phthalocyanine-based dye may be mixed and used as necessary. The dimonium-based dye absorbs near infrared rays in a broad wavelength range of 900 to 1200 nm.

The near-infrared absorbing dye includes a diimmonium dye represented by the following formula (4), a phthalocyanine dye represented by the formula (5), a naphthalocyanine dye represented by the formula (6), a metal represented by the formula (7) and (8)- One or more selected from the group consisting of metal-complex dyes may be used.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formula 4, R ₁ To R ₁₂ Are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted aryl group having 1 to 16 carbon atoms, X is a monovalent or divalent organic acid anion, or monovalent or Divalent inorganic acid anion,

In Formulas 5 and 6, each R is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, A substituted or unsubstituted allyloxy group, a fluorine-substituted alkoxy group, or a pentagonal ring having at least one substituted or unsubstituted nitrogen atom, and M is two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom And any one of oxy metals, preferably M is nickel, platinum, palladium or copper,

In Formulas 7 and 8, R and R ₁ R ₄ are each independently hydrogen, an alkyl group having 1 to 16 carbon atoms, an aryl group, or an alkoxy group, a phenoxy group, a hydroxyl group, an alkyl amino group having 1 to 16 carbon atoms, an aryl amino group, a trifluoromethyl group, or an alkyl tee having 1 to 16 carbon atoms. Group, aryl thi group, nitro group, cyano group, halogen atom, phenyl group, or naphthyl group.

In Formula 4, the organic acid monovalent anion includes organic carboxylic acid ions, organic sulfonic acid ions, organic boric acid ions, and the like. Organic carboxylic acid ions include acetate ions, lactate ions, trifluoroacetate ions, propionate ions, benzoate ions, oxalate ions, succinate ions or stearate ions. As the organic sulfonic acid ions, metal sulfonate ions, toluene sulfonate ions, naphthalene monosulfonate ions, chlorobenzene sulfonate ions, nitrobenzene sulfonate ions, dodecylbenzene sulfonate ions, benzone sulfonate ions, and ethane Sulfonate ions or trifluoromethane sulfonate ions. As for the organic boric acid ion, tetraphenyl borate ion or butyl triphenyl borate ion is preferable.

In the general formula (4), inorganic monovalent anions include halogenide ions, for example, fluoride ions, chloride ions, bromide ions, iodide ions, thiocyanate ions, hexafluoroantimononate ions, perchlorate ions, Preference is given to periodate ions, nitrate ions, tetrafluoroborate ions, hexafluorophosphate ions, molybdate ions, tungstate ions, titanate ions, vanadate ions, phosphate ions and borate ions. As the divalent anion, naphthalene-1,5-disulfonic acid, naphthalene-1,6-disulfonic acid, naphthalene disulfonic acid derivative, and the like are preferable.

Further, in the present invention, the neon-cut dye is a dye having a maximum absorption wavelength of 570-600 nm and a half band width of 50 nm or less, and is an intramolecular or intermolecular metal complex (Metal-complex). Preference is given to using dyes having a form.

Examples of the neon-cut dyes include porphyrin dyes having an intramolecular metal-complex form represented by Formula 1 below; One or more selected from the group consisting of cyanine dyes having an intermolecular metal-complex form represented by the following Chemical Formulas 2 and 3 may be used. Preferably, the neon cut dye is more preferably porphyrin-based.

[Formula 1]

[Formula 2]

[Formula 3]

In Formula 1, R ₁ to R ₈ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted alkoxy group; Pentagonal ring having one or more substituted or unsubstituted phenyl group, substituted or unsubstituted allyloxy group, fluorine substituted alkoxy group, or substituted or unsubstituted nitrogen atom;

M is a metal having a ligand as a hydrogen atom, an oxygen atom, a halogen atom, or a divalent to tetravalent metal atom,

In Chemical Formulas 2 and 3,

Each R is independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon having 1 to 30 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 30 carbon atoms,

X and Y are each independently halogen, nitro group, carboxyl group, alkoxy group having 2 to 8 carbon atoms, phenoxycarbonyl group, carboxylate group, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms or 6 to 30 carbon atoms Is an aryl group.

In the definition of Chemical Formula 1, divalent metal atoms of M include Cu, Zn, Fe, Co, Ni, Ru, Rd, Pd, Mn, Sn, Mg, Ti, and the like, and trivalent monosubstituted metal atoms include Al. Halogen atoms, hydroxyl groups, alkoxy groups may be monosubstituted to metals such as -Cl, Ga-Cl, In-Cl, Fe-Cl, Ru-Cl, and the like, and tetravalent disubstituted metals include SiCl ₂ , GaCl ₂ , TiCl ₂ , Such as SnCl ₂ , Si (OH) ₂ , Ge (OH) ₂ , Mn (OH) ₂ , Sn (OH) _2, and the like, a halogen, a hydroxyl group, an alkoxy group may be substituted on a metal atom, and VO, MnO as an oxy metal. , Oxygen may be bonded to the metal, such as TiO.

The weight ratio of the acrylic adhesive and the near infrared absorbing dye is 10: 1 to 10000: 1. At this time, the weight ratio depends on the weight ratio of the pressure-sensitive adhesive solution to the solvent, the viscosity of the pressure-sensitive adhesive solution, the molar absorption coefficient of the near-infrared absorbing dye used and the transmittance to be blocked.

In the case of a film including a neon-cut dye, the weight ratio of the acrylic pressure-sensitive adhesive and the neon-cut dye is 10: 1 to 10000: 1. At this time, the weight ratio depends on the weight ratio of the pressure-sensitive adhesive solution to the solvent, the viscosity of the pressure-sensitive adhesive solution, the molar extinction coefficient of the neon-cut dye used, the transmittance to be blocked.

The present invention may further include a solvent when preparing a multifunctional adhesive film, and a general organic solvent may be used as the solvent, and preferably methyl ethyl ketone (MEK), tetrahydrofuran (THF), and ethyl acetate (Ethyl Acetate). ), Toluene and the like can be used. The content of the solvent is not particularly limited.

All of the pressure-sensitive adhesive films of the present invention may further use a crosslinking agent and a coupling agent.

The crosslinking agent may include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, or a metal chelate crosslinking agent as a multifunctional compound. More preferably, an isocyanate crosslinking agent is used, and examples thereof include, but are not limited to, tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and the like. The amount of the crosslinking agent may be used in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the acrylic copolymer.

The coupling agent is preferably a silane coupling agent. The silane coupling agent serves to improve the adhesion reliability, especially when left for a long time under high temperature and high humidity. As the silane coupling agent, vinyl silane, epoxy silane, methacryl silane or the like can be used. For example, vinyl trimethoxy silane, vinyl triethoxy silane, γ-glycidoxypropyl trimethoxy silane, or γ-meta Krilloxypropyl trimethoxysilane etc., These can be used individually or in mixture. The content of the silane coupling agent may be used in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the acrylic copolymer.

In the present invention, the method of manufacturing the pressure-sensitive adhesive film is not particularly limited, but the dye and binder are added, a predetermined amount of crosslinking agent and a coupling agent are added thereto, followed by preparing a coating solution and coating the cured release film. can do. It is preferable that the thickness of the coating surface thus obtained is 10 micrometers or more. As the coating method, various methods such as spray coating, roll coating, bar coating, and spin coating may be used.

In addition, the present invention provides a plasma display panel filter including the multi-functional adhesive film for the plasma display panel. The plasma display panel filter is a base film, an antireflection film (AR film), the near-infrared film of the present invention, a multi-functional adhesive film having a color correction or color correction and a near infrared absorption function, electromagnetic shielding film (EMI film), black screen treatment It can be made by laminating layers and the like.

In the method of manufacturing the plasma display panel filter, a filter may be prepared by appropriately laminating the films on a transparent substrate such as glass and polyethylene terephthalate (PET) as necessary. The filter of the present invention may include at least one or more near-infrared film, color correction film, color correction and near-infrared absorbing ability at the same time, the film may be configured in any layer on the upper and lower sides of the substrate. The present invention does not use a separate adhesive when directly stacking at least one of the multifunctional film on the substrate. If the multi-functional film is used to form a layer, a conventional pressure-sensitive adhesive (PSA) can be used. That is, the electromagnetic shielding film and the black screen treatment film may be manufactured by laminating using an adhesive in a conventional method.

In addition, the present invention provides a plasma display panel including the plasma display panel filter. Since the method of manufacturing the plasma display panel is well known in the art and can be sufficiently understood by those skilled in the art, detailed description thereof will be omitted.

The present invention attaches a filter including the pressure-sensitive adhesive film of the present invention on the panel assembly, the plasma display with excellent durability, excellent thermal stability and high transmittance in the visible region due to the small change in transmittance under high temperature and high temperature and high humidity conditions. It has the effect of providing a panel.

As described above, the pressure-sensitive adhesive film for a plasma display panel of the present invention includes an acrylic pressure-sensitive adhesive having excellent adhesive strength and durability as a binder resin, and also includes a color correction dye or color correction dye and a near infrared absorbing dye, at high temperature and high temperature and high humidity conditions. The change of transmittance at is low, which is excellent in durability, excellent in thermal stability, and excellent in near infrared absorption while maintaining transmittance in the visible region. In particular, since the film itself has an adhesive force, it is unnecessary to use a separate pressure-sensitive adhesive as in the conventional manufacture of the plasma display panel filter, thereby simplifying the process and reducing the thickness of the filter.

The following presents a preferred embodiment to help the understanding of the present invention. However, the following examples are merely provided to explain the present invention more easily, and are not limited to the embodiments of the present invention.

EXAMPLE

The multifunctional pressure-sensitive adhesive film according to the present invention was prepared by the following method, and the physical property test conditions for the multifunctional pressure-sensitive adhesive film are as follows.

<Film manufacturing method>

1. Preparation of Coating Liquid: In Examples, using butyl acrylate (BA) / hydroxy ethyl methacrylate (HEMA) copolymer or butyl acrylate (BA) / acrylic acid (AA) copolymer as adhesive resin , A neon-cut dye, a first near infrared absorbing dye, and a second near infrared absorbing dye alone or mixed to prepare a coating liquid for producing a multifunctional pressure-sensitive adhesive film.

2. Coating: The coating solution was coated on the release surface of the release film with a thickness of 15 μm, dried at 120 ° C. for 3 minutes, and then the coating surface was laminated with the release film.

3. Aging: Aged at room temperature for 3 days.

<Durability test condition>

High temperature conditions: The transmittance of each wavelength band before and after 500 hours in an 80 degree chamber was compared.

(Example 1)

Near infrared  Manufacture of Films Containing Dyes

100 parts by weight (15.5% by weight) of a butyl acrylate (BA) / hydroxy ethyl methacrylate (HEMA) copolymer solution dissolved in 84.5 ml of ethyl acetate, a dimonium dye of formula 4 as a near-infrared absorbing dye (trade name: CIR1081 (Manufacturer: Japan Carlit) was added by mixing 0.05 parts by weight, 0.05 parts by weight of T-39M with isocyanate-based crosslinking agent, and 0.07 parts by weight of T-789J with silane coupling agent, and 45 parts by weight of methyl ethyl ketone (MEK). After the coating solution was prepared, it was coated on a base film with a thickness of 23 μm to prepare a multifunctional pressure-sensitive adhesive film.

Then, the durability test by the above-described method and the results are shown in Table 1.

TABLE 1

Visible light transmittance (%) Near infrared ray transmittance (%) 438nm 450 nm 528 nm 550 nm 586 nm 612nm 628 nm 850 nm 950 nm Early 70.4 68.0 71.0 81.4 86.5 87.0 85.3 2.3 3.0 After 500 hours 70.3 67.7 71.7 82.1 87.3 87.4 85.5 2.4 3.1

From the above results, it can be seen that even after the test at a high temperature, the ability to maintain the visible light transmittance and the near infrared transmittance is excellent.

(Example 2)

Near infrared  Manufacture of Films Containing Dyes

A pressure-sensitive adhesive film was prepared in the same manner as in Example 1, except that a phthalocyanine dye (trade name: IR12, manufacturer: Nippon Catalyst Co., Ltd.) of Formula 5 was used as the near-infrared absorbing dye.

(Example 3)

Near infrared  Manufacture of Films Containing Dyes

An adhesive film was prepared in the same manner as in Example 1, except that a butyl acrylate / acrylic acid copolymer solution was used instead of the butyl acrylate (BA) / hydroxy ethyl methacrylate (HEMA) copolymer.

(Example 4)

Manufacture films containing neon-cut dyes

100 parts by weight (15.5% by weight) of a butyl acrylate (BA) / hydroxy ethyl methacrylate (HEMA) copolymer solution dissolved in 84.5 ml of ethyl acetate, 0.05 part by weight of the porphyrin dye of formula 1, a neon-cut dye, 0.05 parts by weight of T-39M as an isocyanate-based crosslinking agent and 0.07 parts by weight of T-789J as a silane coupling agent were added to 45 parts by weight of methyl ethyl ketone (MEK), followed by mixing to prepare a coating solution. Coating to a thickness to prepare a multifunctional pressure-sensitive adhesive film.

After that, the durability was tested by the above method, and the results are shown in Table 2, and the spectral change results of the pressure-sensitive adhesive film are shown in FIG. 2.

TABLE 2

Visible light transmittance (%) 400 nm 450 nm 528 nm 550 nm 593 nm 612nm 628 nm Early 68.8 70.3 60.9 52.5 27.9 53.6 74.0 After 500 hours 68.7 70.5 60.5 52.3 28.0 54.1 74.2

From the durability test results of Table 2 and the spectral change of FIG. 2, it can be seen that the pressure-sensitive adhesive film including the color correction dye of Example 4 of the present invention has excellent retention of visible region transmittance.

(Example 5)

Manufacture films containing neon-cut dyes

100 parts by weight (14.5% by weight) of a butyl acrylate / acrylic acid copolymer solution dissolved in 84.5 ml of ethyl acetate, 0.05 parts by weight of porphyrin-based dye of formula 1 as a neon cut dye, 0.23 parts by weight of T-39M as an isocyanate-based crosslinking agent, and 0.03 parts by weight of T-789J as a coupling agent was added to 45 parts by weight of methyl ethyl ketone (MEK) to prepare a coating solution after mixing, and then coated on a base film to prepare a multifunctional adhesive film.

Then, the durability test by the above-described method is shown in Table 3, the results are shown in Figure 3, the spectrum change results for the pressure-sensitive adhesive film.

TABLE 3

Visible light transmittance (%) 400 nm 450 nm 528 nm 550 nm 593 nm 612nm 628 nm Early 67.9 69.8 60.7 52.3 27.4 53.0 73.6 After 500 hours 67.0 69.6 60.5 52.4 28.0 53.7 73.6

From the durability test results of Table 3 and the spectral change of Figure 3, it can be seen that the pressure-sensitive adhesive film containing the color correction dye of Example 5 of the present invention is excellent in the maintenance of visible region transmittance.

(Example 6)

Neon-Cut Dye + Near infrared  Manufacture of Films Containing Dyes

0.3 parts by weight of dimonium-based dye (first near-infrared absorbing dye) (CIR1081, Japan Carlit Co.) and 0.1 parts by weight of phthalocyanine-based dye (second near-infrared absorbing dye) (IP12, Japan catalyst Co.) A coating solution was prepared in the same manner as in Example 4, and the coating solution was coated on the base film to prepare a multifunctional adhesive film.

Then, the durability test by the above-described method is shown in Table 4, the results are shown in Figure 4, the spectrum change results for the pressure-sensitive adhesive film.

TABLE 4

Visible light transmittance (%) Near infrared ray transmittance (%) 400 nm 450 nm 528 nm 550 nm 586 nm 612nm 628 nm 850 nm 950 nm Early 23.4 583 52.2 48.6 24.3 45.9 63.4 4.2 2.7 After 500 hours 23.6 655.3 52.3 48.5 24.4 45.4 62.9 5.0 4.0

From the durability test results of Table 4 and the spectral change of FIG. 4, it can be seen that the pressure-sensitive adhesive film of Example 6 of the present invention not only has excellent ability to maintain visible light transmittance but also has excellent near-infrared light transmittance.

(Comparative Example 1)

The film was prepared by changing the composition of the coating solution as follows.

Composition of the coating liquid: cyanine dye (0.0214 g, TY102: Asahi denka, trade name) as a neon-cut dye, 14BB (100 g, containing acryl-based adhesive, -OH group), curing agent (0.03 g, T-39M), and coupling agent (0.07g, T-789J)

Coating: Bar coating, Drying thickness 25mm

After that, the durability was tested by the above-described method, and the results are shown in Table 5, and the spectral change results for the pressure-sensitive adhesive film are shown in FIG.

TABLE 5

Visible light transmittance (%) Wavelength (nm) 450 550 587 625 Before durability test 57.6 38.7 11.5 66.5 After 100 degrees 10 minutes 43.6 39.0 11.9 66.6 After high temperature (80 degrees) durability test 43.0 44.3 16.1 67.3

In addition, the results after the 500 hours test at high temperature and high humidity are shown in Table 6, and the results of spectral change for the pressure-sensitive adhesive film are shown in FIG.

TABLE 6

Visible light transmittance (%) Wavelength (nm) 450 550 587 628 Before durability test 56.6 37.0 10.4 65.4 After 100 degrees 10 minutes 56.3 37.3 10.7 65.5 After high temperature (80 degrees) durability test 53.2 46.8 18.1 66.6

From the above results it can be seen that in Comparative Example 1 compared to the present application after the durability test, such as high temperature and high humidity retention of the visible light region transmittance is poor.

(Comparative Example 2)

The composition of the coating solution was changed as follows to prepare a near-infrared absorbing film.

Coating solution composition: cyanine NIR absorbing dye (0.01g, TY102: Asahi denka, trade name), 14BB (20g, acryl-based adhesive, -OH group), curing agent (0.006g, T-39M), couple Ring agent (0.014g, T-789J)

Coating: Bar coating, Drying thickness (20mm)

Curing condition: Room temperature 3 days

Then, the durability test by the method described above is shown in Table 7 and the results, the spectrum change results for the pressure-sensitive adhesive film is shown in FIG.

TABLE 7

Visible light transmittance (%) Wavelength (nm) 450 550 587 628 854 Before durability test 80.9 84.8 84.3 80.7 34.2 After high temperature (80 degrees) durability test 81.2 85.1 84.7 82.5 35.4

From the above results, in the case of Comparative Example 2 includes a cyanine-based dye, it can be seen that after the durability test such as high temperature and high humidity compared to the present application, the ability to maintain the visible light transmittance is poor.

(Example 7)

plasma  Manufacture of display panel filters

Anti-reflective film (AR film) 30) on the glass substrate, the adhesive film 28 of Example 1, the tempered glass 26, pressure-sensitive adhesive layer (PSA) 24, electromagnetic wave shielding film (EMI film) 22 in order A plasma display panel filter having a structure as shown in FIG. 8 (five layers) was manufactured.

(Example 8)

plasma  Manufacture of display panel filters

Anti-reflective film (AR film) 30 on the glass substrate, the adhesive film 28 of Example 4, NIR film 29, PSA 24, tempered glass 26, PSA 24, electromagnetic shielding film (EMI film) 22 in order To produce a plasma display panel filter having a structure as shown in FIG.

(Comparative Example 3)

For each film, a rubber-based adhesive was used as the adhesive for the adhesion (PSA), and the anti-reflective film 30, the pressure-sensitive adhesive layer 24, the color correction film 25 of the comparative example 1, the pressure-sensitive adhesive layer 24, the near-infrared film 29 of the comparative example 2, the pressure-sensitive adhesive layer 24, tempered glass 26, pressure-sensitive adhesive layer 24, and the electromagnetic wave shielding film 22 were formed in this order to prepare a plasma display panel filter. The structure is shown in FIG. 10, and the structure of the filter of the comparative example 3 consists of nine layers.

 As described above, the multifunctional pressure-sensitive adhesive film of the present invention improves durability than the conventional one by using an adhesive-based acrylic pressure-sensitive adhesive as a binder resin, by using a color correction dye and a near infrared absorbing dye to impart a color correction function and near infrared function In addition, it has excellent color correction ability, excellent near-infrared transmittance, and especially excellent adhesive function on the film itself, so that the structure of the plasma display panel filter can be simplified because there is no need to use a separate adhesive. It can be used to manufacture display panels.

Claims (30)

Near infrared absorbing dyes; And Neon-cut dye Plasma display panel film comprising a. The method of claim 1, wherein the near-infrared absorbing dye is a dimonium-based dye represented by the following formula (4), a phthalocyanine-based dye represented by the formula (5), a naphthalocyanine-based dye represented by the formula (6), (7) and (8) A film for plasma display panel is selected from one or more selected from the group consisting of metal-complex dyes represented by: [Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Formula 4, R ₁ To R ₁₂ Each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted aryl group having 1 to 16 carbon atoms, X is a monovalent or divalent organic acid anion, or monovalent or divalent Is an inorganic inorganic acid anion, In Formulas 5 and 6, each R is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, A substituted or unsubstituted allyloxy group, a fluorine-substituted alkoxy group, or a pentagonal ring having at least one substituted or unsubstituted nitrogen atom, and M is two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom And any one of oxy metals, In Formulas 7 and 8, R and R ₁ to R ₄ are each independently hydrogen, an alkyl group having 1 to 16 carbon atoms, an aryl group, or an alkoxy group, a phenoxy group, a hydroxyl group, an alkyl amino group having 1 to 16 carbon atoms, an aryl amino group, It is a trifluoro methyl group, a C1-C16 alkyl thi group, an aryl thi group, a nitro group, a cyano group, a halogen atom, a phenyl group, or a naphthyl group. The film of claim 2, wherein M is a metal selected from the group consisting of nickel, platinum, palladium, and copper. The film for a plasma display panel of claim 2, wherein X in Chemical Formula 4 is a monovalent organic acid anion selected from the group consisting of organic carboxylic acid ions, organic sulfonic acid ions, and organic boric acid ions. According to claim 2, X in formula 4 is selected from the group consisting of acetate ions, lactate ions, trifluoroacetate ions, propionate ions, benzoate ions, oxalate ions, succinate ions and stearate ions Film for plasma display panels which are organic carboxylic acid ions. According to claim 2, X in the formula 4 is a metal sulfonate ion, toluene sulfonate ion, naphthalene monosulfonate ion, chlorobenzene sulfonate ion, nitrobenzene sulfonate ion, dodecylbenzene sulfonate ion, benzone sulfonate A film for plasma display panel which is an organic sulfonic acid ion selected from the group consisting of ions, ethane sulfonate ions and trifluoromethane sulfonate ions. 3. The film of claim 2, wherein X in Formula 4 is an organic boric acid ion selected from the group consisting of tetraphenylborate ions and butyltriphenylborate ions. According to claim 2, X in Formula 4 is halogenide ion, thiocyanate ion, nitrate ion, molybdate ion, tungstate ion, titanate ion, vanadate ion, phosphate ion, borate ion, hexa A film for plasma display panel which is a monovalent inorganic acid anion selected from the group consisting of fluoroantimonate ions, hexafluorophosphate ions, and tetrafluoroborate ions. 3. The film of claim 2, wherein X in Formula 4 is a halogenide ion selected from the group consisting of fluoride ions, chloride ions, bromide ions, iodide ions, perchlorate ions, and periodate ions. The film of claim 2, wherein X in Formula 4 is a divalent inorganic acid anion selected from the group consisting of naphthalene-1,5-disulfonic acid, naphthalene-1,6-disulfonic acid, and naphthalene disulfonic acid derivatives. . The method of claim 1, wherein the near-infrared absorbing dye is 1 from the group consisting of a phthalocyanine-based dye represented by the formula (5), a naphthalocyanine-based dye represented by the formula (6) and a metal-complex dye represented by the formula (7). The film for plasma display panel which is selected from more than one species:  [Formula 5]

[Formula 6]

[Formula 7]

In Formulas 5 and 6, each R is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, A substituted or unsubstituted allyloxy group, a fluorine-substituted alkoxy group, or a pentagonal ring having at least one substituted or unsubstituted nitrogen atom, and M is two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom And any one of oxy metals, In Formula 7, R ₁ and R ₂ are each independently hydrogen, an alkyl group having 1 to 16 carbon atoms, an aryl group, or an alkoxy group, a phenoxy group, a hydroxyl group, an alkyl amino group having 1 to 16 carbon atoms, an aryl amino group, a trifluoromethyl group, An alkyl thi group, an aryl thi group, a nitro group, a cyano group, a halogen atom, a phenyl group, or a naphthyl group having 1 to 16 carbon atoms. The method of claim 1, wherein the neon-cut dye is a porphyrin-based (porphyrin) compound having a binding form of the intramolecular metal-complex represented by the formula (1); Film for plasma display panel is selected from the group consisting of cyanine-based compound having the form of the intermolecular metal-complex represented by the formula (2) and formula (3): [Formula 1]

[Formula 2]

[Formula 3]

In Formula 1, R ₁ to R ₈ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted alkoxy group; Pentagonal ring having one or more substituted or unsubstituted phenyl group, substituted or unsubstituted carbonyl allyloxy group, fluorine substituted alkoxy group, or substituted or unsubstituted nitrogen atom; M is a metal having a divalent to tetravalent ligand, and may be substituted with a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or an alkoxy group, In Chemical Formulas 2 and 3, Each R is independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon having 1 to 30 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 30 carbon atoms, X and Y are each independently halogen, nitro group, carboxyl group, alkoxy group having 2 to 8 carbon atoms, phenoxycarbonyl group, carboxylate group, alkyl group having 1 to 8 carbon atoms, alkoxy group having 1 to 8 carbon atoms, or 6 to 30 carbon atoms Is an aryl group. The film of claim 1, wherein M is a divalent metal atom selected from the group consisting of Cu, Zn, Fe, Co, Ni, Ru, Rd, Pd, Mn, Sn, Mg, and Ti. . The film of claim 12, wherein M in Formula 1 is a trivalent metal atom selected from the group consisting of Al, Ga, In, Fe, and Ru. The film of claim 1, wherein M in Formula 1 is a monosubstituted trivalent metal atom selected from the group consisting of Al-Cl, Ga-Cl, In-Cl, Fe-Cl, and Ru-Cl. The film of claim 12, wherein M in Formula 1 is a tetravalent metal atom selected from the group consisting of Si, Ga, Ti, Sn, Ge, and Mn. The method of claim 12, wherein M in Formula 1 is a group consisting of SiCl ₂ , GaCl ₂ , TiCl ₂ , SnCl ₂ , Si (OH) ₂ , Ge (OH) ₂ , Mn (OH) ₂ and Sn (OH) ₂ A film for plasma display panel which is a disubstituted tetravalent metal atom selected from. 13. The film of claim 12, wherein M in Formula 1 is an oxymetal in the form of oxygen bond selected from the group consisting of VO, MnO and TiO. The film for plasma display panel of claim 1, wherein the neon-cut dye is a porphyrin-based compound having a binding form of an intramolecular metal-complex represented by Formula 1 below: [Formula 1]

In Formula 1, R ₁ to R ₈ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted alkoxy group; Pentagonal ring having one or more substituted or unsubstituted phenyl group, substituted or unsubstituted carbonyl allyloxy group, fluorine substituted alkoxy group, or substituted or unsubstituted nitrogen atom; M is a metal having a divalent to tetravalent ligand and may be substituted with a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or an alkoxy group. The method of claim 1, wherein the neon-cut dye is a porphyrin compound having a combined form of an intramolecular metal-complex represented by Formula 1, and the near-infrared absorbing dye is a phthalocyanine dye represented by Formula 5, A film for plasma display panel selected from the group consisting of a naphthalocyanine dye represented by the formula (6) and a metal-complex dye represented by the formula (7): [Formula 1]

 [Formula 5]

[Formula 6]

[Formula 7]

In Formula 1, R ₁ to R ₈ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted alkoxy group; Pentagonal ring having one or more substituted or unsubstituted phenyl group, substituted or unsubstituted carbonyl allyloxy group, fluorine substituted alkoxy group, or substituted or unsubstituted nitrogen atom; M is a metal having a divalent to tetravalent ligand and may be substituted with a hydrogen atom, an oxygen atom, a halogen atom, a hydroxyl group or an alkoxy group, In Formulas 5 and 6, each R is independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms, A substituted or unsubstituted allyloxy group, a fluorine-substituted alkoxy group, or a pentagonal ring having at least one substituted or unsubstituted nitrogen atom, and M is two hydrogen atoms, a divalent metal atom, a trivalent or tetravalent substituted metal atom And any one of oxy metals, In Formula 7, R ₁ And R ₂ are each independently hydrogen, an alkyl group having 1 to 16 carbon atoms, an aryl group, or an alkoxy group, a phenoxy group, a hydroxyl group, an alkyl amino group having 1 to 16 carbon atoms, an aryl amino group, a trifluoromethyl group, or an alkyl tee having 1 to 16 carbon atoms. Group, aryl thi group, nitro group, cyano group, halogen atom, phenyl group, or naphthyl group. The film of claim 1, wherein the film blocks neon peaks in the 570 nm to 600 nm region or blocks near infrared rays in the 800 nm to 1100 nm region by 10% or less. The dye according to claim 1, wherein the film has a dye in the visible region of 380 nm to 780 nm and the near infrared region of 800 nm to 1100 nm, which the film has after 90 hours RH 500 hours at 60 ° C. after a high temperature test at 80 ° C. for 500 hours. The film for plasma display panels whose density change rate is 10% or less. A plasma display panel filter comprising the film according to any one of claims 1 to 22 in at least one layer of the layer formed on the upper and lower portions of the substrate. 24. The filter of claim 23, wherein the filter further comprises an antireflection film (AR film), an electromagnetic wave shielding film (EMI film), and a black screen treatment layer. 24. The filter of claim 23, wherein the filter further comprises a color correction film or a near infrared film. 24. The filter of claim 23, wherein the filter includes an antireflection film (AR film) disposed at an outermost side thereof. 24. The filter of claim 23, wherein the filter is sequentially laminated in the order of an antireflection film (AR film), a film according to any one of claims 1 to 22, a tempered glass, a pressure-sensitive adhesive layer, and an electromagnetic shielding film (EMI film). The plasma display panel filter. The method of claim 23, wherein the filter is an antireflection film (AR film), the film according to any one of claims 1 to 22, a color correction film or a near infrared film, pressure-sensitive adhesive layer, tempered glass, pressure-sensitive adhesive layer and Plasma display panel filter which is laminated in order of electromagnetic shielding film (EMI film). The method of claim 23, wherein the filter is an antireflection film (AR film), the film according to any one of claims 1 to 22, color correction film, pressure-sensitive adhesive film, near-infrared film, pressure-sensitive adhesive film, tempered glass, pressure-sensitive adhesive film The plasma display panel filter laminated | stacked in order, electromagnetic wave shielding film (EMI film). A plasma display panel comprising the filter of claim 23.

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