KR101340547B1 - Adhesive composition and plasma display panel filter comprising the same - Google Patents

Abstract

The present invention relates to a pressure-sensitive adhesive composition for a plasma display panel which is excellent in viscoelasticity and durability and has no change in haze and near-infrared absorptivity even after reliability evaluation.

Description

Adhesive composition and plasma display panel filter comprising the same

The present invention relates to an adhesive composition for a plasma display panel filter and a plasma display panel filter including the same. More specifically, the present invention has excellent viscoelasticity and excellent deformation and restoration due to external force including the weight of the plasma display panel without changing the haze and near infrared ray absorbing ability even after a long time reliability evaluation with color correction function. The present invention relates to an adhesive composition for a plasma display panel filter and a plasma display panel filter including the same.

Recently, a plasma display has attracted attention in implementing a large screen among flat panel display panels. The plasma display is composed of a plasma display panel and a plasma display panel filter.

The plasma display panel is composed of two glass substrates. Partitions are formed on two substrates, and gas injection tubes are installed on the substrates. A plasma gas is injected between two substrates through a gas injection tube to discharge the screen. The plasma display panel filter serves to correct the color of the spectrum emitted from the plasma display panel and shield near-infrared rays and electromagnetic waves that cause malfunction of the remote control device. For this purpose, the plasma display panel filter should have no change in haze and near-infrared absorption capability even after a long time reliability evaluation together with a color correction function. The plasma display panel filter has a structure in which each layer including an antireflection layer, a color correction layer for correcting color purity, a near infrared absorbing layer, an electromagnetic wave shielding layer, etc. is laminated on a transparent substrate such as glass or polyethylene terephthalate (PET). . In general, a dye having color correction and near infrared absorption ability is mixed with an adhesive to be inserted into a plasma display panel filter.

Meanwhile, as shown in FIG. 1, a plasma display panel is manufactured by directly attaching a plasma display panel to a plasma display panel filter. In this case, since the gas injection pipe installed in the plasma display panel may be damaged, the plasma display panel filter moves while being pressed by the roller. At this time, the pressure-sensitive adhesive included in the plasma display panel filter is easily deformed by being pressed by the weight of the plasma display panel. This eventually increases the failure rate of the plasma display panel.

Therefore, the plasma display has excellent viscoelasticity and excellent deformation and restoration due to external force including the weight of the plasma display panel without changing the haze and near-infrared absorption ability even after the long-term reliability evaluation with the color correction function. It is necessary to manufacture panel filters.

An object of the present invention is to provide a plasma display panel filter having excellent durability without change in haze and near-infrared absorbing ability even after a long time reliability evaluation.

Another object of the present invention is to provide a plasma display panel filter which is excellent in resilience and deformation ability to external forces due to its excellent viscoelasticity.

Pressure-sensitive adhesive composition for a plasma display panel filter of the present invention

Acrylic pressure-sensitive adhesives;

And color correction dyes,

The acrylic pressure-sensitive adhesive may have a glass transition temperature (Tg) of −40 ° C. or more and a modulus measured by ARES (advanced rheometric expansion system) after curing to be 10 ⁵ dyne / cm ^{2 or} more.

In one embodiment, the acrylic pressure-sensitive adhesive may include 30 to 70 parts by weight of 4 to 10 (meth) acrylic acid alkyl ester having a glass transition temperature of 0 ° C. or more in 100 parts by weight of the acrylic pressure sensitive adhesive.

In one embodiment, the acrylic pressure-sensitive adhesive is a) 25-60 parts by weight of 4-10 carbon (meth) acrylic acid alkyl ester having a glass transition temperature of -20 ℃ or less; b) 5 to 10 parts by weight of a (meth) acrylic monomer including a hydroxyl group; And c) 30 to 70 parts by weight of 4 to 10 (meth) acrylic acid alkyl esters having a glass transition temperature of 0 ° C. or more.

In one embodiment, the weight ratio of the a) to c) in the acrylic pressure-sensitive adhesive may be 1: 0.5 to 1: 1.5.

In one embodiment, the weight average molecular weight (Mw) of the acrylic pressure-sensitive adhesive may be 800,000 ~ 1 million g / mol.

In one embodiment, PDI (polydispersity index, Mw / Mn) of the acrylic pressure-sensitive adhesive may be 5 or less.

The plasma display panel filter of the present invention may include an adhesive film on which the adhesive composition is coated on a release film.

In one embodiment, the filter may have a yellowness index (YI) of 1 or less.

The plasma display panel of the present invention may include the plasma display panel filter.

The present invention can provide a plasma display panel filter having no change in haze and near-infrared absorbing ability even after a long time reliability evaluation. In addition, the present invention can provide a plasma display panel filter having excellent viscoelasticity and excellent in deformation and restoration by an external force including the weight of the plasma display panel.

1 schematically illustrates a shape in which a plasma display panel is attached to a plasma display panel filter.
2A and 2B show a schematic method of evaluating the pressing characteristics for a plasma display filter according to an embodiment of the present invention.
3 is a view illustrating a transmittance (T,%) at a wavelength band of 380 nm to 980 nm according to a standing time for a plasma display filter including an adhesive film according to an embodiment of the present invention.

Pressure-sensitive adhesive composition for a plasma display panel filter according to the present invention

Acrylic pressure-sensitive adhesives; And

Contains color correction dye,

The acrylic pressure-sensitive adhesive has a glass transition temperature (Tg) of above -40 ℃ and ARES (advanced rheometric expansion system) method modulus (modulus) measured by a 10 ⁵ be equal to or greater than dyne / cm ² after cure. Preferably, the modulus of elasticity may be 10 ^{6-10 8} dyne / cm ² .

Acrylic adhesive

In the present invention, the acrylic pressure sensitive adhesive may have a glass transition temperature of -40 ° C or higher, preferably -30 to -10 ° C. If the glass transition temperature is lower than −40 ° C., the pressure-sensitive adhesive may be easily deformed by external stress.

In the present invention, the acrylic adhesive may have an elastic modulus of 10 ⁵ dyne / cm ² or more, preferably 10 ⁶ or more and 10 ⁸ or less dyne / cm ² , measured by the ARES method after curing. Below 10 ⁵ dyne / cm ² , the adhesive can be easily deformed by external stress.

In the present invention, the acrylic pressure sensitive adhesive may include 4-10 carbon (meth) acrylic acid alkyl ester having a glass transition temperature of 0 ° C. or more. Preferably, the glass transition temperature may be between 10 and 100 ° C.

In the present invention, "(meth) acrylic acid alkyl ester" includes not only acrylic acid alkyl esters but also alkyl esters of methacrylic acid. In the present invention, the carbon number in the "carbon 4-10 (meth) acrylic acid alkyl ester" means the carbon number of the entire ester.

In the present invention, the acrylic pressure sensitive adhesive may include, for example, 30 to 70 parts by weight of 4 to 10 carbon (meth) acrylic acid alkyl ester having a glass transition temperature of 0 ° C. or more in 100 parts by weight of the acrylic pressure sensitive adhesive. In the above range, the pressure-sensitive adhesive is not easily deformed by external stress, and excellent in reliability.

In the present invention, the acrylic pressure-sensitive adhesive a) 25 to 60 parts by weight of (meth) acrylic acid alkyl ester of 4 to 10 carbons having a glass transition temperature of -20 ° C. or less, b) 5 to 10 parts by weight of a (meth) acrylic monomer including a hydroxy group, And c) 30 to 70 parts by weight of 4 to 10 (meth) acrylic acid alkyl esters having a glass transition temperature of 0 ° C. or more.

When the a) (meth) acrylic acid alkyl ester is within the above weight part range, the reliability may be high, the elastic modulus may be high, and there may be no crushing during crushing measurement.

When the b) (meth) acrylic monomer is in the above weight part range, the crosslinking density is sufficient, there is no crushing during crushing measurement, and reliability may be good.

When the c) (meth) acrylic acid alkyl ester is within the above weight part range, there may be no crushing when measuring crushing, and reliability may be good.

The weight ratio of the a) (meth) acrylic acid alkyl ester to the c) (meth) acrylic acid alkyl ester in the acrylic pressure sensitive adhesive may be 1: 0.5 to 1: 1.5. Within this weight ratio range, the pressing characteristics may not be weak, and the reworkability and reliability may be good.

PDI (polydispersity index, Mw / Mn) of the acrylic adhesive may be 5 or less.

The weight average molecular weight (Mw) of the acrylic pressure-sensitive adhesive may be 800,000 to 1 million g / mol, preferably 800,000 to 900,000 g / mol. Within this range, the reliability may be good and the coating workability may not be reduced.

The a) (meth) acrylic acid alkyl ester may be included without limitation as long as the glass transition temperature is -20 ° C. or lower and 4 to 10 carbon (meth) acrylic acid alkyl esters. For example, it may include one or more selected from the group consisting of n-butyl (meth) acrylate and ethyl (meth) acrylate.

The (meth) acrylic monomer including the b) hydroxy group may be included without limitation as long as it is a monomer having at least one hydroxyl group and a polymerizable unsaturated bond in the molecule. For example, from the group consisting of 4-hydroxy butyl (meth) acrylate and 2-hydroxy ethyl (meth) acrylate, having from 3 to 10 carbon atoms containing at least one hydroxy group and at least one unsaturated bond It may include one or more selected.

The c) (meth) acrylic acid alkyl ester may be included without limitation as long as the glass transition temperature is 0 ° C. or higher and 4 to 10 carbon (meth) acrylic acid alkyl esters. For example, it may include one or more selected from the group consisting of methyl acrylate and methyl methacrylate.

In the present invention, the acrylic pressure-sensitive adhesive may further include a monomer d) polymerizable with any one of the monomers a), b) and c). For example, it may include one or more selected from the group consisting of methacrylic acid and acrylic acid.

The monomer d) may be included in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the acrylic pressure sensitive adhesive.

Color correction dye

In the present invention, the color correction dye may be used that is commonly used in the manufacture of the plasma display panel filter. For example, the color correction dye may use a near infrared absorbing dye. The near-infrared absorbing dye can be used one or more selected from the group consisting of phthalocyanine dyes, dithiol dyes, diimnium dyes and naphthalocyanine dyes. Preferably, a phthalocyanine type near-infrared absorbing dye can be used. The dye may be a dye that absorbs near infrared rays in the wavelength range of 750 nm to 3000 nm, preferably 800 nm to 1100 nm.

The color correction dye may be included in 0.1 to 10 parts by weight, preferably 2 to 3 parts by weight based on 100 parts by weight of the acrylic pressure-sensitive adhesive.

Adhesive composition for plasma display panel filter

In the present invention, the pressure-sensitive adhesive composition may further include one or more selected from the group consisting of a polymerization reaction initiator, a curing agent, a coupling agent, a visible light control dye, a heat stabilizer, an antioxidant, and the like, in addition to the acrylic pressure-sensitive adhesive and color correction dye.

The polymerization initiator is for the polymerization of the acrylic pressure-sensitive adhesive, it can be used a polymerization reaction initiator commonly used in the polymerization reaction. For example, azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, etc. can be used. The polymerization initiator may be included in an amount of 0.01 to 1.0 parts by weight based on 100 parts by weight of the a) (meth) acrylic acid alkyl ester.

The curing agent may be used for curing the acrylic adhesive and the color correction dye as a multifunctional compound. The curing agent may include, for example, an isocyanate curing agent, an epoxy curing agent, an aziridine curing agent, or a metal chelate curing agent. Preferably, an isocyanate hardener can be used, and the hexamethylene diisocyanate (HMDI) hardener can be used as an example. The curing agent may be included in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the acrylic adhesive.

Coupling agent is preferably a silane coupling agent. When the silane coupling agent is left for a long time under high temperature and high humidity, the adhesion reliability can be improved. The silane coupling agent can use vinyl silane, epoxy silane, (meth) acryl silane, etc. For example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, or γ- (meth) acryloxypropyltrimethoxysilane can be used alone or in combination, but these It is not limited to. The coupling agent may be included in an amount of 0.01 to 1.0 parts by weight based on 100 parts by weight of the acrylic adhesive.

As the visible light control dye, conventional dyes representing red, green, blue, and the like can be used. The visible light control dye may be added in various amounts depending on the transmittance of the pressure-sensitive adhesive composition.

In the present invention, the pressure-sensitive adhesive composition may further include a solvent. The solvent may be a conventionally used organic solvent. Preferably, one or more selected from the group consisting of ethyl acetate, methyl ethyl ketone and toluene can be used, but is not limited thereto. The content of the solvent may vary depending on the physical properties or the content of the acrylic pressure-sensitive adhesive, the near-infrared absorbing dye and the additional components included in the pressure-sensitive adhesive composition.

The present invention can provide a plasma display panel filter.

The plasma display panel filter may include an adhesive film made of the adhesive composition according to the present invention. The method of manufacturing the said adhesive film is not specifically limited. For example, polymerizing the monomers a) to c) to prepare an acrylic pressure-sensitive adhesive, mixing the acrylic pressure-sensitive adhesive with color correction dyes and curing agents to prepare a coating solution, and coating the coating solution on a release film and curing It can manufacture. Spray coating, roll coating, bar coating, spin coating may be used as the coating method.

The pressure-sensitive adhesive film may have a coating thickness of 10 μm or more, for example, 10-30 μm.

The PDI of the filter may be 5 or less.

The yellowness index (YI) of the filter may be 1 or less. YI is a measure of evaluating the clear or near-colorless of the pressure-sensitive adhesive. When the YI value of the pressure-sensitive adhesive is less than 1, there is no color variation according to lot.

The plasma display panel filter may include a base film, an antireflection film, an electromagnetic wave shielding film, a black screen treatment layer, etc., in addition to the adhesive film. The filter may be manufactured by laminating an adhesive film, a base film, an antireflection film, an electromagnetic wave shielding film, a black screen treatment layer, or the like by a conventional method.

The present invention can provide a plasma display panel including the plasma display panel filter. The plasma display panel can be manufactured using conventional methods known in the art.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since the description can be inferred by those skilled in the art.

Example

A pressure-sensitive adhesive film and a filter were prepared using the components listed below.

a): n-butyl acrylate (BA)

b): 4-hydroxybutyl acrylate (4HBA)

c): methyl acrylate (MA)

Color correction dye: PC970 (phthalocyanine-based near infrared absorption dye, Uksung chemical)

Curing agent: DN-950 (HMDI isocyanate-based trifunctional curing agent, Aekyung Chemical)

Visible light control dyes: RED233, Green250, Blue163 (Orient Chemical)

Examples 1 to 5: preparation of pressure-sensitive adhesive film and filter

(1) Preparation of acrylic pressure-sensitive adhesive: In a mixed solvent containing 60 parts by weight of ethyl acetate and 30 parts by weight of methyl ethyl ketone, 0.04 parts by weight of the monomers listed in Table 1 and the polymerization initiator AIBN (azobisisobutyronitrile) were placed in a reaction vessel. A nitrogen stream was supplied to replace the inside of the reaction vessel with nitrogen air. The temperature of the reaction vessel was raised, and the internal temperature of the reaction vessel was reacted at 60 ° C. for 4 hours. 40 parts by weight of methyl ethyl ketone was further added and reacted at 60 ° C. for 4 hours. After the reaction was completed, the mixture was cooled and 120 parts by weight of methyl ethyl ketone was added thereto.

(2) Preparation of coating liquid: To the acrylic pressure-sensitive adhesive prepared above, 0.5 parts by weight of a curing agent, a color correction dye, visible light control dye, and 45 parts by weight of methyl ethyl ketone were added and mixed to prepare a coating solution.

(3) Preparation of adhesive film: The coating solution prepared above was coated on a polyethylene terephthalate (PET) release film with a thickness of 20 μm, cured at 80 ° C. for 5 minutes, and then laminated with the same release film to prepare an adhesive film.

(4) Preparation of filter: The pressure-sensitive adhesive film was laminated on a hard coat or antireflection coated PET film using a pressing roller to prepare a color correction filter for directly attaching a panel.

Comparative Examples 1 to 2: preparation of pressure-sensitive adhesive film and filter

A pressure-sensitive adhesive film and a filter were prepared in the same manner as described above, except that the components according to Table 1 were modified.

About the said Examples 1-5 and Comparative Examples 1-2, the glass transition temperature, molecular weight, PDI value, and elastic modulus of an acrylic adhesive were measured. Pressing was evaluated on the filters produced. The results are shown in Table 1.

≪ Method for measuring physical properties &

1. Molecular weight and PDI: The molecular weight and PDI of the acrylic pressure-sensitive adhesive were measured using GPC (waters, GPC410).

2. Elastic modulus: The elastic modulus was measured by ARES.

3.Pressing of the filter: When the filter is pressed for 3 minutes with 3kg Load, the filter is "good" if there is no crushing. If pressing is observed for 2 minutes with 3kg Load, it is "weak" and 3kg Load. If pressing was observed when pressed for minutes, it was rated as “very fragile”.

Example Comparative Example One 2 3 4 5 One 2 Acrylic adhesive BA 40 50 55 50 49.5 99 80 4HBA 5 5 5 10 One One 5 MA 55 45 40 40 49.5 - 15 Color correction dye 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Hardener 1.0 1.0 1.0 1.5 0.5 0.2 1.0 MA / BA
Weight ratio value 1.3 0.9 0.73 0.8 1.0 - 0.1875 Glass transition temperature (℃) -20 -25 -28 -33 -22 -55 -45 Acrylic pressure sensitive adhesive (g / mol) 83 萬 73 萬 97 yen 90 萬 87 萬 160 萬 98 萬 PDI 4.7 4.6 4.4 4.5 4.5 4.5 4.5 Modulus (dyne / cm ² ) 1.02
x 10E6 9.28 x 10E5 9.03 x 10E5 1.64 x 10E6 1.81
x
10E5 8.123
x
10E3 7.48
x
10E4 pressed Good Good Good Good Good Extremely
Vulnerable Vulnerable

As shown in Table 1, the filter including the pressure-sensitive adhesive film according to the present invention can be seen that the acrylic pressure-sensitive adhesive has excellent viscoelastic properties. In addition, it can be seen that the filter of the present invention has better pressing characteristics compared to Comparative Examples 1 and 2.

After the filter prepared in Example 1 was left at 80 ° C. for 1000 hours, durability was measured. The results are shown in Table 2 and FIG. 3.

≪ Method for measuring physical properties &

1. Haze: Measured using an NDH-2000 instrument.

2. Total light transmittance: It measured using NDH-2000 instrument.

3. Y, x, y: Measured using a UV-VIS spectrometer (Lambda-950, Perkin Elmer).

4. Transmittance: Measured using an NDH-2000 instrument.

0 hours 1000 hours Variation Haze (%) 0.20 0.21 0.01 Total light transmittance (%) 42.06 43.11 0.63 Y 42.26 43.17 0.57 x 0.2992 0.3002 0.0008 y 0.3099 0.3125 0.0018 % Transmittance at 850 nm 12.8755 12.1839 0.99 % Transmittance at 950nm 4.9076 5.1949 0.25

As shown in Table 2 and Figure 3, it can be seen that the filter including the pressure-sensitive adhesive film according to the present invention has excellent durability in both visible and near infrared parts.

0 hours 1000 hours Variation Haze (%) 0.20 0.25 0.05 Total light transmittance (%) 41.58 42.15 0.57 Y 41.85 42.23 0.38 x 0.2983 0.2995 0.0012 y 0.3089 0.3105 0.0016 % Transmittance at 850 nm 11.5843 12.5315 0.95 % Transmittance at 950nm 4.6325 4.8945 0.26

Table 3 is a heat resistance reliability results of Example 2, and the durability was measured in the same manner for the filter prepared in the other Example 3-5, it was confirmed that has the same excellent durability as in Example 1.

0 hours 1000 hours Variation Haze (%) 0.34 0.45 0.11 Total light transmittance (%) 40.95 41.67 0.72 Y 41.05 41.45 0.40 x 0.2993 0.3005 0.0012 y 0.3095 0.3117 0.002 % Transmittance at 850 nm 10.9816 12.1856 1.20 % Transmittance at 950nm 4.5462 5.3154 0.77

Table 4 is a heat resistance reliability evaluation results for Comparative Example 1, it can be seen that the durability is poor compared to Example 1-2.

Claims (15)

Acrylic pressure-sensitive adhesives; And
Contains color correction dye,
The acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive composition for a plasma display panel filter having a glass transition temperature (Tg) of -40 ℃ or more and a modulus measured by ARES (advanced rheometric expansion system) after curing is 10 ⁵ dyne / cm ² or more.
The pressure-sensitive adhesive composition of claim 1, wherein the glass transition temperature is -30 ° C to -10 ° C.
The pressure-sensitive adhesive composition of claim 1, wherein the elastic modulus is 10 ⁶ -10 ⁸ dyne / cm ² .
The pressure sensitive adhesive composition according to claim 1, wherein the acrylic pressure sensitive adhesive comprises 30 to 70 parts by weight of 4 to 10 carbon (meth) acrylic acid alkyl esters having a glass transition temperature of 0 ° C or higher in 100 parts by weight of the acrylic pressure sensitive adhesive.
According to claim 1, wherein the acrylic pressure-sensitive adhesive is a) 25 to 60 parts by weight of a (meth) acrylic acid alkyl ester of 4 to 10 carbons having a glass transition temperature of -20 ℃ or less; b) 5 to 10 parts by weight of a (meth) acrylic monomer including a hydroxy group; And c) 30 to 70 parts by weight of (meth) acrylic acid alkyl ester of 4 to 10 carbons having a glass transition temperature of 0 ° C. or higher.
The pressure-sensitive adhesive composition of claim 5, wherein the weight ratio of a) to c) is from 1: 0.5 to 1: 1.5.
The pressure-sensitive adhesive composition of claim 5, wherein the acrylic pressure-sensitive adhesive further comprises a polymerizable monomer.
The pressure-sensitive adhesive composition of claim 1, wherein the weight average molecular weight (Mw) of the acrylic pressure-sensitive adhesive is 800,000-1 million g / mol.
The pressure-sensitive adhesive composition of claim 1, wherein a polydispersity index (PDI) of the acrylic pressure-sensitive adhesive is 5 or less.
The pressure-sensitive adhesive composition of claim 1, wherein the color correction dye is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic pressure-sensitive adhesive.
The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition further comprises one or more selected from the group consisting of a polymerization initiator, a curing agent, a coupling agent, a visible light control dye, and a solvent.
A plasma display panel filter comprising a pressure-sensitive adhesive film coated with the pressure-sensitive adhesive composition according to any one of claims 1 to 11.
The filter of claim 12, wherein the filter has a yellowness index (YI) of 1 or less.
The filter of claim 12, wherein the pressure-sensitive adhesive film has a coating thickness of 10 to 30 μm.
A plasma display panel comprising the filter of claim 12.

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