WO2023128581A1 - Adhesive composition - Google Patents

Abstract

The present invention provides: an adhesive composition including a curable resin, an initiator, a getter, and a cross-linking agent; a cured body and a dam structure, in which the adhesive composition is cured; and a display device including the dam structure.

Description

adhesive composition

The present invention relates to adhesive compositions.

Since the advent of the 4th industrial revolution, electronic devices are now with people 24 hours a day in daily life. At the same time, most electronic devices are placed together in an environment close to life. In particular, mobile devices are often placed in environments with high humidity. For example, in line with the epidemic of COVID-19, exposure to moisture and chemicals such as hand washing, use of sanitizers, etc. is typical. In addition, as various domestic activities become active due to the difficulties of overseas travel, there are situations in which electronic devices are exposed to a relatively high temperature external environment.

Meanwhile, along with the development of the semiconductor industry, the performance of materials is also being leveled up. It is a hot topic that the function of electronic devices is maintained for a long time as the performance is improved. After all, it is of interest that high-performance electronic devices are maintained without deterioration in the external environment. Here, it is a high-temperature, high-humidity environment that degrades the performance of the electronic device, and oxygen in the air is also a factor that degrades the performance of the electronic device.

Korean Patent Publication No. 10-2016-0011310 discloses an organic light emitting display device including a dam (DAM) structure disposed on a substrate and spaced apart from a display unit. The dam structure may be disposed outside the display unit and may be disposed to surround the display unit. As the dam structure exists outside the display unit, the permeation path of moisture or oxygen penetrating into the display unit from the outside of the organic light emitting display device is lengthened, and thus moisture permeability resistance of the organic light emitting display device may be further improved.

An object of the present invention is to provide an adhesive composition that helps to maintain the performance of electronic devices from the external environment.

In addition, it is an object of the present invention to provide an adhesive composition having excellent reliability under high-temperature-high-humidity conditions.

The above tasks and additional tasks are described in detail below.

As a means for solving the above problems,

The present invention provides an adhesive composition comprising a curable resin, a getter and a crosslinking agent, wherein the crosslinking agent includes a compound represented by Formula 1 or Formula 2 below.

<Formula 1>

(In Formula 1 above,

Ring A may or may not exist, and when present is a substituted or unsubstituted C3-C10 cycloalkyl group or a substituted or unsubstituted C3-C10 cycloalkenyl group,

X is hydrogen, a substituted or unsubstituted C2~C20 alkenyl group, a substituted or unsubstituted C1~C20 alkylidene group, (meth)acrylate or a substituted or unsubstituted C1~C30 in which (meth)acrylic acid is present. A substituted or unsubstituted C2-C30 alkenyl group in which an alkyl group or (meth)acrylate or (meth)acrylic acid is present, and the alkyl group or alkenyl group may have one or more -CH2- substituted with oxygen,

R1 is each independently hydrogen, heavy hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkoxy group group, a substituted or unsubstituted C1~C30 sulfide group, a substituted or unsubstituted C6~C50 aryl group, or a substituted or unsubstituted C2~C50 heteroaryl group,

m is an integer from 0 to 4;

Although not shown in Formula 1, the norbonane structure has or does not have a double bond, and the total number of double bonds present in the norbonane structure and ring A is 1 or 2, and the position of the double bond is not limited)

<Formula 2>

(In Formula 2 above,

Ring B may or may not be present, and if present is a substituted or unsubstituted C3-C10 cycloalkyl group (one or more -CH2- may be substituted with -CO-), or an epoxy ring;

Ring C may or may not be present, and if present, a substituted or unsubstituted C3-C10 cycloalkyl group (one or more -CH2- may be substituted with -CO-), an epoxy ring, or a cyclic anhydride a nobonanic group with or without a carboxylic acid;

Ring D may or may not exist, and if present, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group with an epoxy group, a cyclic dicarboxylic acid, Or an epoxy ring,

Y is hydrogen, a hydroxy group, a substituted or unsubstituted C1~C30 alkyl group in which (meth)acrylic acid is present (one or more -CH2- may be substituted with oxygen), a substituted or unsubstituted C1~ in which carboxylic acid is present A C30 alkenyl group, a substituted or unsubstituted C1~C30 hydroxyalkyl group or a carboxylic acid group,

Z is CH2, O, S, NR3, P=0 or PR4;

R2 is each independently hydrogen, heavy hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C1~C30 hydroxyalkyl group, carboxylic acid group, substituted or unsubstituted C1~C30 carboxylic acid alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkoxy group, substituted or unsubstituted C1~C30 sulfide group, substituted or unsubstituted A C6~C50 aryl group, or a substituted or unsubstituted C2~C50 heteroaryl group,

R3 and R4 are each independently hydrogen, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C2~C30 alkenyl group, a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C2~C30 aryl group. A C2~C30 heteroaryl group,

n is an integer from 0 to 4;

Although not shown in Formula 2, the norbonane structure has or does not have a double bond, the total number of double bonds present in the norbonane structure and ring A is 0 or 1, and the position of the double bond is not limited,

Although not shown in Chemical Formula 2, 0 to 2 epoxy structures in which oxygen is bonded to two adjacent carbons may be included,

Although not shown in Chemical Formula 2, 0 to 2 cyclic anhydride structures formed by bonding with neighboring carbons may be included).

The present invention also provides a cured product in which the adhesive composition is cured.

The present invention also provides a dam (DAM) structure in which the adhesive composition is cured.

The present invention also provides a display device including the dam structure.

The adhesive composition according to the present invention has a high cross-linking density, decreases the space between resins, thereby lowering the water permeation rate (moisture permeation rate), and has a cyclic structure, especially a bicyclic or bridged structure, which has a higher polarity than the linear structure, so that the attractive force between the resins is reduced. It acts strongly and has excellent adhesion and reliability.

The above effects and additional effects are described in detail below.

Prior to describing the present invention in detail below, it is understood that the terms used herein are intended to describe specific embodiments and are not intended to limit the scope of the present invention, which is limited only by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art unless otherwise specified.

Throughout this specification and claims, the terms "comprise", "comprise" and "comprising", unless stated otherwise, are meant to include a stated object, step or group of objects, and steps, and any other object However, it is not used in the sense of excluding a step or a group of objects or a group of steps.

Throughout this specification and claims, the term "aryl" refers to a C5-50 aromatic hydrocarbon ring group such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, fluorene, phenanthrenyl, triphenyl It may mean containing an aromatic ring such as renyl, perylenyl, chrysenyl, fluoranthenyl, benzofluorenyl, benzotriphenylenyl, benzochrysenyl, anthracenyl, stilbenyl, pyrenyl, etc., and "hetero "Aryl" is a C2-50 aromatic ring containing one or more heteroatoms, for example, pyrrolyl, pyrazinyl, pyridinyl, indolyl, isoindolyl, furyl, benzofuranyl, isobenzofuranyl, Dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, quinolyl group, isoquinolyl, quinoxalinyl, carbazolyl, phenanthridinyl, acridinyl, phenanthrolinyl, thienyl, and pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, indole ring, quinoline ring, acridine ring, pyrrolidine ring, dioxane ring, piperidine ring, morpholine ring, piperazine ring, carbazole ring , Furan ring, thiophene ring, oxazole ring, oxadiazole ring, benzofuran ring, thiazole ring, thiadiazole ring, benzothiophene ring, triazole ring, imidazole ring, benzoimidazole ring, pyran ring , It may mean including a heterocyclic group formed from a dibenzofuran ring and the like.

In addition, in the formula, Ar _x (where x is an integer) means a substituted or unsubstituted C6-C50 aryl group or a substituted or unsubstituted C2-C50 heteroaryl group, unless otherwise defined, and L _x ( Where x is an integer) means a direct bond, a substituted or unsubstituted C6~C50 arylene group, or a substituted or unsubstituted C2~C50 heteroarylene group, unless otherwise defined, and R _x (where x is If not particularly defined, hydrogen, deuterium, halogen, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1 ~C30 alkoxy group, substituted or unsubstituted C1~C30 sulfide group, substituted or unsubstituted C6~C50 aryl group, or substituted or unsubstituted C2~C50 heteroaryl group.

Throughout this specification and claims, the term “substituted or unsubstituted” refers to deuterium, halogen, amino, cyano, nitrile, nitro, nitroso, sulfamoyl, isothiocyanate, thiocyanate groups. , carboxyl group, or C1~C30 alkyl group, C1~C30 alkylsulfinyl group, C1~C30 alkylsulfonyl group, C1~C30 alkylsulfanyl group, C1~C12 fluoroalkyl group, C2~C30 alkenyl group, C1 ~C30 alkoxy group, C1~C12 N-alkylamino group, C2~C20 N,N-dialkylamino group, substituted or unsubstituted C1~C30 sulfide group, C1~C6 N-alkylsulfamoyl group, C2~C12 N,N-dialkylsulfamoyl group, C3~C30 silyl group, C3~C20 cycloalkyl group, C3~C20 heterocycloalkyl group, C6~C50 aryl group and C2~C50 heteroaryl group It may mean that it is substituted or unsubstituted with one or more groups selected from the group consisting of, but is not particularly limited thereto. In addition, the same symbol throughout the present specification may have the same meaning unless otherwise specified. On the other hand, * means a binding position.

On the other hand, various embodiments of the present invention can be combined with any other embodiments unless clearly indicated to the contrary. Hereinafter, embodiments of the present invention and effects thereof will be described.

Hereinafter, the present invention will be described in detail.

An adhesive composition according to an embodiment of the present invention includes a curable resin, a getter and a crosslinking agent. The adhesive composition may further include an initiator. The content of the crosslinking agent in the total composition may be included in the range of 0.5 to 30% by weight.

The curable resin may include an epoxy-based resin, an acrylic-based resin, or a mixture thereof. Types of the epoxy-based resin and the acrylic-based resin are not limited, and known resins and commercially available resins may be used.

Among the curable resins, as the epoxy-based resin, resins having an epoxy group applicable as an adhesive composition may be used without particular limitation. As an example, (3,4-epoxycyclohexyl)methyl-3',4'-epoxycyclohexanecarboxylate , 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, bis ((3 ,4-epoxy-6-methylcyclohexyl)methyl)adipate, bis(3,4-epoxycyclohexylmethyl)malonate, bis(3,4-epoxycyclohexylmethyl)succinate, bis(3,4- Epoxycyclohexylmethyl)glutarate, bis(3,4-epoxycyclohexylmethyl)pimelate, bis(3,4-epoxycyclohexylmethyl)azelate and bis(3,4-epoxycyclohexylmethyl)sebacate etc. can be used.

Among the curable resins, as the acrylic resin, resins having an acrylic group may be used without particular limitation, for example, Aliphatic difunctional urethane acrylate and Aliphatic trifunctional urethane acrylate. ), Aliphatic hexafunctional urethane acrylate, Aromatic difunctional urethane acrylate, Aliphatic trifunctional urethane acrylate and Aromatic hexafunctional urethane An acrylic resin having a urethane group such as acrylate (aromatic hexafunctional urethane acrylate) may be used.

When the epoxy resin and the acrylic resin are used together, the mixing ratio thereof may be 1:99 to 99:1, and more specifically, 25:75 to 75:25. It is not limited thereto.

As the initiator, a cationic initiator or a radical initiator may be used, and when an epoxy-based resin and an acrylic-based resin are used simultaneously, a cationic initiator and a radical initiator may be simultaneously used as the initiator. A cationic initiator is a material that initiates a ring-opening reaction of an epoxy group, and refers to a compound capable of initiating cationic polymerization by irradiation of electromagnetic waves or a compound capable of generating a compound capable of initiating cationic polymerization by irradiation of electromagnetic waves. . The content of the cationic initiator is preferably adjusted based on the content of the epoxy resin, for example, 0.1 to 10 parts by weight of the cationic initiator is preferably included with respect to 100 parts by weight of the epoxy resin, and 0.3 to 7 parts by weight is used. It is more preferred for efficient polymerization.

The type of the cationic initiator is not particularly limited, and for example, one or more cationic polymerization initiators selected from among aromatic diazonium salts, aromatic iodine aluminum salts, aromatic sulfonium salts, and iron-arene complexes may be used, among which aromatic sulfonium salts It may be preferred to use, but is not limited to the above example.

The radical initiator is, for example, a substance that reacts with an acrylate group to start an addition polymerization reaction, and the content of the radical initiator is preferably adjusted based on the content of the acrylic resin. For example, a radical initiator based on 100 parts by weight of the acrylic resin It is preferable to include 0.1 to 10 parts by weight, and it is more preferable to include 0.3 to 7 parts by weight for an effective polymerization reaction.

The radical initiator may be a thermal initiator or a photoinitiator. Thermal radical initiators include azo compounds such as 2,2'-azobis(isobutyronitrile); hydroperoxides such as tert-butyl hydroperoxide; and peroxides such as benzoyl peroxide and cyclohexanone peroxide, but one or more of them may be used, but is not limited thereto.

Getter is a material that absorbs and removes all gases and moisture very quickly by chemical reaction except for inert gas. It helps to maintain, and may be included in 0.1 to 40% by weight based on the total weight of the adhesive composition. When the adhesive composition contains less than 0.1% by weight of the getter, an excessively small amount of the getter may cause a problem in that the adhesive retention of the cured adhesive composition is greatly reduced. It is better to adjust with The content of the getter may be adjusted according to the desired characteristics of the adhesive composition, and the content of the getter is preferably 30% by weight or less in order to impart better adhesion, and the content of the getter is 10% by weight in order to realize a high crosslinking density of the adhesive composition. % or less may be preferred to be included in the adhesive composition.

Specifically, the getter may be included in the range of 0.5% by weight to 10% by weight. More specifically, the getter may be included within the range of 1% to 8% by weight. If it is less than the above range, the moisture blocking properties of the adhesive composition may be deteriorated and a problem of deterioration of adhesive strength may occur, and if it exceeds the above range, optical properties such as light transmittance may be deteriorated.

The getter is included in the adhesive composition, absorbs moisture penetrating into the cured body after the adhesive composition is cured, and functions to prevent deterioration of adhesive strength of the cured body due to moisture permeation, and metal oxides or alloys thereof may be used. As the metal oxide, for example, one or more of CaO, MgO, Al2O3, ZrO2, TiO2, PbO, and ZnO may be used, and an alloy of the metal oxide may be, for example, Al-Zn-O (AZO) and In-Sb. One or more of -O(ITO) may be used, and two or more getters may be mixed and used.

Among the getters, CaO has the best water absorption ability, and in order to further improve the adhesive retention of the cured adhesive composition, a CaO getter can be used, and since MgO has better optical properties such as light transmittance and haze, the cured adhesive composition In order to implement higher optical properties of , it is recommended to use MgO getter.

The crosslinking agent includes a compound represented by Formula 1 or Formula 2 below.

<Formula 1>

In Formula 1,

Ring A may or may not exist, and when present is a substituted or unsubstituted C3-C10 cycloalkyl group or a substituted or unsubstituted C3-C10 cycloalkenyl group,

X is hydrogen, a substituted or unsubstituted C2~C20 alkenyl group, a substituted or unsubstituted C1~C20 alkylidene group, (meth)acrylate or a substituted or unsubstituted C1~C30 in which (meth)acrylic acid is present. A substituted or unsubstituted C2-C30 alkenyl group in which an alkyl group or (meth)acrylate or (meth)acrylic acid is present, and the alkyl group or alkenyl group may have one or more -CH2- substituted with oxygen,

R1 is each independently hydrogen, heavy hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkoxy group group, a substituted or unsubstituted C1~C30 sulfide group, a substituted or unsubstituted C6~C50 aryl group, or a substituted or unsubstituted C2~C50 heteroaryl group,

m is an integer from 0 to 4;

Although not shown in Formula 1, the norbonane structure may or may not have a double bond, and the total number of double bonds present in the norbonane structure and ring A is one or two, and the position of the double bond is not limited.

The crosslinking agent of Chemical Formula 1 may be used together with an acrylic resin. More specifically, crosslinking is possible through a bond between a double bond of norbornane and a carboxyl group or a vinyl group of an acrylic resin.

Examples of the crosslinking agent of Formula 1 are shown in Table 1 below, but are not limited thereto.

Meanwhile, Chemical Formula 2 is as follows.

<Formula 2>

In Formula 2,

Ring B may or may not be present, and if present is a substituted or unsubstituted C3-C10 cycloalkyl group (one or more -CH2- may be substituted with -CO-), or an epoxy ring;

Ring C may or may not be present, and if present, a substituted or unsubstituted C3-C10 cycloalkyl group (one or more -CH2- may be substituted with -CO-), an epoxy ring, or a cyclic anhydride a nobonanic group with or without a carboxylic acid;

Ring D may or may not exist, and if present, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group with an epoxy group, a cyclic dicarboxylic acid, Or an epoxy ring,

Y is hydrogen, a hydroxy group, a substituted or unsubstituted C1~C30 alkyl group in which (meth)acrylic acid is present (one or more -CH2- may be substituted with oxygen), a substituted or unsubstituted C1~ in which carboxylic acid is present A C30 alkenyl group, a substituted or unsubstituted C1~C30 hydroxyalkyl group or a carboxylic acid group,

Z is CH2, O, S, NR3, P=0 or PR4;

R2 is each independently hydrogen, heavy hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C1~C30 hydroxyalkyl group, carboxylic acid group, substituted or unsubstituted C1~C30 carboxylic acid alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkoxy group, substituted or unsubstituted C1~C30 sulfide group, substituted or unsubstituted A C6~C50 aryl group, or a substituted or unsubstituted C2~C50 heteroaryl group,

R3 and R4 are each independently hydrogen, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C2~C30 alkenyl group, a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C2~C30 aryl group. A C2~C30 heteroaryl group,

n is an integer from 0 to 4;

Although not shown in Formula 2, the norbonane structure has or does not have a double bond, the total number of double bonds present in the norbonane structure and ring A is 0 or 1, and the position of the double bond is not limited,

Although not shown in Chemical Formula 2, 0 to 2 epoxy structures in which oxygen is bonded to two adjacent carbons may be included,

Although not shown in Chemical Formula 2, 0 to 2 cyclic anhydride structures formed by bonding with neighboring carbons may be included.

The crosslinking agent of Chemical Formula 2 may be used when an epoxy-based resin or a mixture of an epoxy-based resin and an acrylic-based resin is used. More specifically, crosslinking with an epoxy-based resin is possible through an epoxy group, an acid anhydride group, or a hydroxyl group of norbornane.

Examples of the crosslinking agent of Formula 2 are shown in Table 2 below, but are not limited thereto.

When two or more types of resins are used in the adhesive composition, two or more types of crosslinking agents of Chemical Formulas 1 and 2 may be mixed and used, and may be formulated according to the type and content of the resin. When applying acrylic resins, the norbornane crosslinking agent of Chemical Formula 1 is suitable, and when applying epoxy resins, it is preferable to apply the norbornane crosslinking agent of Chemical Formula 2, but is not limited thereto.

The adhesive composition of the present invention may further include one or more additives selected from a thickener, a thixotropy agent, and a spacer. A thickener and a thixotropic agent are materials that impart thickening properties and thixotropy to the adhesive composition, respectively, and may include, for example, fumed silica, and may be further included in the adhesive composition in an amount of 0.1 to 20% by weight.

The spacer is a material that helps to maintain a constant distance between the upper and lower plates when an adhesive composition is used in the upper and lower plates that need to be attached. Any material that does not chemically react with the adhesive composition can be used without particular limitation. do.

The adhesive composition of the present invention may exhibit a viscosity of 50,000 to 350,000 cP. When the adhesive composition exhibits a viscosity within the above range, it may be advantageous to secure excellent processability. In addition, according to the viscosity range, for example, it may have thixotropy which is advantageous for a process of forming a dam structure of a display device. When the adhesive composition is out of the above viscosity range, it is difficult to form a cured body with a desired thickness, and a problem of poor fairness may occur.

A thickener may be included as an additive so as to exhibit a viscosity within the above range, and as the thickener, conventional thickeners may be used without limitation.

A display device, which is another embodiment of the present invention, includes the hardened body, and may be specifically applied to a dam outside the display device.

When forming a dam structure of a display device using the composition of the present invention, the forming process may follow a conventional process. For example, UV curing, thermal curing, or a curing process using both UV and heat may be used. The dam structure formed from the dam material composition according to the embodiment may exhibit excellent adhesion and oxygen/moisture barrier properties. In addition, the dam structure formed from the dam material composition according to the embodiment may have flexible characteristics and may be applicable to various flexible/bendable/foldable display devices. In addition, a dam structure formed from the dam material composition according to the embodiment may have excellent reliability and durability. Therefore, using the dam material composition according to the embodiment, a display device having excellent reliability and durability can be manufactured. In particular, the dam material composition according to the embodiment can be usefully applied to the manufacture of deformable display devices such as flexible/bendable/foldable.

Hereinafter, the present invention will be described in more detail through specific examples of the adhesive composition of the present invention. The following examples are merely illustrative of the present invention, but the scope of the present invention is not limited to the following examples.

Moisture permeation evaluation_Measurement of water permeation time

The DAM to be evaluated is located outside the center of the glass substrate, and the opaque DAM for checking whether moisture permeates is located inside the DAM for evaluation. When moisture permeates the external evaluation DAM, it also affects the opaque DAM located inside. This was identified and the moisture penetration time was confirmed. All DAMs were evaluated with a fixed width of 5 mm. The distance between the DAM for external evaluation and the DAM for internal evaluation must have the same distance. For example, if the internal opaque DAM is a circle with a diameter of 5 cm, the external DAM for evaluation should be at least 6 cm. For another example, if the DAM for internal evaluation is in the shape of a square, the external DAM should also be drawn with its center coincident with the internal rectangle and maintained at a certain distance.

In summary, after drawing the DAM to be evaluated on the lower glass substrate, draw the opaque DAM to check whether moisture penetrates inside. Thereafter, the upper glass substrate is covered and bonded in a vacuum, and a specimen is prepared and evaluated after bonding through UV exposure.

For the internal opaque DAM, a mixture of 30% CaO getter, 2% radical initiator, and 68% ester-based acrylate was used as a material for checking moisture permeation.

When the moisture penetration confirmation material absorbs moisture, the opaque material changes to transparent due to the nature of CaO, and the moisture absorption can be confirmed, and the time required for the opaque DAM to become transparent by consuming moisture was measured (unit: hr).

Specimen fabrication for water penetration evaluation

(1) Musashi's dispenser was used.

(2) MUSASHI's Shotmaster-300DS was used for the model of the equipment, and the desired shape was written using MuCAD V for the drawing program.

(3) The needle size of the discharge nozzle was 22~18ø,

(4) The speed of the discharge head was between 5 and 80 cm/min depending on the viscosity and surface characteristics of the material.

(5) The discharge pressure was 0.3~0.8 Mpa.

(6) Bonding of the upper and lower substrates was performed using vacuum bonding equipment.

(7) Exposure was performed at 1000 to 5000 mJ.

(8) Curing was performed on a 100 °C Hot Plate for 30 min after exposure.

Fabrication of specimens for measuring adhesion

Put 0.5~2mg of resin complex on a 2.5x4cm, 0.7T size glass. Then, rotate the same glass at the top by 90° and raise it. Place a 500g weight here and press it for about 15 to 30 seconds. Make the dot size about 5mm.

After that, it is exposed to 1000 to 5000 mJ in a UV exposure machine. After exposure, Curing is performed on a 100 ℃ Hot Plate for 30 min. Adhesion is measured using UTM.

Severe evaluation conditions

(1) Put it in an oven under 85℃/85RH% (relative humidity) conditions to evaluate the water penetration and adhesion reliability of the material.

(2) The Oven used was SORITECH's high-temperature-high-humidity equipment.

Examples 1 to 10 and Comparative Examples 1 to 6

In Table 3 below, components used in Examples and Comparative Examples were specified.

The specified components were added to a 300 ml paste mixer container at the component ratio of Table 4, then put into a revolution-rotation mixer, and then mixed at a revolution of 1200 rpm and a rotation of 1200 rpm for 60 minutes to prepare an adhesive composition. After that, the moisture inhibitory power and adhesion reliability of the cured body of the adhesive composition were evaluated by the above method, and are shown in Tables 5 and 6 below.

division cross-linking agent epoxy acryl initiator Comparative Example 1 Urethane Acrylate
(product name:
SUO-,4140I10 SHIN-A T&C)
Bis(4-methylphenyl)iodonium hexafluorophosphate
(cationic initiator)
/
2-Methyl-4′-(methylthio)-2-
Morpholinopropiophenone
(radical initiator) Comparative Example 2 isobornyl acrylate Example 1 5-Vinyl-2-norbornene Example 2 5-Ethylidene-2-norbornene Example 3 Ethylene glycol dicyclopentenyl ether methacrylate Example 4 5-Norbornene-2-methylolacrylate Comparative Example 3 1,4-Cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate) Comparative Example 4 4-Methylcyclohexane-1,2-dicarboxylic Comparative Example 5 3 or 4-methyl-
1,2,3,6-tetrahydrophthalic anhydride Comparative Example 6 Hexahydro-4,7-methanoisobenzofuran-1,3-dione Example 5 5-Norbornene-2-acrylic acid Example 6 5-Norbornene-2,3-dicarboxylic anhydride Example 7 Methyl-5-norbornene-2,3-dicarboxylic anhydride Example 8 3,6-Epoxy-1,2,3,6-tetrahydrophthalic Anhydride Example 9 5-Norbornene-2,3-dicarboxylic anhydride Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 5-Norbornene-2,3-dicarboxylic anhydride 1,4-Cyclohexanedimethanol bis(3,4-epoxycyclohexanecarboxylate) Urethane Acrylate
(product name:
SUO-,4140I10 SHIN-A T&C)
Bis(4-methylphenyl)iodonium hexafluorophosphate
(cationic initiator)
/
2-Methyl-4′-(methylthio)-2-
Morpholinopropiophenone
(radical initiator) Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25

division cross-linking agent epoxy acryl radical
initiator cation
initiator CaO Spcaer Silica Comparative Example 1 0.0 0.0 88.0 2.0 0.0 8.8 0.2 1.0 Comparative Example 2 8 81 One Example 1 Example 2 Example 3 Example 4 Comparative Example 3 0.0 44.0 44.0 1.0 1.0 Comparative Example 4 8 40.0 40.0 Comparative Example 5 Comparative Example 6 Example 5 Example 6 Example 7 Example 8 Example 9 0.2 43.9 43.9 Example 10 0.6 43.7 43.7 Example 11 4 42 42 Example 12 10 39 39 Example 13 18 35 35 Example 14 26 31.6 31.6 0.8 0.8 Example 15 36 26.2 26.2 Example 16 8.65 43.27 43.27 1.30 1.30 1.00 Example 17 8.61 43.05 43.05 1.29 1.29 1.50 Example 18 8.57 42.83 42.83 1.28 1.28 2.00 Example 19 8.48 42.39 42.39 1.27 1.27 3.00 Example 20 8.30 41.50 41.50 1.25 1.25 5.00 Example 21 7.42 37.08 37.08 1.11 1.11 15.00 Example 22 6.53 32.65 32.65 0.98 0.98 25.00 Example 23 5.65 28.23 28.23 0.85 0.85 35.00 Example 24 5.20 26.02 26.02 0.78 0.78 40.00 Example 25 4.32 21.59 21.59 0.65 0.65 50.00

Experiment example Moisture penetration evaluation
(hr) Attachment reliability
(kgf/cm2) Crash Reliability Conditions: 85℃/85RH% Based on DAM width 5 mm 0 hours 1000 hours Δ(%) Comparative Example 1 102 2.3 1.0 -1.3 Comparative Example 2 183 2.4 1.4 -1.0 Example 1 209 2.8 2.6 -0.2 Example 2 191 3.2 3.3 0.1 Example 3 224 2.9 2.7 -0.2 Example 4 217 3.0 2.7 -0.3 Comparative Example 3 301 1.5 0.4 -1.1 Comparative Example 4 574 2.1 1.6 -0.5 Comparative Example 5 555 2.4 1.7 -0.7 Comparative Example 6 604 2.5 1.5 -1.0 Example 5 967 3.2 2.9 -0.3 Example 6 957 4.4 4.4 0.0 Example 7 1006 4.0 4.0 0.0 Example 8 1051 4.1 4.2 0.1 Example 9 857 1.9 1.2 -0.7 Example 10 903 2.5 2.3 -0.2 Example 11 992 2.9 2.6 -0.3 Example 12 1021 4.4 4.0 -0.4 Example 13 954 4.6 4.6 0.0 Example 14 892 4.8 4.2 -0.6 Example 15 772 4.0 2.9 -1.1

Experiment optical properties
(turbidity, %) Moisture penetration evaluation
(hr) Attachment reliability
(kgf/cm2) Crash Reliability Conditions: 85℃/85RH% Thickness 10~12㎛ DAM width mm 0 hours 1000 hours Δ(%) Example 16 1.73 995 4.5 4.5 0.0 Example 17 2.22 980 4.4 4.2 -0.2 Example 18 3.55 1023 4.6 4.3 -0.3 Example 19 5.01 1097 4.0 4.0 0.0 Example 20 9.86 1203 4.4 4.0 -0.4 Example 21 30.99 1309 3.5 3.1 -0.2 Example 22 58.07 1372 2.6 2.3 -0.3 Example 23 63.54 1462 2.6 2.2 -0.3 Example 24 72.63 1458 2.7 2.2 -0.5 Example 25 84.17 1502 2.2 2.0 -0.2

Experimental group Ⅰ_Comparative Example 1~Example 4_The role of crosslinking agent in the composition of acrylate alone

(1) When a crosslinking agent is used in the composition of acrylic alone, the effect of improving adhesion reliability is shown.

(2) Due to the nature of (urethane) acrylic, it has good moisture permeability, so its moisture suppression ability is insufficient compared to other resins, but it can be seen that the properties are improved by adding a crosslinking agent.

experimental group II_ Comparative Example 3 ~ Example 8 _ acrylate +In the composition of the epoxy Norbornen cross-linking agent introduction

(1) Among the norbornene crosslinking agents, it was confirmed that the norbornene acid anhydride structure, among others, having a bridged structure in a similar structure further improved the physical properties.

(2) Both the moisture resistance and adhesion reliability characteristics were improved.

(3) Although it is a cyclic structure, it can be seen that the bridged crosslinking agent has excellent properties. In addition, since the polarity of the material is high, attraction such as the van der Waals force between resins acts strongly, and moisture is difficult to penetrate, so the reliability of the material may be excellent.

experimental group III_ Example 9~ Example 15_ Norbornen acid anhydride Check the change in physical properties according to the content

(1) The content of the crosslinking agent exhibited excellent water permeation inhibition within the range of 0.5 to 30% by weight, and particularly excellent water penetration ability within the range of 1.0 to 20% by weight. In the case of Example 9, the content of the crosslinking agent was low, and the moisture permeation inhibition was low, and in the case of Example 15, it can be seen that the physical properties rather deteriorated due to the excessive content of norbornene acid anhydride. Under conditions of high temperature and high humidity, excess acid anhydride is converted into carboxylic acid, which is expected to play a role in reducing durability of the material.

Experimental group IV_Example 16~Example 25_Optical characteristics according to getter content

It can be seen that even when the content of the getter is used within the range of 0.5% to 10% by weight, the optical properties are greatly improved and at the same time, sufficient water penetration inhibition is obtained. Rather, in the case of initial attachment reliability, it was 4.0 kgf/cm ² or more, and a satisfactory result was obtained at a fine level of change after 1000 hours of evaluation. Looking at the water permeation evaluation, it was confirmed that the average time was quite good at about 900 to 1200 hr, and the turbidity, which is an optical characteristic, was also greatly improved.

Claims (13)

An adhesive composition comprising a curable resin, a getter and a crosslinking agent, Wherein the crosslinking agent comprises a compound represented by Chemical Formula 1 or Chemical Formula 2 below. <Formula 1>

(In Formula 1, Ring A may or may not exist, and when present is a substituted or unsubstituted C3-C10 cycloalkyl group or a substituted or unsubstituted C3-C10 cycloalkenyl group, X is hydrogen, a substituted or unsubstituted C2~C20 alkenyl group, a substituted or unsubstituted C1~C20 alkylidene group, (meth)acrylate or a substituted or unsubstituted C1~C30 in which (meth)acrylic acid is present. A substituted or unsubstituted C2-C30 alkenyl group in which an alkyl group or (meth)acrylate or (meth)acrylic acid is present, and the alkyl group or alkenyl group may have one or more -CH2- substituted with oxygen, R1 is each independently hydrogen, heavy hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkoxy group group, a substituted or unsubstituted C1~C30 sulfide group, a substituted or unsubstituted C6~C50 aryl group, or a substituted or unsubstituted C2~C50 heteroaryl group, m is an integer from 0 to 4; Although not shown in Formula 1, the norbonane structure has or does not have a double bond, and the total number of double bonds present in the norbonane structure and ring A is 1 or 2, and the position of the double bond is not limited) <Formula 2>

(In Formula 2 above, Ring B may or may not be present, and if present is a substituted or unsubstituted C3-C10 cycloalkyl group (one or more -CH2- may be substituted with -CO-), or an epoxy ring; Ring C may or may not be present, and if present, a substituted or unsubstituted C3-C10 cycloalkyl group (one or more -CH2- may be substituted with -CO-), an epoxy ring, or a cyclic anhydride a nobonanic group with or without a carboxylic acid; Ring D may or may not exist, and if present, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group with an epoxy group, a cyclic dicarboxylic acid, Or an epoxy ring, Y is hydrogen, a hydroxy group, a substituted or unsubstituted C1~C30 alkyl group in which (meth)acrylic acid is present (one or more -CH2- may be substituted with oxygen), a substituted or unsubstituted C1~ in which carboxylic acid is present A C30 alkenyl group, a substituted or unsubstituted C1~C30 hydroxyalkyl group or a carboxylic acid group, Z is CH2, O, S, NR3, P=0 or PR4; R2 is each independently hydrogen, heavy hydrogen, halogen, nitro group, nitrile group, substituted or unsubstituted C1~C30 alkyl group, substituted or unsubstituted C1~C30 hydroxyalkyl group, carboxylic acid group, substituted or unsubstituted C1~C30 carboxylic acid alkyl group, substituted or unsubstituted C2~C30 alkenyl group, substituted or unsubstituted C1~C30 alkoxy group, substituted or unsubstituted C1~C30 sulfide group, substituted or unsubstituted A C6~C50 aryl group, or a substituted or unsubstituted C2~C50 heteroaryl group, R3 and R4 are each independently hydrogen, a substituted or unsubstituted C1~C30 alkyl group, a substituted or unsubstituted C2~C30 alkenyl group, a substituted or unsubstituted C6~C30 aryl group, or a substituted or unsubstituted C2~C30 aryl group. A C2~C30 heteroaryl group, n is an integer from 0 to 4; Although not shown in Formula 2, the norbonane structure has or does not have a double bond, the total number of double bonds present in the norbonane structure and ring A is 0 or 1, and the position of the double bond is not limited, Although not shown in Chemical Formula 2, 0 to 2 epoxy structures in which oxygen is bonded to two adjacent carbons may be included, Although not shown in Chemical Formula 2, 0 to 2 cyclic anhydride structures formed by bonding with neighboring carbons may be included). According to claim 1, Chemical Formula 1 is an adhesive composition represented by any one of the following Chemical Formulas 1-1 to 1-3. <Formula 1-1>

<Formula 1-2>

<Formula 1-3>

(In Chemical Formulas 1-1 to 1-3, the same symbols as those in Chemical Formula 1 are the same as those defined in Chemical Formula 1) According to claim 1, X in Formula 1 is an adhesive composition selected from the following chemical formulas A-1 to A-6.

(* in the above chemical structure means a binding position) According to claim 1, Formula 1 is an adhesive composition selected from the following compounds.

According to claim 1, Chemical Formula 2 is an adhesive composition represented by any one of the following Chemical Formulas 2-1 to 2-7. <Formula 2-1>

<Formula 2-2>

<Formula 2-3>

<Formula 2-4>

<Formula 2-5>

<Formula 2-6>

<Formula 2-7>

(In Chemical Formulas 2-1 to 2-7, the same symbols as those in Chemical Formula 2 are the same as those defined in Chemical Formula 2) According to claim 1, Y in Formula 2 is an adhesive composition selected from the following chemical formulas B-1 to B-4.

(* in the above chemical structure means a binding position) According to claim 1, Formula 2 is an adhesive composition selected from the following compounds.

According to claim 1, The curable resin is an adhesive composition containing an epoxy resin, an acrylic resin or a mixture thereof. According to claim 1, An adhesive composition further comprising an initiator. According to claim 1, The getter is an adhesive composition included in the range of 0.5% by weight to 10% by weight. A cured product in which the adhesive composition of claim 1 is cured. A dam (DAM) structure in which the adhesive composition of claim 1 is cured. A display device comprising the dam structure of claim 12.