KR20210062810A - Adhesive composition with excellent heat-resistance and preparation method thereof - Google Patents

Abstract

The present invention relates to a high-heat-resistant adhesive composition and a manufacturing method thereof, in which the high-heat-resistant adhesive composition includes: an acryl monomer mixture including 10 to 15 parts by weight of 2-ethylhexyl acrylate, 10 to 15 parts by weight of butyl acrylate, 1 to 2 parts by weight of methyl acrylate, 10 to 20 parts by weight of methoxy polyethylene glycol methacrylate, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, and 1 to 2 parts by weight of 2-hydroxy methacrylate; 0.1 to 0.2 parts by weight of an azobisnitrile thermal initiator; 0.001 to 0.002 parts by weight of N,N,N',N'-tetraglycidyl-m-xylenediamine; and 40 to 50 parts by weight of ethyl acetate. An adhesive or an adhesive material manufactured by using the adhesive composition according to the present invention obtains heat resistance during a semiconductor or mobile phone manufacturing process performed at 180 ℃ for several minutes, and no remnant or residue remains even after a high-temperature treatment.

Description

High heat-resistance pressure-sensitive adhesive composition and its manufacturing method {ADHESIVE COMPOSITION WITH EXCELLENT HEAT-RESISTANCE AND PREPARATION METHOD THEREOF}

The present invention relates to a high heat-resistant pressure-sensitive adhesive composition and a method for producing the same, and more particularly, to a high heat-resistant pressure-sensitive adhesive composition having excellent heat resistance at 180° C. exceeding the heat resistance limit of an acrylic pressure-sensitive adhesive, and having no pressure-sensitive adhesive residue, and a method for producing the same will be.

The pressure-sensitive adhesive composition is currently widely used in industrial fields such as special label paper or tape, surface protection adhesive sheet and masking adhesive tape, wafer manufacturing process tape, mobile phone manufacturing process tape, and the like.

In the case of an acrylic adhesive, it is difficult to realize high heat resistance due to the limitation of the material itself, and silicone-based adhesives have been mainly used for applications requiring heat resistance. Domestic Patent No. 1178712 discloses a silicone pressure-sensitive adhesive composition. The silicone-based adhesive has the advantage of excellent heat resistance and adhesion, but there is a problem that the silicone monomer is transferred to the adherend and remains in the package later, thereby reducing the package reliability, and the unit price is higher than that of the acrylic adhesive. In addition, since a defect occurs when mixing the silicone pressure-sensitive adhesive and the acrylic pressure-sensitive adhesive, the acrylic pressure-sensitive adhesive process and the silicone-based pressure-sensitive adhesive process cannot be performed in parallel, and the process must be performed separately. As a result, the unit price of the product increased due to an increase in additional logistics and processing costs.

Korean Patent No. 0165527 discloses a heat-resistant acrylic adhesive prepared by emulsion polymerization by heating acrylate, carboxylic acryl, acryl having an epoxy group, acrylamide and acrylonitrile in a water phase form in batches. However, since such an acrylic emulsion adhesive is manufactured by a very complicated reaction in which polymerization and crosslinking occur, the manufacturing process is complicated, heat resistance of 150°C or higher is difficult to implement, and transfer remains at a high temperature of 150°C or higher.

In the process of attaching the adhesive film during the semiconductor manufacturing process or the mobile phone manufacturing process and then going through the high-temperature process, the problem that the adhesive layer of the adhesive film is transferred to the substrate frequently occurs, and there is a problem that the yield and productivity are lowered. Controlling is one of the very important properties.

The present invention is to solve the problems of the prior art described above, and one object of the present invention is that heat resistance can be secured while a semiconductor manufacturing process or a mobile phone manufacturing process is performed at 180° C. for several minutes, and An object of the present invention is to provide a high heat-resistant pressure-sensitive adhesive composition capable of controlling pressure-sensitive adhesive transfer properties.

Another object of the present invention is to overcome the limitation in which it is difficult to mix the conventional silicone pressure-sensitive adhesive and the acrylic pressure-sensitive adhesive to reduce defects in the manufacturing process of mobile phones, semiconductors, and the like.

Another object of the present invention is to replace the silicone pressure-sensitive adhesive having excellent heat resistance by improving the cohesive force and substrate adhesion of the acrylic pressure-sensitive adhesive.

One aspect of the present invention for solving the above problems is,

2-ethylhexyl acrylate 10-15 parts by weight, butyl acrylate 10-15 parts by weight, methyl acrylate 1-2 parts by weight, methoxy polyethyleneglycol methacrylate 10-20 parts by weight, 2-hydroxyethyl acrylate 1 to 2 parts by weight, an acrylic monomer mixture composed of 1-2 parts by weight of 2-hydroxy methacrylate, 0.1 to 0.2 parts by weight of azobisnitrile thermal initiator; It relates to a highly heat-resistant pressure-sensitive adhesive composition comprising 0.001 to 0.002 parts by weight of N,N,N',N'-tetraglycidyl-m-xylenediamine and 40 to 50 parts by weight of ethyl acetate.

Another aspect of the present invention for solving the above problems is,

base layer; an adhesive layer formed by coating an adhesive composition on one surface of the base layer; and a release film for protecting the adhesive layer, wherein the adhesive layer includes 10 to 15 parts by weight of 2-ethylhexyl acrylate, 10 to 15 parts by weight of butyl acrylate, 1 to 2 parts by weight of methyl acrylate, and methoxy polyethylene. Acryl monomer mixture consisting of 10-20 parts by weight of glycol methacrylate, 1-2 parts by weight of 2-hydroxyethyl acrylate, and 1-2 parts by weight of 2-hydroxy methacrylate, 0.1-0.2 parts by weight of azobisnitrile thermal initiator part; It relates to an adhesive material comprising 0.001 to 0.002 parts by weight of N,N,N',N'-tetraglycidyl-m-xylenediamine and 40 to 50 parts by weight of ethyl acetate.

Another aspect of the present invention for solving the above problems is,

2-ethylhexyl acrylate 10-15 parts by weight, butyl acrylate 10-15 parts by weight, methyl acrylate 1-2 parts by weight, methoxy polyethyleneglycol methacrylate 10-20 parts by weight, 2-hydroxyethyl acrylate 1 to 2 parts by weight, 1 to 2 parts by weight of 2-hydroxy methacrylate, an acrylic monomer mixture, 0.1 to 0.2 parts by weight of azobisnitrile thermal initiator, and 40 to 50 parts by weight of ethyl acetate are introduced into the reactor to 80° C. to 90 performing a polymerization reaction for 9 to 10 hours while raising the temperature at ℃;

After completion of the polymerization reaction, proceeding with natural descending aging at 55 ℃ to 65 ℃ for 8 hours to 10 hours; And

Mixing 0.001 to 0.002 parts by weight of N,N,N',N'-tetraglycidyl-m-xylenediamine and 1 to 5 parts by weight of a hexadiisocyanate curing agent to the aged composition to obtain a pressure-sensitive adhesive composition It relates to a method for producing a pressure-sensitive adhesive composition, characterized in that.

The pressure-sensitive adhesive composition of the present invention has a remarkable effect such as securing heat resistance during a semiconductor manufacturing process or a mobile phone manufacturing process at 180° C. for several minutes.

The pressure-sensitive adhesive of the present invention is an adhesive with strong heat resistance, and can exhibit excellent heat resistance, cohesion, and adhesion to the substrate to the extent that transfer or transfer due to cohesive failure does not occur in a state of being attached to the substrate to be adhered at 180° C. for 2 hours or more.

The pressure-sensitive adhesive of the present invention provides remarkable advantages in that there is no transfer or transfer even after 2 years by improving weather resistance compared to the existing acrylic pressure-sensitive adhesive, and wettability, which is a characteristic of a silicone pressure-sensitive adhesive, can be implemented.

Hereinafter, the present invention will be described in more detail.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Unless otherwise stated, all percentages, parts, ratios, etc. are by weight. It is also to be understood that when parameters such as amounts, concentrations, etc. are given as ranges, they specifically disclose all ranges formed from any pair within that range, whether the ranges are separately disclosed or not.

One aspect of the present invention is 2-ethylhexyl acrylate 10-15 parts by weight, butyl acrylate 10-15 parts by weight, methyl acrylate 1-2 parts by weight, methoxy polyethylene glycol methacrylate 10-20 parts by weight, 1 to 2 parts by weight of 2-hydroxyethyl acrylate, 1 to 2 parts by weight of 2-hydroxy methacrylate, an acrylic monomer mixture, 0.1 to 0.2 parts by weight of azobisnitrile thermal initiator; It relates to a high heat-resistant pressure-sensitive adhesive composition comprising 0.001 to 0.002 parts by weight of N,N,N',N'-tetraglycidyl-m-xylenediamine and 40 to 50 parts by weight of ethyl acetate.

The pressure-sensitive adhesive of the present invention is 2-ethylhexyl acrylate 10-15 parts by weight, butyl acrylate 10-15 parts by weight, methyl acrylate 1-2 parts by weight, methoxy polyethylene glycol methacrylate 10-20 parts by weight, 2- 1 to 2 parts by weight of hydroxyethyl acrylate, 1 to 2 parts by weight of 2-hydroxy methacrylate, an acrylic monomer mixture, 0.1 to 0.2 parts by weight of azobisnitrile thermal initiator; A pressure-sensitive adhesive containing a solvent composed of 40 to 50 parts by weight of ethyl acetate is included as a main component, and N,N,N',N'-tetraglycidyl-m-xylenediamine (TETRAD-X), which is a crosslinking catalyst includes

The heat-resistant pressure-sensitive adhesive composition of the present invention is characterized in that it contains methoxy polyethylene glycol methacrylate, a special monomer, in order to overcome the heat resistance, which is a limitation of the acrylic pressure-sensitive adhesive.

The pressure-sensitive adhesive of the present invention induces a urethane reaction by introducing a hydroxyl group into the polymer of the acrylic pressure-sensitive adhesive and cross-linking it with hexadiisocyanate, which is a polyisocyanate.

The acrylic copolymer may use a thermal initiator during polymerization, for example, an initiator such as azobisnitrile, benzoyl peroxide, or peroxide such as acetyl peroxide, which is an azo thermal initiator, may be used, one or two of the above More than one species can be mixed and used.

As the crosslinking agent of the present invention, it is preferable to use an isocyanate-based crosslinking agent, hexadiisocyanate, and other isocyanate-based crosslinking agents may be used in combination. In some cases, by using an epoxy-based and aziridine-based resin as a crosslinking agent, heat resistance and adhesion to the substrate can be further improved.

As said other isocyanate type crosslinking agent, toluene diisocyanate, naphtha-1,5-diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, trimethylolpropane modified toluene diisocyanate, etc. can be used.

The adhesive of the present invention is a disadvantage of hexadiisocyanate. In order to control the slow reactivity, a N,N,N',N'-tetraglycidyl-m-xylenediamine (TETRAD-X) curing catalyst is added, and in addition An acid-based curing catalyst may be added.

The high heat-resistant pressure-sensitive adhesive composition of the present invention includes a component for controlling the crosslinking reaction of the pressure-sensitive adhesive. The high heat-resistant pressure-sensitive adhesive composition of the present invention includes hexadiisocyanate, which provides non-yellowing properties and reduces weather resistance and change over time, as a post-curing curing agent in order to control strong adhesion, which is a problem of conventional pressure-sensitive adhesives for adhesive materials. Such a post-curing curing agent has a tendency to decrease cohesive force due to steric hindrance when curing is performed too quickly. To control this, a delayed catalyst is used, and it is advantageous to perform aging at room temperature rather than forced aging.

The post-curing curing agent is preferably included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the acrylic monomer mixture. When the content is included within the above range, it is better in adhesive strength, heat resistance and pressure resistance.

Various additives, such as an antioxidant, antioxidant, a light stabilizer, an antistatic agent, a lubricant, a colorant, and a plasticizer, may be further mix|blended with the high heat-resistant adhesive composition of this invention. The type and content of these additives may be the same as those of a general type and content in the field of general pressure-sensitive adhesives. In addition, a ketone-based retarder may be additionally added to the pressure-sensitive adhesive composition of the present invention to improve pot life.

By containing an antioxidant, the pressure-sensitive adhesive composition of the present invention can suppress oxidation and deterioration of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer, thereby further improving the weather resistance of the pressure-sensitive adhesive layer. The antioxidant is not particularly limited and may be arbitrarily selected depending on the influence on the heat resistance, weather resistance, etc. of the adhesive layer. For example, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and the like can be appropriately used as needed.

The content of the antioxidant in the composition of the present invention is, for example, preferably 0.05 parts by weight or more and 5.0 parts by weight or less. This is because, when the content of the antioxidant is 0.05 parts by weight or more, the effect of the addition of the antioxidant can be sufficiently exhibited in the adhesive layer. In addition, when the content is 5.0 parts by weight or less, it is possible to more reliably prevent the antioxidant from precipitating in the adhesive layer, and this is because it does not significantly affect the transparency of the adhesive layer.

Another aspect of the present invention provides a pressure-sensitive adhesive formed by curing the above-described heat-resistant pressure-sensitive adhesive composition. Another aspect of the present invention includes a base layer, an adhesive layer formed by applying an adhesive composition to one surface of the base layer, and a release film protecting the adhesive layer, wherein the adhesive layer is 2-ethylhexyl acrylate 10 to 15 parts by weight, butyl acrylate 10-15 parts by weight, methyl acrylate 1-2 parts by weight, methoxy polyethylene glycol methacrylate 10-20 parts by weight, 2-hydroxyethyl acrylate 1-2 parts by weight, 2-hydroxy Acrylic monomer mixture composed of 1 to 2 parts by weight of hydroxy methacrylate, 0.1 to 0.2 parts by weight of azobisnitrile thermal initiator; It relates to an adhesive material comprising 0.001 to 0.002 parts by weight of N,N,N',N'-tetraglycidyl-m-xylenediamine and 40 to 50 parts by weight of ethyl acetate.

The base layer is a component that serves as a support for the adhesive material, and the material used for the base layer is not particularly limited. For example, the base layer may include a polyester-based resin, polyimide-based resin, acetate-based resin, polyethersulfone-based resin, polycarbonate-based resin, (meth)acrylate-based resin, polyvinyl chloride-based resin, polystyrene-based resin, It may include at least one selected from the group consisting of polyvinyl alcohol-based resins, and polyarylate-based resins.

The thickness of the base layer is usually 10 to 100 μm, preferably 10 to 50 μm. In addition, the base film may be a single-layer product or a laminate of various films. One side of the base layer may be subjected to conventional physical or chemical surface treatment, such as mat treatment, corona discharge treatment, primer treatment, and crosslinking treatment, in order to increase adhesion with the adhesive layer.

In the present invention, the pressure-sensitive adhesive layer may be covered with a release film if necessary, and paper material, a plastic film, a silicone release film, etc. may be used as the release film, but the present invention is not necessarily limited thereto.

Another aspect of the present invention relates to a method for preparing a pressure-sensitive adhesive composition. In the method of the present invention, 10-15 parts by weight of 2-ethylhexyl acrylate, 10-15 parts by weight of butyl acrylate, 1-2 parts by weight of methyl acrylate, 10-20 parts by weight of methoxy polyethylene glycol methacrylate, 2- 1 to 2 parts by weight of hydroxyethyl acrylate, 1 to 2 parts by weight of 2-hydroxy methacrylate, an acrylic monomer mixture, 0.1 to 0.2 parts by weight of azobisnitrile thermal initiator, and 40 to 50 parts by weight of ethyl acetate are introduced into the reactor The polymerization reaction proceeds for 9 hours to 10 hours while the temperature is raised from 80°C to 90°C. Then, after completion of the polymerization reaction, natural descending aging is performed at 55°C to 65°C for 8 hours to 10 hours. A pressure-sensitive adhesive composition is obtained by mixing 0.001 to 0.002 parts by weight of N,N,N',N'-tetraglycidyl-m-xylenediamine and 1 to 5 parts by weight of a hexadiisocyanate curing agent to the aged composition.

In more detail, first, an acrylic monomer mixture, a thermal initiator, and a solvent are polymerized, and then N,N,N',N'-tetraglycidyl-m-xylenediamine (TETRAD X, Mitsubishi Gas Chemical) as a crosslinking catalyst Company, Inc.) and a hexadiisocyanate curing agent are mixed to form an adhesive composition.

The acrylic polymer can be prepared by various polymerization methods. The polymerization method of the acrylic polymer includes, for example, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a polymerization method by ultraviolet irradiation, etc., but solution polymerization from the viewpoint of transparency, water resistance, cost, etc. method is appropriate. When preparing the acrylic polymer, the acrylic monomer mixture is dissolved in an organic solvent, and an appropriate free radical initiator that exhibits activity by heat is added for polymerization. As the thermally activated initiator, an azo compound such as azobisnitrile is suitable. The amount of the polymerization initiator used may be a normal amount, for example, the polymerization initiator may be selected in the range of about 0.1 to 0.2 parts by weight based on 100 parts by weight of the total acrylic monomer mixture constituting the acrylic polymer.

The organic solvent used for the solution polymerization method is preferably inert to the monomers and polymers mentioned in the above group and does not adversely affect the polymerization reaction, and ethyl acetate is used as a suitable solvent, and the polymerization temperature is 80° C. to 90 degreeC is preferable and, as for reaction time, 9 to 10 hours are preferable.

The acrylic polymer may be prepared by copolymerizing monomers having the above composition. The molecular weight of the acrylic polymer preferably has a molecular weight in the range of 200,000 to 300,000 in consideration of adhesive properties and coating properties. When the weight average molecular weight of the acrylic polymer increases, the viscosity of the pressure-sensitive adhesive composition at the same solid content concentration increases as compared with the case where the weight average molecular weight is low. Therefore, when the weight average molecular weight of the acrylic polymer exceeds 300,000, the solid content concentration of the pressure-sensitive adhesive composition cannot be increased, and the thickness variation of the pressure-sensitive adhesive layer may increase. Therefore, the weight average molecular weight of the acrylic polymer is preferably 300,000 or less as described above.

A pressure-sensitive adhesive material can be prepared by coating the pressure-sensitive adhesive composition obtained as described above on a substrate. The method of forming the pressure-sensitive adhesive layer on the substrate as described above is not particularly limited, and for example, a method of applying and drying the pressure-sensitive adhesive directly on the surface of the substrate using a bar coater, etc., after applying the pressure-sensitive adhesive to the surface of the releasable substrate and drying it , a method of transferring and aging the adhesive layer formed on the surface of the peelable substrate to the surface of the substrate may be applied.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are only for illustrating preferred embodiments of the present invention, and should not be construed as limiting the present invention by this in any sense. do. In addition, in the following examples, "part" and "%" are by weight.

1. Preparation of high heat-resistance pressure-sensitive adhesive composition

Example 1

<Preparation of adhesive composition>

12 parts by weight of 2-ethylhexyl acrylate (2-EHA), 13 parts by weight of butyl acrylate (BA), 1 part by weight of methyl acrylate (MA), methoxypolyethylene glycol methacrylate ( MPEGMA) 15 parts by weight, 2-hydroxyethyl acrylate (HEA) 1 part by weight, 2-hydroxymethacrylate (HEMA) acrylic monomer mixture consisting of 2 parts by weight, N,N,N',N'-tetra 0.002 parts by weight of glycidyl-m-xylenediamine (TETRAD-X) and 45 parts by weight of ethyl acetate (EA) were added to slowly induce an exothermic reaction while the temperature was increased to 85°C. After the exothermic reaction, the main reaction was carried out for 8 hours, and 0.15 parts by weight of an azobisnitrile (AIBN) thermal initiator was additionally added to remove the intermediate residual monomer. After completion of the reaction, aging was carried out at 60° C. for 8 hours to prepare an acrylic polymer adhesive. To the finished pressure-sensitive adhesive, 2 parts by weight of a hexadiisocyanate (HDI) post-curing curing agent was added and uniformly mixed to obtain a pressure-sensitive adhesive composition.

<Production of adhesive film>

The pressure-sensitive adhesive composition was coated on the prepared polyimide film, dried in a hot air circulation dryer at 120° C. for 2 minutes, and the release film was laminated to prepare an adhesive film. Physical properties of the prepared adhesive material were measured by the method described later, and the results are shown in Table 1 below. In Table 1 below, the content of each component is in units of parts by weight.

Examples 2-3

Except for changing the components and content of the high heat-resistant adhesive composition as shown in Table 1 below, an adhesive material was prepared in the same manner as in Example 1, and the physical properties of the prepared adhesive material were evaluated in the same manner. The results are shown together in Table 1 below.

Comparative Example 1

An adhesive material was prepared in the same manner as in Example 1, except that N,N,N',N'-tetraglycidyl-m-xylenediamine (TETRAD-X) was not added to the pressure-sensitive adhesive composition. , the physical properties of the prepared adhesive material were evaluated in the same manner, and the results are shown in Table 1 below.

Comparative Examples 2 to 4

Except for changing the components and content of the high heat-resistant adhesive composition as shown in Table 1 below, an adhesive material was prepared in the same manner as in Example 1, and the physical properties of the prepared adhesive material were evaluated in the same manner. The results are shown together in Table 1 below.

Test Example: Method for evaluating physical properties of adhesive materials

The physical properties of the adhesive films prepared in Examples and Comparative Examples were evaluated by the following method, and the results are shown in Table 1 below.

1) Adhesion

A release film was laminated on each adhesive film, stored at a temperature of 43° C. for 3 days, aged, and then attached to glass to test adhesive strength. The glass to be used for measuring the adhesive strength was cleaned with ethyl acetate (EA), and then the prepared specimen was attached with a roller of 2 kg, and then left at room temperature (a temperature of 25° C. and a relative humidity of 50%) for 1 hour. Measurements were made using a tensile tester at an angle of 180° and a peeling speed of 0.3 m/min.

2) High-temperature adhesive force measurement

After removing the release film from the adhesive films of Examples 1 to 2 and Comparative Examples 1 to 4 prepared above, laminating it on a polyimide film, leaving it at 180° C. for 10 minutes, measuring the peel force of a width of 25 mm and a length of 150 mm Specimens were produced

The glass to be used for peel force measurement was cleaned with ethyl acetate (EA), and then the prepared specimen was attached with a roller of 2 kg, and then left at room temperature for 1 hour. Measurements were made using a tensile tester at an angle of 180° and a peeling speed of 0.3 m/min.

3) wettability

The prepared adhesive film was cut to a size of 2.54 cm in width and 10 cm in length to prepare a sample, and after peeling the adhesive film, measure the time for the adhesive film to completely wet the glass surface by itself without applying external pressure, and the following standards was evaluated according to

○: less than 10 seconds, △: 10 to 30 seconds, ×: more than 30 seconds

4) Residue of appearance after peeling after high temperature treatment

After the prepared specimen was treated at 180° C. for 10 minutes and left at room temperature for 60 minutes, when the adhesive film was peeled from the substrate, it was visually checked whether adhesive residues remained on the surface of the polyimide substrate. As a result, it was evaluated based on the following criteria.

- Excellent: There is no transfer of the adhesive that can be observed with the naked eye on the polyimide surface.

- Defect: Some transfer of the adhesive that can be observed with the naked eye occurs on the polyimide surface.

5) Adhesion to the substrate

After pressing the adhesive film prepared in the embodiment of the present invention to the polyimide film substrate through a roll-shaped bar at a temperature of 65° C. using a tape mounting facility (DT-MWM 1230A, Dynatech), between the substrate and the adhesive film Adhesion to the substrate was evaluated in the presence or absence of voids.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 acryl
monomer
mixture 2-EHA 12 12 13 12 12 13 13 BA 13 13 13 13 13 13 13 MA One One One One One One One MEGMA 15 18 20 5 6 7 9 2-HEA One One One One One One One 2-HEMA 2 2 2 2 2 2 2 catalyst TETRAD-X 0.001 0.015 0.002 - - 0.002 - Heat
initiator AIBN 0.1 0.15 0.2 0.1 0.15 0.15 0.2 Hardener HDI 2 2 2 - 2 - - oxazoline - - - - - - 2 solvent EA 45 41 48 45 41 48 45 Properties room temperature
adhesiveness
(gf/25mm) 8 9 10 15 13 14 16 High temperature
adhesiveness
(gf/25mm) 16 21 22 30 26 28 27 wettability ○ ○ ○ X X X X Adhesive residue after high temperature treatment Great Great Great bad bad bad bad substrate adhesion
(With or without Void) none none none has exist has exist has exist has exist

As shown in Table 1, Examples 1 and 2 exhibited excellent heat resistance due to excellent adhesion at room temperature as well as adhesion at high temperature, and exhibited excellent wettability and residue characteristics with almost no residue. On the other hand, in the case of Comparative Examples 1 to 4, it was confirmed that the wettability and adhesion to the substrate were poor, the adhesion was quite high and the re-peelability was relatively low, and it was confirmed that the surface contamination was severe during peeling after high-temperature heat treatment.

The present invention described above is not limited to the above-described embodiments, and various modifications and changes made by those skilled in the art within the scope not departing from the spirit and scope of the present invention described in the claims below It is, of course, also included within the scope of the present invention.

Claims (6)

2-ethylhexyl acrylate 10-15 parts by weight, butyl acrylate 10-15 parts by weight, methyl acrylate 1-2 parts by weight, methoxy polyethylene glycol methacrylate 10-20 parts by weight, 2-hydroxyethyl acrylate 1 to 2 parts by weight, an acrylic monomer mixture composed of 1-2 parts by weight of 2-hydroxy methacrylate, 0.1 to 0.2 parts by weight of azobisnitrile thermal initiator; A highly heat-resistant pressure-sensitive adhesive composition comprising 0.001 to 0.002 parts by weight of N,N,N',N'-tetraglycidyl-m-xylenediamine and 40 to 50 parts by weight of ethyl acetate.
The high heat resistance pressure-sensitive adhesive composition according to claim 1, wherein the composition further comprises 1 to 5 parts by weight of the hexadiisocyanate post-curing curing agent based on 100 parts by weight of the acrylic monomer mixture.
A pressure-sensitive adhesive formed by curing the high heat-resistant pressure-sensitive adhesive composition of claim 1 or 2.
2-ethylhexyl acrylate 10-15 parts by weight, butyl acrylate 10-15 parts by weight, methyl acrylate 1-2 parts by weight, methoxy polyethylene glycol methacrylate 10-20 parts by weight, 2-hydroxyethyl acrylate 1 to 2 parts by weight, 1 to 2 parts by weight of 2-hydroxy methacrylate, an acrylic monomer mixture, 0.1 to 0.2 parts by weight of azobisnitrile thermal initiator, and 40 to 50 parts by weight of ethyl acetate are introduced into the reactor at 80° C. to 90 Proceeding the polymerization reaction for 9 hours to 10 hours while raising the temperature at ℃;
After completion of the polymerization reaction, proceeding the natural aging aging at 55 ℃ to 65 ℃ for 8 hours to 10 hours; and
Mixing 0.001 to 0.002 parts by weight of N,N,N',N'-tetraglycidyl-m-xylenediamine and 1 to 5 parts by weight of a hexadiisocyanate curing agent to the aged composition to obtain a pressure-sensitive adhesive composition A method for producing an adhesive composition, characterized in that
[Claim 5] The method of claim 4, wherein the method comprises polymerizing the acrylic pressure-sensitive adhesive to have a molecular weight of 200,000 to 300,000.
According to claim 4, wherein the base layer is a polyester-based resin, polyimide-based resin, acetate-based resin, polyethersulfone-based resin, polycarbonate-based resin, (meth) acrylate-based resin, polyvinyl chloride-based resin, polystyrene A method for producing a pressure-sensitive adhesive composition, characterized in that the film is composed of at least one selected from the group consisting of a resin-based resin, a polyvinyl alcohol-based resin, and a polyarylate-based resin.