KR20020034109A - The method for manufacturing and adhesive composition - Google Patents

Abstract

PURPOSE: Provided is an adhesive composition excellent in compatibility with dyes, discoloration-resistance, heat-resistance, and moisture-resistance, which can be used for a film controlling the permeation of sunlight. CONSTITUTION: The adhesive composition is produced by a process comprising the steps of: reacting 50-100 parts of 2-ethylhexyl acrylate, 15-20 parts of butyl acrylate, 5-30 parts of vinyl acetate, 1-6 parts of acrylic acid, 0.5-5 parts of 2-hydroxy ethyl methacrylate, 0.1-0.6 parts of a radical initiator, 1-30pts.wt. of a solvent, and 0.1-0.5pts.wt. of an improving agent at 80deg.C for 7-8 hours; aging the resultant at 55deg.C for 14 hours; adding 60-150pts.wt. of ethyl acetate to the resultant and adding 11pts.wt. of a dye, and 0.01-11pts.wt. of a curing agent. The radical initiator is at least one selected from benzoyl peroxide, azobis isobutyronitrile, and etc., the solvent is at least two selected from ethyl acetate, toluene, acetone, methanol, and etc., the curing agent is one compound selected from a melamine, a metal chelate, an isocyanate, and etc., and the improver is one selected from functional monomers of glycidyl methacrylate, N-methylol acrylamide, and acrylamide.

Description

Adhesive composition and its manufacturing method {The method for manufacturing and adhesive composition}

The present invention relates to a pressure-sensitive adhesive composition for a solar light transmission control film suitable for solar light transmission control and partial blocking (hereinafter referred to as transmission control) film by applying an acrylic solution-type pressure-sensitive adhesive (hereinafter referred to as adhesive), and a method of manufacturing the same.

Conventional solar light control film can be divided into two types, first, as shown in Figure 1 is a type that processed a transparent pressure-sensitive adhesive by putting a color on the polyethylene terephthalate film (hereinafter referred to as polyester film) itself. The pressure sensitive adhesive used only focused on the adhesion and transparency to the polyester film, the adhesion to the adherend,

In addition, there are types of dyes mixed with the adhesive and coated on the transparent polyester film. In this case, the compatibility between the adhesive and the dye is insufficient, which does not have a uniform color or causes gelation. As the color changes over time (hereinafter, referred to as a change over time), the effect of trying to control the transmission of sunlight is often rapidly deteriorated.

In order to produce a product suitable for the taste of consumers who demand a variety of colors with low demand as in an industrial environment like our country, a method of making a final product by producing polyester films having respective colors as in the first case Is not able to produce multi-lot sorts, so the cost burden is high due to the load of inventory due to mass production.

Since no colored polyester film is produced in Korea, foreign colored polyester film, which is dependent on imports, is burdened by consumers because of the high price of products and long import period.

In the second case, even though the conventional pressure-sensitive adhesive was prepared by mixing dyes to produce a film for controlling the transmittance of sunlight, the compatibility between the pressure-sensitive adhesive and the dye was poor, resulting in poor coating properties, resulting in uneven color or changes in the original sun-ray due to changes over time. It decreased in a short period of time and had many disadvantages in terms of quality, such as a phenomenon caused by curled edges of the film due to variations in temperature and humidity, that is, curling.

For this reason, in the present invention, when mixed with a variety of dyes and the like as the pressure-sensitive adhesive that can be applied in the second way, the compatibility with the dye is good and uniform coating property, so the color is uniform, and the coating on the film actually When applied to automobile glass windows or building windows, there is no problem of deterioration of the light-receiving part due to the influence of ultraviolet rays in the sun, and deterioration of the function as a solar light transmission control film. It was necessary to develop a pressure-sensitive adhesive without curling, that is, a phenomenon caused by the edges of the film curled due to the variation of temperature and humidity according to the season.

In the present invention, an alkyl group having 4 to 14 carbon atoms of acrylic and methacrylic acid ester monomers, copolymerizable monomers for imparting adhesive strength, copolymerizable monomers containing carboxyl groups and hydroxyl groups, and amides are contained. Two or more of the copolymerizable monomers, one or more of the reaction and compounding solvents, and radical initiators are adhesives made from oil-soluble initiators such as peroxides and azo compounds as raw materials. It is possible to improve the compatibility between the adhesive and the dye when blending the dye to prevent gelation of the formulation and to maintain the physical properties of the adhesive, coating processing is easy, prevent the discoloration of the dye in exposure to sunlight, moisture resistance and heat resistance This enhancement prevents the lifting of the edges of the attached film. An object of the present invention is to provide a pressure-sensitive adhesive composition for solar light transmission control film and a method of manufacturing the same.

In order to achieve the above object, the present invention is 50 to 100 parts of 2-ethylhexyl acrylate, 15 to 20 parts of butyl acrylate, 5 to 30 parts of vinyl acetate, 1 to 6 parts of acrylic acid, 2-hydroxyethyl It is composed of 0.1 to 0.6 parts of radical initiator, 1 to 30 parts by weight of solvent, 0.01 to 10 parts by weight of curing agent, 0.1 to 0.5 parts by weight of enhancer and 11 parts by weight of dye in at least three compounds selected from 0.5 to 5 parts of methacrylate. The present invention relates to a pressure-sensitive adhesive composition and a method of manufacturing the same.

In the present invention, in preparing a pressure-sensitive adhesive for controlling solar light transmission by using an acrylic solution polymerization method, a monomer having a relatively low glass transition temperature as a main monomer, and an alkyl group having 2 to 8 carbon atoms, specifically, 2-ethylhexyl group and isoxyl group By using acrylic and methacrylic acid ester monomers having a butyl group and an ethyl group, the glass transition temperature was designed to be -60 to -40 ° C to have an appropriate initial adhesive force.

Adhesion is achieved using vinyl acetate, which has a relatively high glass transition temperature, and an acryl and methacrylic acid ester monomer in which an alkyl group has a methyl group, and functional group monomers such as glycidyl methacrylate, en-metholacrylamide, and acrylamide are used. Heat resistance and moisture resistance were used.

Examples of the acrylic and methacrylic acid ester functional monomers containing a carboxyl group or a hydroxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, When hydroxypropyl methacrylate or the like is used, the cohesion and heat resistance of the pressure-sensitive adhesive and the adhesion and adhesion to the film can be improved when a certain amount of the curing agent is simultaneously mixed with the pressure-sensitive adhesive and the dye.

When the amount of the monomer containing carboxyl groups is large, the compatibility with the dye and the pot life are shortened due to the shortage of compatibility and pot life. Thus, the work efficiency and workability are reduced during the work. When blending, gel development occurs before the operation, that is, shortening of the pot life may not be possible, and when the working film is exposed to sunlight after the film is attached to the actual application, the change of dye over time, that is, discoloration may occur. In order to improve this problem, the level of the carboxyl group-containing monomer was lowered to improve the compatibility and pot life in the discoloration or dye formulation, and the hydroxyl group-containing monomer and the functional monomer were added to adjust the balance of the crosslinking origin. .

The radical initiator used alone or in combination with peroxide compounds such as benzoyl peroxide and lauroyl peroxide, and azo compounds such as azobisisobutylonitrile and azodimethylvaleronitrile.

In the present invention, one or more of ethyl acetate, toluene, acetone, methanol, isopropyl alcohol, cyclonucleic acid, nomal nucleic acid and nomal pantan was used as a polymerization solvent or a compounding solvent, and it acts as an inhibitor to the reaction to maintain reactivity. In order to remove dissolved oxygen, nitrogen gas was added or reacted at the reflux temperature of the reactants in a jacketed reactor (bath batch reactor).

Specifically, after nitrogen gas is introduced into a reactor equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen inlet tube, 50 to 150 parts of 2-ethylnuclear acrylate (or oxyl acrylate), 10 to 30 parts of butyl acrylate, Two or more of monomers of 5 to 30 parts of vinyl acetate, 0.5 to 8 parts of hydroxyethyl methacrylate (or hydroxyethyl acrylate or hydroxypropyl methacrylate), and 1 to 10 parts of acrylic acid (or methacrylic acid); , 200-300 parts of ethyl acetate and 0.1 to 3.0 parts of benzoyl peroxide, lauroyl peroxide and azobisisobutyronitrile, individually or in combination, were used as initiators.

When the raw material is placed in a reactor and warmed up to an exothermic temperature, when the exotherm starts, the external temperature is forcibly cooled to control the exothermic temperature. After the completion of the reaction, the temperature is adjusted again to maintain a constant temperature for 10 to 20 hours at a predetermined temperature at 50 to 60 DEG C, followed by aging, and the reaction is terminated.

One or more of solvents such as ethyl acetate, normal nucleic acid, cyclonucleic acid, toluene, and methanol are added to the mixture, and then cooled to room temperature to adjust the appropriate solid content and viscosity.

When the dye is blended into the pressure-sensitive adhesive, the curing agent may be mixed at the same time to increase the cohesion, heat resistance and adhesion to the film, and control the pressure-sensitive adhesive strength of the pressure-sensitive adhesive. At this time, the curing agent used may be melamine, metal chelate, isocyanate, aziridine, epoxy or the like.

The dye is to use a conventional dye used in the art as a detailed description will be omitted in the present invention.

Hereinafter, an embodiment of the present invention will be described.

Example 1

80 g of 2-ethylhexyl acrylate, 20 g of vinyl acetate, 4 g of acrylic acid, 0.25 g of azobisisobutylonitrile with reaction initiation and 100 g of ethyl acetate are added to a reactor with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube, and mixed. The mixture was allowed to react at 80 ° C. for 7 to 8 hours, and then aged at 14 ° C. by adjusting the reactor temperature to 55 ° C., and then 145 g of ethyl acetate was added to the mixture to prepare a mixture (adhesive) of 30% solids.

Example 2

70 g of 2-ethylhexyl acrylate, 15 g of butyl acrylate, 15 g of vinyl acetate, 3 g of acrylic acid, 1 g of 2-hydroxyethyl methacrylate, 2 g of benzoyl peroxide, lauroyl peroxide, and 100 g of ethyl acetate were mixed with a stirrer, a thermometer, Into the reactor with a reflux condenser and nitrogen inlet tube, mixed and reacted at 80 ℃ for 7 to 8 hours, and after aging for 14 hours by adjusting the reactor temperature to 55 ℃, 142 g of ethyl acetate was added after the completion of the reaction A mixture (adhesive) of 30% solids was prepared.

Example 3

50 g of 2-ethylhexyl acrylate, 40 g of butyl acrylate, 10 g of vinyl acetate, 2 g of acrylic acid, 1 g of 2-hydroxyethyl acrylate, 0.1 g of en-metholacrylamide, 0.25 parts of azobisisobutylonitrile and ethyl 100 parts of acetate was added to a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, mixed, and reacted at 80 ° C. for 7 to 8 hours, and then aged at 14 ° C. by adjusting the reactor temperature to 55 ° C., after completion of the reaction, ethyl 145 g of acetate were added to form a mixture (adhesive) of 30% solids.

Example 4

70 g of 2-ethylhexyl acrylate, 15 g of butyl acrylate, 15 g of vinyl acetate, 1 g of acrylic acid, 3 g of 2-hydroxyethyl methacrylate, 0.5 g of glycidyl methacrylate, 0.25 g of azobisisobutylonitrile and 0.25 g of ethyl 100 parts of acetate was added to a reactor with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube, mixed and reacted at 80 ° C. for 7 to 8 hours, and then aged at 14 ° C. by adjusting the reactor temperature to 55 ° C., and then the reaction was completed. Then, 142 g of ethyl acetate was added to the mixture to prepare a mixture (adhesive) of 30% solids.

Example 5

80 g of 2-ethylhexyl acrylate, 20 g of vinyl acetate, 1 g of acrylic acid, 3 g of 2-hydroxyethyl acryl, 2 g of benzoyl peroxide, lauroyl peroxide and 100 g of ethyl acetate were added to a stirrer, thermometer, reflux cooler, and nitrogen injection. The mixture was added to a reactor with a tube, mixed, and reacted at 80 ° C. for 7 to 8 hours, and then the reactor temperature was adjusted to 55 ° C. for 14 hours. After completion of the reaction, 143 g of ethyl acetate was added to the mixture, and the mixture was mixed with 30% solids. (Adhesive) was prepared.

The properties of the pressure-sensitive adhesive of the above examples are shown in the table.

Example 1 Example 2 Example 3 Example 4 Example 5 Imitation devil 2-EHA 80 70 50 70 80 BA 15 40 15 VAc 20 15 10 15 20 AAc 4 3 2 One One 2-HEMA One 3 2-HEA One 3 GMA 0.5 N-MAM 0.1 Lagadicecal BPO 0.2 0.2 LPO 0.2 0.2 ABN 0.25 0.25 0.25 solvent EA 100 100 100 100 100 Theoretical solids (%) 30.48 30.48 30.48 30.48 30.48 Solid content 30.1 30.0 30.1 30.2 30.1 Viscosity (cps / 30 ℃) 500 540 600 545 470

Note 1) The above example is adjusted to 30% solids by EA. Note 2) 2-EHA: 2-ethylhexyl acrylate, BA: butyl acrylate, VAc: vinyl acetate, 2-HEMA: 2-hydroxyethyl methacrylate, 2-HEA: 2-hydroxyethyl acrylate, GMA: Glycidyl methacrylate, N-MAM: N-metholacrylamide, BPO: benzoyl peroxide, LPO: lauroyl peroxide, ABN: azobisisobutylonitrile, EA: ethyl acetate

(Examples 6-20)

Example 1 to 0.3 g of a butylated melamine compound, 0.5 g of polyisocyanate, 0.5 g of epoxy, 0.5 g of metal chelate, 0.05 g of azadine, 0.5 g of dye, 7 g of 4 g, to the mixture (adhesive) prepared in Example 5 , 10 g of methyl ethyl ketone, 10 g of ethyl acetate, 10 g of ethyl acetate were mixed as shown in Table 2 and Table 3, respectively, and mixed in a stirrer to prepare a pressure-sensitive adhesive composition.

Table 2

Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Remarks Example 1 100 - 100 - 100 - 100 - 100 - - Example 4 - 100 - 100 - 100 - 100 - 100 - Butylated Melamine 0.3 0.3 - - - - - - - - - Polyisocyanate - - 0.5 0.5 - - - - - - - Epoxy - - - - 0.5 0.5 - - - - - Metal chelate system - - - - - - 0.05 0.05 - - - Aziridine series - - - - - - - - 0.5 0.5 -

Table 3

Example 16 Example 17 Example 18 Example 19 Example 20 Comparative Example 1 Comparative Example 2 Remarks adhesive 100 100 100 100 100 100 100 - Dye (black) (1) 7 7 7 7 7 7 7 - Dye (brown) (2) 4 4 4 4 4 4 4 - Methyl ethyl ketone 10 10 10 10 10 10 10 - Ethyl acetate 10 10 10 10 10 10 10 - Butylated Melamine 0.3 0.3 0.3 0.3 0.3 0.3 0.3 -

Experimental Example 1 (Physical experiment by adhesive according to the example)

1. Selection of curing agent

Butylated melamine-based, polyisocyanate-based, epoxy-based, metal chelate-based, and aziridine-based curing agents were added to Examples 1 and 4, and the pot life was determined by measuring the compatibility and viscosity change to select a curing agent.

Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Remarks Example 1 100 - 100 - 100 - 100 - 100 - - Example 4 - 100 - 100 - 100 - 100 - 100 - Butylated Melamine 0.3 0.3 - - - - - - - - - Polyisocyanate - - 0.5 0.5 - - - - - - - Epoxy - - - - 0.5 0.5 - - - - - Metal chelate system - - - - - - 0.05 0.05 - - - Aziridine series - - - - - - - - 0.5 0.5 - Initial Example 510 545 500 550 500 550 500 545 500 545 cps / 30 ℃ Viscosity after 1 day 540 560 Gelation Gelation 1,200 980 510 550 1,300 1,100 cps / 30 ℃ Judgment ◎ ◎ × × × × ◎ ◎ × × ×: Poor O: Good ◎: Very good

Note 1) Butylated melamine-based curing agent: Abutylated melamine-based curing agent having a solidity of 60% butylated urea melamine resin as the main component is 40% degree of butylation in the present invention, Aekyung Chemical J-820-60 was used. .

Note 2) Polyisocyanate-based curing agent: Songwon Industrial CA-75NY was used in the present invention as a general-purpose isocyanate-based curing agent with a solid content of 50 to 75% having two or more isocyanates at its terminals.

Note 3) Epoxy curing agent: Epoxy curing agent between 5 to 10% of solid content having two or more glycidyl groups at the terminal. In the present invention, N, N, N ', N'-tetraglycidyl-m-kisylene AX-1 from Soken Kagaku, Japan, which is a diamine, was used.

Note 4) Metal chelate-based curing agent: As a metal chelate-based curing agent whose main component is aluminum acetacetonate and a solid content of 100%, in the present invention, Japanese chemical industry Nasemite aluminum was used.

Note 5) Aziridine-based curing agent: 100% of aziridine-based curing agent having a solid having two or more aziridyl groups at the terminal. Used.

As a result of the above experiment, it was found that as a low-soluble hardener, butyl melamine and metal chelates were used. Isocyanate-based, epoxy-based and aziridine-based curing agents were found to be difficult to apply due to the viscosity increase due to gelation after 1 day of blending. Therefore, in the present invention, only butyl melamine and a metal chelate system were used as a curing agent in subsequent experiments.

Experimental Example 2. (Experiment according to the example of the dye)

In the example test of the dye, the compatibility with the pressure-sensitive adhesive, the color clarity of the example, and the decolorization degree of the dye are examined for each example.

The hardening | curing agent selected the butylated melamine type hardening | curing agent with favorable compatibility with an adhesive, and performed the Example test.

Example 16 Example 17 Example 18 Example 19 Example 20 Comparative Example 1 Comparative Example 2 Remarks adhesive 100 100 100 100 100 100 100 - Dye (black) (1) 7 7 7 7 7 7 7 - Dye (brown) (2) 4 4 4 4 4 4 4 - Methyl ethyl ketone 10 10 10 10 10 10 10 - Ethyl acetate 10 10 10 10 10 10 10 - Butylated Melamine 0.3 0.3 0.3 0.3 0.3 0.3 0.3 - Initial Example 370 390 430 390 300 440 460 cps / 30 ℃ Viscosity after 1 day 410 395 460 400 310 920 720 cps / 30 ℃ Judgment Compatibility O ◎ O ◎ ◎ △ △ ×: Poor △: Normal O: Good ◎: Very good Discoloration ◎ ◎ O ◎ O △ ×

Note 1) The dyes (1) and (2) belong to azo dyes containing amino or hydroxyl groups as metal complex salt-soluble dyes. In the present invention, Shivagagi and Hodogaya products under the trade names Eisen, Spielon, and SOT are used.

Note 2) Comparative Examples 1 and 2 used an adhesive applied to the existing solar light control film.

Note 3) Dye was applied to existing solar light control film due to its usefulness.

In Comparative Examples 1 and 2, the dyes were poor in compatibility due to poor compatibility, and when exposed to sunlight, the change over time (color fading) also progressed rapidly.

Experimental Example 3. (Heat and moisture resistance test)

Adhesive-coated film is attached to the glass plate as a sample Phenomena that peels off easily from the glass plate due to the discoloration of the pressure-sensitive adhesive and the dye and the effect of moisture and temperature at 60 ℃ × 95% RH × 72 hours. Examine the presence or absence of applicability depending on whether

Examples of pressure-sensitive adhesives, dyes, and curing agents used the same examples as the dye example experiments.

Example 16 Example 17 Example 18 Example 19 Example 20 Comparative Example 1 Comparative Example 2 Remarks adhesive 100 100 100 100 100 100 100 - Dye (black) 7 7 7 7 7 7 7 - Dye (brown) 4 4 4 4 4 4 4 - Methyl ethyl ketone 10 10 10 10 10 10 10 - Ethyl acetate 10 10 10 10 10 10 10 - Butylated Melamine 0.3 0.3 0.3 0.3 0.3 0.3 0.3 - Peel force 550 480 450 450 520 430 450 Glass / g / 25mm Lifting clear clear clear clear clear Uplifting Uplifting edge Dye Discoloration ◎ ◎ O ◎ O △ × ×: Poor △: Normal O: Good ◎: Very good

As in the dye example, heat resistance and moisture resistance, discoloration experiment results, the conventional pressure-sensitive adhesive for solar light transmission control film has poor compatibility and shows discoloration to sunlight, and also has poor heat and moisture resistance. The good results were shown as 1-5.

The pressure-sensitive adhesive of the present invention has excellent adhesion between the dye and the dye in the embodiment while having the proper adhesive force as shown in the examples, does not cause gelation, and has excellent discoloration resistance to prevent discoloration of the dye, heat and moisture resistance. Since the edge of the adhesion film does not occur it can be used as a pressure-sensitive adhesive suitable for solar light transmission control film.

Claims (7)

In the pressure-sensitive adhesive composition, 50 to 100 parts of 2-ethylhexyl acrylate, 15 to 20 parts of butyl acrylate, 5 to 30 parts of vinyl acetate, 1 to 6 parts of acrylic acid, and 0.5 to 5 parts of 2-hydroxyethyl methacrylate A pressure-sensitive adhesive composition comprising 0.1 to 0.6 parts of a radical initiator, 1 to 30 parts by weight of a solvent, 0.01 to 10 parts by weight of a curing agent, 0.1 to 0.5 parts by weight of an improving agent, and 11 parts by weight of a dye. The compound according to claim 1, wherein the radical initiator is selected from a peroxide-based compound such as benzoyl peroxide and lauroyl peroxide, and an azo-based compound such as azobisisobutylonitrile and azodimethylvalellonitrile. Or an adhesive composition comprising two or more compounds. The pressure-sensitive adhesive composition of claim 1, wherein the solvent comprises two compounds selected from ethyl acetate, toluene, acetone, methanol, isopropyl alcohol, cyclonucleic acid, nomal nucleic acid, and nomal pantan. The pressure-sensitive adhesive composition of claim 1, wherein the curing agent is any one compound selected from melamine-based, metal chelate-based, isocyanate-based, aziridine-based, and epoxy-based compounds. The pressure-sensitive adhesive composition of claim 1, wherein the enhancer is any one compound selected from functional monomers such as glycidyl methacrylate, en-metholacrylamide, and acrylamide. In the manufacturing method of an adhesive composition, 50-100 parts of 2-ethylhexyl acrylate, 15-20 parts of butyl acrylate, 5-30 parts of vinyl acetate, 1-6 parts of acrylic acid, 0.5-5 parts of 2-hydroxyethyl methacrylate, and 0.1-radical initiator 0.6 parts, 1 to 30 parts by weight of solvent, 0.1 to 0.5 parts by weight of enhancer were added to a reactor equipped with an agitator, thermometer, reflux condenser and nitrogen inlet tube, mixed, and reacted at 80 ° C. for 7 to 8 hours. After aging for 14 hours, the mixture was added by mixing 60 to 150 parts by weight of ethyl acetate to prepare a mixture (adhesive), and then 11 parts by weight of dye and 0.01 to 10 parts by weight of a curing agent were added to the stirrer. Method for producing a pressure-sensitive adhesive composition, characterized in that. In the manufacturing method of an adhesive composition, 50-100 parts of 2-ethylhexyl acrylate, 15-20 parts of butyl acrylate, 5-30 parts of vinyl acetate, 1-6 parts of acrylic acid, 0.1-0.6 parts of radical initiators, solvent 1-30 parts, improver 0.1-0.5 The weight part was added to a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen input tube, mixed, and reacted at 80 ° C. for 7 to 8 hours. After aging for 14 hours by adjusting the reactor temperature to 55 ° C., the reaction was completed with ethyl acetate. A method of producing a pressure-sensitive adhesive composition comprising adding 60 to 150 parts by weight to prepare a mixture (adhesive) of 30% solids, and then adding 11 parts by weight of dye and 0.01 to 10 parts by weight of a curing agent to prepare a mixture.