KR100822731B1 - Adhesive composition of one component for adhering metal film on plated steel sheet - Google Patents

Abstract

The present invention relates to a one-component adhesive composition for adhering a metal film to a plated steel sheet, wherein the ring-opening epoxy resin is 5 to 30 parts by weight, gamma-glycidoxypropyltrimethoxy with respect to 100 parts by weight of thermoplastic polyurethane resin. 1 to 10 parts by weight of silane, 1 to 10 parts by weight of blocked isocyanate, 1 to 10 parts by weight of amorphous finely divided silica, 10 to 100 parts by weight of mixed organic solvent, and the thermoplastic polyurethane resin Is 20 parts by weight to 350 parts by weight of polytetraethylene ether glycol having a molecular weight in the range of 1,000 to 2,000, and 1 part by weight to 40 parts by weight of ethylene glycol as a chain extender, based on 100 parts by weight of polyester polyol in the range of 1,000 to 2,000, 1 1 to 40 parts by weight of 4-butanediol, 20 to 200 parts by weight of isocyanate The one-component adhesive composition for bonding the metal film to the plated steel sheet is stable at room temperature, and has only one-time adhesiveness, so that the adhesive strength becomes weak even when heat is again applied to the color steel sheet, so that the adhesive is not deformed or separated from each other. It shows excellent corrosion resistance, processability and boiling resistance, so it can be used in various fields such as industrial, home and building materials.

Metal film, plated steel sheet, thermoplastic polyurethane resin, color steel sheet, PCM, aluminum, laminate, adhesive.

Description

Adhesive composition of one component for adhering metal film on plated steel sheet

1 is a color steel sheet manufactured using the adhesive composition prepared according to an embodiment of the present invention.

Figure 2 is an automated production facility for producing a color steel sheet using the adhesive composition prepared according to an embodiment of the present invention.

3 is a flowchart showing each step of the method for producing a color steel sheet using the adhesive composition prepared according to an embodiment of the present invention over time.

<Description of the symbols for the main parts of the drawings>

10 metal film 20 adhesive composition

30: plated steel sheet 41: coil uncoiler (Uncoiler)

42: Clearing 43: Accumulator

44: pretreatment 45: conveyor

46: coat coater 47: automatic oven (Oven)

48: Lamination 49: Water quenching

50: exit accumulator 51: shear

52: coil winding device (Recoiler)

The present invention relates to a one-part adhesive composition for bonding a metal film to a plated steel sheet, and more particularly, by bonding a metal film and a plated steel sheet using a one-part adhesive composition stable at room temperature to which thermoplastic polyurethane resin is applied. The present invention relates to a one-component adhesive composition for bonding a metal film to a plated steel sheet, which may have a shortening time and a cost saving effect of a product.

Adhesive compositions useful for bonding metal films to each other have been disclosed in Korean Patent Publication No. 1992-0001492, and the adhesive composition according to the present invention is prepared by vacuuming a metal film, and combining the two metal films with each other, Alkaline, high pressure hot water, etc. must be used in the coloring and post-treatment steps, which increases the manufacturing cost and lengthens the product manufacturing time.

In general, a metal or a metal is bonded to each other by welding or adhesive. In the bonding method using an adhesive, an adhesive such as an instant adhesive or a bond is applied to an adherend, and then metals are bonded to each other and heat treated or aged. However, due to its chemical properties, bonds and instant adhesives are hard to handle at room temperature when they come into contact with air. Therefore, they are difficult to handle, and their productivity is low. Especially, they are not suitable for the Premetalled metal process, which is characterized by a continuous process. .

Common metal coating methods include a post-coating method for coating after molding and a pre-coating method for coating before molding. Here, the steel plate coated with the metal to be formed by a pre-coating method is called a pre-coated metal or color steel sheet, and the paint used therein is called a PM paint. Here, the metal is mainly used a steel plate coated with zinc. Here, there are two types of metal plates: sheets cut to a certain size and coils wound. Most PC manufacturing plants employ a coil coating method for automatically and continuously coating metal coils. It is often used together. The PCM has the advantages of rationalizing the process, stabilizing the quality, improving the quality, saving resources, preventing pollution, saving energy, reducing the construction period, and reducing the cost.

A method of manufacturing a color steel sheet by applying a polymer polyester-based paint through such a PCM process has been disclosed in Korean Patent No. 10-0342913, and the color steel sheet is plated with zinc or aluminum on a steel sheet and chromated. As a method of processing, there is a limit in expressing a texture of a soft and special form.

When discussing colored steel in a broader sense, not only steel plates coated with paint in advance, but also polymer laminate films such as polyethylene and polyethylene terephtalate, which can be textured by forming special patterns. It may include a steel sheet and the like bonded through a PCM process. Such steel sheet is a high value-added product that is used for various applications such as a case of a home appliance, an interior finishing material of a building, etc., but since the price of the polymer film itself is poor and its flame retardancy is poor, its use is limited to building materials such as fire doors. In particular, the adhesive used to adhere the polymer laminate film to the steel sheet in the PCM mainly consists of a two-component form in which the main material and the curing agent are separated, which is characterized by a continuous process because of the difficulties in handling and storage. It is relatively inadequate in the manufacturing process of PCM, and it is impossible to use it because of poor adhesion ability for metal-to-metal adhesion.

Color steel sheets for construction materials are mainly used as steel sheets coated with the top and bottom coats, or steel sheets with beautiful patterns by coating the top coat after transferring the printing ink. Despite its beautiful appearance and many advantages, its mechanical properties are inferior to plated steel sheets, and are generally more than twice as expensive and have large fluctuations. However, when aluminum is thinned and adhered to the plated steel sheet, it is possible to simultaneously utilize the excellent mechanical properties of the steel sheet while maintaining the texture and appearance of the aluminum as it is, and to produce a steel sheet having a relatively lower price than aluminum.

Therefore, there is an urgent need in the art for the development of an adhesive composition that is very suitable for the PCM process and can strongly adhere the metal to the metal.

Therefore, the technical problem of the present invention for solving the above problems is that of a color steel sheet bonded to a metal film and a plated steel sheet using an adhesive composition produced by applying a ring-opening epoxy resin and a silane compound to a thermoplastic polyurethane resin composite In addition to shortening the manufacturing time and cost, a one-component adhesive composition for bonding a metal film having a peel strength of 4 kg / cm ² or more and excellent corrosion resistance, boiling resistance, and bendability (processability) to the plated steel sheet To provide.

In order to achieve the above technical problem, the present invention provides 5 to 30 parts by weight of the ring-opening epoxy resin based on 100 parts by weight of the thermoplastic polyurethane resin, and gamma-glycidoxy

1 to 10 parts by weight of propyltrimethoxysilane, 1 to 10 parts by weight of blocked isocyanate, 1 to 10 parts by weight of amorphous finely divided silica, and 10 to 100 parts by weight of mixed organic solvent It provides a one-part adhesive composition for bonding a metal film to a plated steel sheet.

The thermoplastic polyurethane resin is 20 parts by weight to 350 parts by weight of polytetraethylene ether glycol having a molecular weight in the range of 1,000 to 2,000 with respect to 100 parts by weight of polyester polyol in the range of 1,000 to 2,000, and 1 part by weight of ethylene glycol as a chain extender. To 40 parts by weight, 1 to 4 parts by weight of 1,4-butanediol, and 20 parts to 200 parts by weight of isocyanate.

The ring-opening epoxy resin may be one in which the epoxy functional group of the epoxy resin itself is ring-opened and replaced with a hydroxyl group.

The ring-opening epoxy resin may have a molecular weight in the range of 15,000 to 35,000.

The blocked isocyanate may have an NCO functional group of isophorone diisocyanate blocked by methyl ethyl ketoxim to have a dissociation temperature at 120 degrees Celsius or more.

 The amorphous fine silica may have an oil absorption of 200 to 300 ml / 100 g, an average particle size of 1.0 to 2.0 μm, and a pH of 4 wt% water suspension in the range of 6.0 to 7.5.

The mixed organic solvent may be applied as xylene: PMG = 1: 1.

Hereinafter, the one-part adhesive composition for adhering the metal film of the present invention to a plated steel sheet will be described in more detail.

Polyurethane resin of the thermoplastic polyurethane resin composition of the present invention is characterized in that it is synthesized through an exothermic reaction at 20 degrees to 130 degrees Celsius, with respect to 100 parts by weight of the polyester polyol (Polyesterpolyol), a soft segment, polytetraethylene ether Preference is given to 20 parts by weight to 350 parts by weight of polytetraethyleneether glycol.

When the polytetraethylene ether glycol is less than 20 parts by weight with respect to the polyester polyol in the synthesis of the thermoplastic polyurethane resin composition, the adhesion is improved, but the boiling resistance, the corrosion resistance, etc. are lowered due to the decrease in the hydrolysis resistance, and the polyester polyol If the polytetraethylene ether glycol is 350 parts by weight or more, there is a problem in that the adhesive strength remains low even at low temperatures.

Ethylene glycol used as the chain extender as the hard segment is 1 to 40 parts by weight, 1,4-butanediol (1,4-butandiol) is preferably 1 to 40 parts by weight, the ethylene glycol When the content of 1,4-butanediol is less than 1 part by weight, the coating film is too soft and the adhesive strength is lowered because the adhesiveness remains at room temperature. When the content of the ethylene glycol and the 1,4-butanediol is 40 parts by weight or more, a problem arises in that the viscosity of the ethylene glycol and the 1,4-butanediol are high and the coating film is excessively brittle, and the adhesiveness becomes low, and the adhesion of aluminum is poor after the coating film is dried when the adhesive is adhesive. .

Isocyanate, which is a curing agent in synthesizing the thermoplastic polyurethane resin composition, refers to a compound having an NCO functional group in a molecular structure, and is used in the synthesis of a polyurethane resin to serve as a hard segment. There are various kinds of Toluenediisocyanate (TDI), Diphenylmethanediisocyanate (MDI), Isoporondiisocyanate (IPDI), Naphthalenendiisocyanate (NDI), and Hexamethylene diisocyanate (HDI) depending on the molecular structure. In the synthesis of the thermoplastic polyurethane resin of the present invention, it is preferable to use 20 parts by weight to 200 parts by weight of TiDi (TDI) in the isocyanate as the curing agent.

The epoxy resin of the epoxy resin composition is mainly used to compensate for the weak heat resistance of the thermoplastic polyurethane resin and the adhesiveness at room temperature, and in particular, the ring opening epoxy resin (Kukdo Chemical) having a molecular weight in the range of 15,000 to 35,000 is applied. Can be found in the epoxy resin molecular structure.

Since the ring-opening epoxy resin used in the present invention has more hydroxyl groups than the general epoxy resin of the same molecular weight because the epoxy functional group of the epoxy resin itself is ring-opened, it is strongly adsorbed with iron and aluminum to give stronger adhesion. In addition, the epoxy resin itself gives the physical and chemical advantages of heat stability, corrosion resistance, boiling resistance, and the like.

In the present invention, when the molecular weight of the ring-opening epoxy resin is less than 15,000, the adhesive strength is lowered or the boiling resistance is lowered, and when the molecular weight is 35,000 or more, the viscosity is increased, making the adhesive production and painting difficult.

In the present invention, the ratio of the ring-opening epoxy resin is suitably 5 parts by weight to 30 parts by weight based on 100 parts by weight of the thermoplastic polyurethane resin, but when the ring-opening epoxy resin content is less than 5 parts by weight with respect to the thermoplastic polyurethane resin, When the content of the ring-opening epoxy resin is 30 parts by weight or more with respect to the thermoplastic polyurethane resin, the coating film becomes brittle, which causes problems in adhesion of the metal film.

In addition, 1 to 10 parts by weight of isocyanate (methylethylketoxime blocked isophoronediisocyanate, BAXENDEN CHEMICALS) which is blocked by methyl ethyl ketoxim and dissociated at about 120 degrees Celsius is used as an isocyanate as a crosslinking agent (curing agent) in the present invention. The reason for using the blocked isocyanate is that the adhesive composition is prepared because it may react even at room temperature with the unreacted hydroxyl group and the hydroxyl group of the ring-opening epoxy resin remaining in the synthesis step of the thermoplastic polyurethane resin when not blocked due to the nature of the NCO functional group of the isocyanate. After several hours to several tens of hours after gelation is not able to maintain a stable state at room temperature can not be used. Therefore, when isophorone diisocyanate with NCO functional group blocked by methyl ethyl ketoxim is not reactive at room temperature, it remains stable and when heated to 120 degrees Celsius or more, NCO functional group and methyl ethyl ketoxim dissociate to activate NCO functional group. In the range of 180 to 200 degrees Celsius, an unreacted hydroxyl group of the thermoplastic polyurethane resin and a hydroxyl group of the ring-opening epoxy resin may be rapidly reacted to obtain an adhesive coating film capable of adhering a metal film. When the blocked isophorone diisocyanate content is less than 1 part by weight, the adhesion strength is lowered, and when the content is 10 parts by weight or more, the boiling resistance is adversely affected.

As an adhesion aid, 1 to 10 parts by weight of gamma-glycidoxypropyltrimethoxysilane is used. The epoxy functional group of the silane reacts with the organic functional group of the epoxy composition, and the silane functional group is rapidly hydrolyzed upon heating. It provides a strong adhesion through the hydrogen bond with the metal material, and the epoxy functional group reacts with the curing agent and the like to improve the adhesion strength.

In the present invention, when the content of gamma-glycidoxypropyltrimethoxysilane is less than 1 part by weight, the adhesion shows a tendency to decrease the strength, and when the content of gamma-glycidoxypropyltrimethoxysilane is 10 parts by weight or more. Has a tendency to lower the boiling resistance because of its hydrolytic property.

In the present invention, 1 part by weight of amorphous finely divided silica (Nipsil) having an oil absorption of 200 to 300 ml / 100 g, an average particle size of 1.0 to 2.0 μm, and a pH of about 6.0 to 7.5 of a 4 wt% water suspension as a curing and coating durability aid. If the content of amorphous fine silica is less than 1 part by weight, the adhesion strength is weakened. If the content of the amorphous fine silica is more than 10 parts by weight, the viscosity of the adhesive is increased so that the anti-foaming property is poor and the fluidity is poor. It does not benefit workability apart. In particular, when the pH of silica 4% by weight aqueous suspension is out of the range of 6.0 to 7.5 it does not benefit the long-term storage of the adhesive composition. If the oil absorption is less than 200 ml / 100g, the dispersibility during the manufacture of the adhesive is not good, so that it is not beneficial to the productivity, and if it exceeds 300 ml / 100g, the viscoelasticity and viscosity is too high, which is not beneficial to the manufacturing and workability. In addition, when the average particle size of the amorphous fine silica exceeds 2 μm, it is not beneficial for obtaining a smooth adhesive coating film and for rapid dispersion of the silica particles.

Mixed organic solvent (Xylene) based on 100 parts by weight of the mixed composition:

PGMA (PGMEA, Propylene Glycol Methyl Ether Acetate (PGMEA = 1 = 1)) by mixing 10 parts by weight to 100 parts by weight of high-speed stirring to prepare an adhesive. It is preferable to use the organic solvent having a boiling point of between 120 and 150 degrees Celsius. If the boiling point of the organic solvent is lower than 120 degrees Celsius, drying of the coating film proceeds too fast and the metal film does not adhere. If the boiling point is higher than 150 degrees Celsius, the solvent may not be sufficiently volatilized during the drying process, and thus adhesive strength may remain on the coating film, thereby reducing the strength of adhesion.

Hereinafter, the preparation examples will be described in more detail. These preparations are only for illustrating the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. .

In this preparation example, the weight ratio of polytetraethylene ether glycol, polyester polyol, ethylene glycol, 1,4-butanediol, cyclohexanone, isocyanate (TDI), DBTDL (Dibutyltin dilaurate) catalyst, toluene, methyl ethyl ketone, methyl alcohol Alternatively, the thermoplastic polyurethane resin was synthesized, and the metal film of the present invention was prepared using the ring-opening epoxy resin, gamma-glycidoxypropylmethoxysilane, blocked isophorone diisocyanate, amorphous finely divided silica, and a mixed solvent. A one-part adhesive composition for adhering to the plated steel sheet was prepared.

Production Example  1: thermoplastic Polyurethane resin  Synthesis method of 1

Thermoplastic polyurethane resin 1 is 3.9 parts by weight of ethylene glycol, 3 parts by weight of 1,4-butanediol, 43 parts by weight of cyclohexanone, 35 parts by weight of isocyanate (TDI), DBTDL with respect to 100 parts by weight of polyester polyol in a four-necked flask. (Dibutyltin dilaurate) 0.04 parts by weight of catalyst, 156 parts by weight of toluene, 144 parts by weight of methyl ethyl ketone, 0.4 parts by weight of methyl alcohol, and then the temperature is raised to about 80 ℃ while mixing and stirring, and when the exotherm starts to cool the inside of the reactor It is synthesized by cooling to room temperature after maintaining for 4 hours while maintaining at 80 ℃. 70.0% of the synthesized thermoplastic polyurethane resin 1, ring opening epoxy resin 10.0%, gamma-glycidoxypropylmethoxysilane 2.0%, blocked isophorone diisocyanate 2.0%, amorphous fine silica 1.0%, mixed solvent 15% Preparation Example 1 was prepared.

Production Example  2: thermoplastic Polyurethane resin  2 synthesis method

Thermoplastic polyurethane resin 2 is 6.9 parts by weight of ethylene glycol, 108 parts by weight of cyclohexanone, 61.5 parts by weight of isocyanate (TDI), 0.08 parts by weight of dibutyltin dilaurate catalyst (DBTDL), based on 100 parts by weight of polyester polyol in a four-necked flask. After 185 parts by weight of toluene, 215 parts by weight of methyl ethyl ketone and 0.8 parts by weight of methyl alcohol, the temperature was raised to about 80 ° C. while mixing and stirring, and when the exotherm started, it was cooled and maintained inside the reactor at 80 ° C. for 4 hours. It is synthesized by cooling to room temperature. 70.0% of the synthesized thermoplastic polyurethane resin 2, ring opening epoxy resin 10.0%, gamma-glycidoxypropylmethoxysilane 2.0%, blocked isophorone diisocyanate 2.0%, amorphous fine silica 1.0%, mixed solvent 15% Preparation Example 2 is prepared.

Production Example  3: thermoplastic Polyurethane resin  3 synthesis method

Thermoplastic polyurethane resin 3 is 360 parts by weight of polytetraethylene ether glycol, 20 parts by weight of ethylene glycol, 30 parts by weight of 1,4-butanediol, 200 parts by weight of cyclohexanone, based on 100 parts by weight of polyester polyol in a four-neck flask. 180 parts by weight of isocyanate (TDI), 0.04 parts by weight of a DBTDL (Dibutyltin dilaurate) catalyst, 340 parts by weight of toluene, 40 parts by weight of methyl ethyl ketone, and 2 parts by weight of methyl alcohol were quantitatively added, and the temperature was raised to about 80 ° C while mixing and stirring. When the exotherm starts, the mixture is cooled and maintained at 80 ° C. for 4 hours, followed by cooling to room temperature for synthesis. 70.0% of the synthesized thermoplastic polyurethane resin 3, ring opening epoxy resin 10.0%, gamma-glycidoxypropylmethoxysilane 2.0%, blocked isophorone diisocyanate 2.0%, amorphous fine silica 1.0%, mixed solvent 15% Preparation Example 3 is prepared.

Production Example  4 to Production Example  9: thermoplastic Polyurethane resin  4 synthesis method

Thermoplastic polyurethane resin 4 is 150 parts by weight of polytetraethylene ether glycol, 16.7 parts by weight of ethylene glycol, 33 parts by weight of 1,4-butanediol, 83 parts by weight of cyclohexanone, based on 100 parts by weight of polyester polyol in a four-necked flask. 141 parts by weight of isocyanate (TDI), 0.033 parts by weight of DBTDL (Dibutyltin dilaurate) catalyst, 167 parts by weight of toluene, 150 parts by weight of methyl ethyl ketone, and 1.7 parts by weight of methyl alcohol were added thereto in a fixed amount, and the temperature was raised to about 80 ° C. while mixing and stirring, When the exotherm starts, the mixture is cooled and maintained at 80 ° C. for 4 hours, followed by cooling to room temperature for synthesis.

In Preparation Example 4, 70.0% of the synthesized thermoplastic polyurethane resin 4, ring opening epoxy resin 10.0%, gamma-glycidoxypropylmethoxysilane 2.0%, blocked isophorone diisocyanate 2.0%, amorphous fine silica 1.0%, mixed solvent Prepare Example 4 using 15.0%.

Preparation Example 5 was prepared using 70.0% of the synthesized thermoplastic polyurethane resin 4, gamma-glycidoxypropylmethoxysilane, 2.0% blocked isophorone diisocyanate, 1.0% amorphous fine silica, 25.0% mixed solvent. Prepare Example 5.

In Preparation Example 6, 70.0% of the synthesized thermoplastic polyurethane resin 4, ring-opening epoxy resin 15.0%, gamma-glycidoxypropylmethoxysilane 2.0%, blocked isophorone diisocyanate 2.0%, amorphous fine silica 1.0%, mixed solvent Preparation Example 6 was prepared using 10.0%.

Preparation Example 7 is 70.0% of the synthesized thermoplastic polyurethane resin 4, 7.0% ring-opening epoxy resin, 4.0% gamma-glycidoxypropylmethoxysilane, 2.0% blocked isophorone diisocyanate, 3.0% amorphous fine silica, mixed solvent Preparation Example 7 was prepared using 14.0%.

Preparation Example 8 was prepared using 70.0% of the synthesized thermoplastic polyurethane resin 4, ring-open epoxy resin 7.0%, gamma-glycidoxypropylmethoxysilane 2.0%, blocked isophorone diisocyanate 2.0%, mixed solvent 19.0% Example 8 is prepared.

In Preparation Example 9, 70.0% of the synthesized thermoplastic polyurethane resin 4, 7.0% ring-opening epoxy resin, 2.0% gamma-glycidoxypropylmethoxysilane, 2.0% blocked isophorone diisocyanate, 1.0% amorphous fine silica, mixed solvent Preparation Example 9 was prepared using 18.0%.

division Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Polyurethane Resin 1 (40% Solids, Samwha Paint) 70.0% - - - Polyurethane Resin 2 (40% Solids, Samwha Paint) - 70.0% - - Polyurethane Resin 3 (40% Solids, Samwha Paint) - - 70.0% - Polyurethane Resin 4 (40% Solids, Samwha Paint) - - - 70.0% Ring opening epoxy resin (40% solids, Kukdo Chemical) 10.0% 10.0% 10.0% 10.0% Gamma-glycidoxypropyltrimethoxysilane 2.0% 2.0% 2.0% 2.0% Blocked isophorone disocyanate (70% of solids, BAXENDEN CHEMICALS) 2.0% 2.0% 2.0% 2.0% Amorphous Fine Silica (NIPSIL) 1.0% 1.0% 1.0% 1.0% Mixed Solvent (Xylene: PGMEA = 1: 1) 15.0% 15.0% 15.0% 15.0% sub Total 100.0% 100.0% 100.0% 100.0%

※ The ratio of manufacturing example means weight% as compounding ratio.

division Preparation Example 5 Preparation Example 6 Preparation Example 7 Preparation Example 8 Preparation Example 9 Polyurethane Resin 4 (40% Solids, Samwha Paint) 70.0% 70.0% 70.0% 70.0% 70.0% Ring opening epoxy resin (40% solids, Kukdo Chemical) - 15.0% 7.0% 7.0% 7.0% Gamma-glycidoxypropyltrimethoxysilane 2.0% 2.0% 4.0% 2.0% 2.0% Blocked isophorone disocyanate (70% of solids, BAXENDEN CHEMICALS) 2.0% 2.0% 2.0% 2.0% 2.0% Amorphous Fine Silica (NIPSIL) 1.0% 1.0% 3.0% - 1.0% Mixed Solvent (Xylene: PGMEA = 1: 1) 25.0% 10.0% 14.0% 19.0% 18.0% sub Total 100.0% 100.0% 100.0% 100.0% 100.0%

※ The ratio of manufacturing example means weight% as compounding ratio.

Test Example  One

In one embodiment, by using a one-component adhesive composition for bonding the metal film prepared in the above manner to the plated steel sheet, the aluminum laminate film, which is a metal film, and the hot dip galvanized steel sheet, which is a plated steel sheet, are bonded as follows. An example was carried out.

The physical properties of the adhesive steel sheet include 180 ° peeling strength, boiling water resistance, corrosion resistance, workability (C.E.T), and workability (bendability).

The 180 ° peeling strength was measured according to the test method of ASTM D903-93, and then the peel strength was measured. The boiling resistance was measured by preparing the adhesive specimen in a predetermined size and leaving it in boiling water for at least 1 hour. Immediately or after leaving at room temperature for 2 hours or more, it is evaluated whether the adhesion site is peeled off. In addition, the corrosion resistance is evaluated according to the salt spray test method of KSM D9502 and ASTM B117-97 by damaging the aluminum laminate film portion of the adhesive specimen with a sharp knife by X-shape, and after 750hr, the degree of peeling of the adhesive portion and the degree of rusting of the X portion were evaluated. do.

The corrosion resistance was evaluated as follows:?: When peeling of the cut (adhesive) part was not 1 mm or less, ○: When peeling of the cut (adhesive) part was 5 mm or less and the corrosion of the X part was 2 mm or less,?: Cut (adhesive) part When peeling is 10 mm or less and the rust of X part is 3 mm or less, it shows with the case where X: peeling of a cut | disconnected (adhesion) part is 10 mm or more, and the rust of X part is 3 mm or more.

The processability (CET) is a 6 mm by using an Ericsson cupping tester by using a Ericsson cupping tester to draw two horizontal and two vertical lines at 5 mm intervals with a sharp knife for the aluminum laminate film portion of the specimen according to the test method of KS B0812 and ISO 1520. After the modifications are made, the damaged area is evaluated for damage. The evaluation of the workability is as follows:?: When there is no damage to the processed part,?: When the peeled off part is 1 mm or less,?: When the peeled off part is 2 mm or less, X: when the peeled off part is 2 mm or more.

The test plate of the workability (bendability) is about 70 to 100mm in width and twice the width of the appropriate length, and unless otherwise specified, parallel to the rolling effect of the disc, the bending is 180 by using a manual vice ˚ After bending and pressing, the machined area is evaluated with the naked eye or using a magnifying glass.

In the present invention, it is based on the fact that the aluminum of the processed part is not damaged such as cracks or peelings.

Physical properties of the steel sheet to which the metal film is bonded using the paint prepared in Preparation Examples 1 to 9 are shown in Table 3 below.

division 180˚ peeling strength Boiling water resistance Corrosion resistance Machinability (C.E.T) Machinability (Bending) Preparation Example 1 2.3kgf / cm ² Defective ◎ x 0T No Crack Preparation Example 2 3.2kgf / cm ² Good ○ △ 0T No Crack Preparation Example 3 3.7kgf / cm ² Defective ○ ○ 0T No Crack Preparation Example 4 4.2kgf / cm ² Defective ◎ ◎ 0T No Crack Preparation Example 5 3.5kgf / cm ² Good ◎ ◎ 0T No Crack Preparation Example 6 2.5kgf / cm ² Defective ○ △ 0T No Crack Preparation Example 7 4.0kgf / cm ² Defective ○ ○ 0T No Crack Preparation Example 8 3.8kgf / cm ² Good ◎ ◎ 0T No Crack Preparation Example 9 4.3kgf / cm ² Good ◎ ◎ 0T No Crack

As a result, in relation to the content of polytetraethylene ether glycol and polyester polyol of the thermoplastic polyurethane resin 4 composite of Preparation Examples 4 to 9, the thermoplastic polyurethane resins 1 to 3 of Preparation Examples 1 to 3 above It affects the physical properties of the adhesive steel sheet except boiling resistance.

Examples of the present invention include 70.0% of a thermoplastic polyurethane resin 4 composite, 7.0% of a ring-opening epoxy resin, 2.0% of gamma-glycidoxypropyltrimethoxysilane, 2.0% of isophorone diisocyanate, 1.0% of amorphous fine silica, mixed solvent Preparation Example 9 using 18.0% of an adhesive composition. The adhesive composition of Preparation Example 9 has a higher peel strength and excellent boiling resistance in the physical property comparison of the adhesive steel sheet than when using the one-component adhesive composition for bonding the metal film of Preparation Examples 1 to 8 to the plated steel sheet, Corrosion resistance and workability were exhibited.

Hereinafter, a method for manufacturing a color steel sheet and a color steel sheet according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

The color steel sheet using the adhesive composition according to the embodiment of FIG. 1 is rolled on the plated steel sheet 30 and the adhesive composition layer 20 of the present invention coated on the steel sheet 30 and the adhesive composition layer 20. It consists of a metal film 10 bonded in a manner.

Using the adhesive composition 20, the dry coating thickness is 5 to 10 μm on the plated steel sheet 30 coated with the coating material for the bottom coat of about 5 μm or the plated steel sheet 30 which is only chromium pretreated. It is a color steel sheet which is painted to adhere to the metal film (10).

Method for producing a color steel sheet using the adhesive composition of the present invention will be described in detail with reference to FIGS. 2 and 3 as follows. 2 is a configuration diagram showing a production facility for manufacturing a color steel sheet, Figure 3 is a flow chart showing the manufacturing step of the color steel sheet over time.

As a production facility for manufacturing a color steel sheet, as shown in Figure 2, the coil unwinding device 41, the cleaning device 42, the entrance reservoir 43, the cleaning device 42, the pretreatment device 44, Conveyor 45, roll sprayer 46, automatic dryer 47, gluing device 48, water cooling device 49, exit reservoir 50, cutter 51 and coiling device 52 It is configured by.

As shown in Figure 3 as an embodiment of the present invention, the step of smoothly releasing the plated steel sheet in the form of a roll (S1), the cleaning and side storage step (S2) for removing contaminants, chromium, etc. Pretreatment of the surface of the plated steel sheet using chemicals (S3), coating the plated steel sheet by a roll coating method using the adhesive composition of the present invention (S4), and drying by using an automated hot air oven (S5), bonding the metal film in a rolling manner and water-cooling (S6), exiting storage step (S7), and the step of making a cut and roll form the color steel sheet produced in the same way (S8) do.

The first step (S1) is a step of releasing the plated steel sheet 30 in the form of a roll, the end of the roll is introduced into the coil unwinding device 41 to smoothly release the plated steel sheet to be introduced into a flat form. .

And, the second step (S2) is introduced into the cleaning device 42 at a constant speed into the end of the plate-like plated steel sheet 30 introduced through the first step through the entry reservoir 43 of the vertical form Once again pass through the cleaning device 42, in order to remove the dirt and rust by using water or chemicals on the surface of the plated steel plate to increase the adhesive force and to compensate the time during the connection work at the entrance for continuous operation of the plated steel sheet Store the side plate to store the steel plate length.

The third step S3 is a step of inserting the end of the plated steel sheet 30 introduced through the second step into a pretreatment device 44 installed in a horizontal state. Because of poor adhesion, the surface is pretreated with reactive zinc phosphate and non-reactive coated chromate solution to improve the adhesion of the paint and to improve the corrosion resistance.

And, the fourth step (S4) is a step of injecting the plated steel sheet 30 introduced through the third step into the roll coating machine 46 in order from the end of the plated steel sheet using a conveyor 45 of a constant speed, The coating method is the natural coating method in which the rotational direction of the two roll coating plates and the paint roll is the same direction, the reverse coating method in which the plate and the roll are opposite directions, and the full reverse coating of the three roller coatings. (Full Reverse Coating) method, which uses a reverse coating method, the one-component adhesive composition for bonding the metal film prepared in the above embodiment to the plated steel sheet on the plated steel sheet with a dry coating thickness of about 5 to 10 ㎛ Paint so that

In addition, the fifth step (S5) is a step of passing the plated steel sheet 30 introduced in the process from the fourth step through the dryer 47 from the end in the form of a flat plate, the temperature control in the hot air oven is the adhesion of the coating film, As it directly affects the product quality such as the surface condition, the coated coated steel sheet is dried for 30 seconds to 60 seconds using an automated hot air oven to obtain a high quality product, and the maximum temperature of the coated plated steel sheet is in degrees Celsius. Maintain 180 to 200 degrees.

In the sixth step S6, the plated steel sheet 30 coated with the adhesive composition in the form of a flat plate is introduced into the bonding device 48 sequentially from an end thereof, and the heated plated steel sheet is heated. Passing through the water-cooling device 49, through the dryer 47, a coating film is formed on the surface of the plated steel sheet coated with the adhesive composition in a short time, and the metal film is bonded by a rolling method and the heated plating before the coating film is cooled. The steel sheet is cooled as water.

In addition, the seventh step (S7) is a step in which the plated steel plate 30 of the flat plate form coated with the adhesive composition is introduced into the exit reservoir 50 at a constant speed in a process subsequent to the sixth step. When the flatness is adjusted for high flatness of the finished plated steel sheet and the coated steel sheet wound on the bottom side is taken out in roll form, the production equipment does not stop when the steel sheet is finished to be stored.

Then, the eighth step (S8) is a process from the seventh step through the cutter 51 to cut the color steel sheet manufactured by the method to a suitable weight and coil the device 52 for coiling the cut color steel sheet In the step of forming a roll by using, before the color steel sheet introduced from the step 7 is made into a roll through the coiling device, the defective portion is removed, cut to a suitable weight, and the cut color steel sheet is rolled.

The color steel sheet made by bonding the aluminum laminate film and the plated steel sheet using the adhesive composition prepared by the method of Preparation Example 9 exhibited bendability and peel strength (180 °) of 4 kgf / cm 2 or more, corrosion resistance, and boiling resistance. .

The present invention can provide a one-part adhesive composition using a thermoplastic polyurethane resin for bonding a plated steel sheet and a metal film to produce a color steel sheet. Since the adhesive composition according to the present invention is stable at room temperature and has only one-time adhesiveness, after the metal film and the plated steel sheet are adhered, the adhesive composition becomes weak even when heat is applied, and thus the adhesive composition is not deformed or separated from each other. It is very suitable for the process, maximizing the production time and cost-saving effect of the product.As the adhesive shows the peel strength (180˚) of 4 kgf / ㎠ or more and excellent corrosion resistance, processability and boiling resistance, It can be used in various fields such as construction materials.

As described above in detail specific parts of the present invention, those skilled in the art, these specific descriptions are only preferred embodiments, and the scope of the present invention is not limited thereby. It is intended that the scope of the invention be defined by the claims appended hereto and their equivalents.

Claims (7)

5 parts by weight to 30 parts by weight of ring-opening epoxy resin, 1 part by weight to 10 parts by weight of gamma-glycidoxypropyltrimethoxysilane, 1 part by weight to 10 parts by weight of blocked isocyanate as a curing agent, based on 100 parts by weight of thermoplastic polyurethane resin, 1 part by weight to 10 parts by weight of amorphous finely divided silica, 10 parts by weight to 100 parts by weight of the mixed organic solvent. The method of claim 1, wherein the thermoplastic polyurethane resin, 20 parts by weight to 350 parts by weight of polytetraethylene ether glycol having a molecular weight in the range of 1,000 to 2,000 with respect to 100 parts by weight of polyester polyol in the range of 1,000 to 2,000, chain extender 1 to 40 parts by weight of ethylene glycol, 1 to 40 parts by weight of 1,4-butanediol, and 20 parts by weight to 200 parts by weight of isocyanate. The one-pack adhesive composition according to claim 1, wherein the ring-opening epoxy resin is replaced with a hydroxyl group by ring opening an epoxy functional group of the epoxy resin itself. The one-part adhesive composition of claim 1, wherein the ring-opening epoxy resin has a molecular weight in the range of 15,000 to 35,000. The one-part adhesive composition according to claim 1, wherein the blocked isocyanate is dissociated at 120 degrees Celsius or more due to blocking of NCO functional groups of isophorone diisocyanate with methyl ethyl ketoxime. The one-part adhesive composition according to claim 1, wherein the amorphous fine silica has an oil absorption of 200 to 300 ml / 100 g, an average particle size of 1.0 to 2.0 mu m, and a pH of 4 wt% water suspension of 6.0 to 7.5. The one-part adhesive composition according to claim 1, wherein the mixed organic solvent is xylene: figgeA = 1: 1.

Images